Systematic Survey on Petrochemical Technology 2 Keizo Tajima

 Abstract The petrochemical industry involves the production of basic petrochemicals, industrial organic chemicals and polymers using petroleum or natural gas as the raw material. The industry took hold in Japan in the 1950s and almost immediately dominated the chemical industry; to this day, the petrochemical industry still remains a key industry, providing raw materials to a wide range of sectors in the Japanese chemical industry, including pharmaceuticals, cosmetics, synthetic detergents, paints, plastic molding and rubber molding. By the 1960s, a mass supply of plastic products had dramatically impacted society, triggering a polymer revolution and undergirding Japan’s rapid economic growth. New chemical factory conglomerates sprang up along the coastlines, known as petrochemical industrial complexes or kombinats. The petrochemical industry originated in the 1920s in the United States. However, up until the early 1940s, it was little more than a chemical industry that existed only in the United States, supplying a few industrial organic chemicals. Wood chemistry, oleochemistry, fermentation chemistry and coal chemistry had all long flourished to the point of mass production prior to the advent of petrochemistry, in Europe, the United States and Japan alike. Petrochemistry co-existed with these in the United States as yet another type of chemical industry. The development of naphtha steam-cracking technology in the 1940s and the European migration of the petrochemical industry in the 1950s had a major impact on petrochemical technology. Innovations in petrochemical technology suddenly began to proliferate as the technology began to be combined with conventional European chemical technology. The petrochemical industry swallowed up many of the existing mass-producing chemical industries and quickly assumed a key role among the other chemical industries. It was at this time that Japan entered the petrochemicals arena. Since it already had mass-producing chemical industries in place, it was in a position to do more than simply adopt the new petrochemical technology being introduced; it took an active role in new technological innovations. Japan’s prior experience meant that by the late 1960s it was absorbing petrochemical technologies and successively developing its own. By the late 1970s, the intensive developments in petrochemical technology had eased, and petrochemistry began to spread across the developing nations. It was during this time that the negative aspects of petrochemistry began to emerge, such as environmental issues and chemical pollution issues. On top of this, the two oil crises in the 1970s escalated the cost of petrochemical products, resulting in a demand for low-emission technology and energy-conserving technology. By this time the Japanese petrochemical industry was no longer simply relying on technology imports and was developing its own technology. From the 1980s, the challenge was to develop olefins-based products with at least three carbon atoms, rather than ethylene products with two carbon atoms. The Japanese petrochemical industry was very active in this field. Petrochemistry became a substantial chemical industry with a wide range of products in its arsenal. Meanwhile, significant changes started taking place on the petrochemical industrial world map with the emergence of the Middle Eastern petrochemical industry in the 1980s. This trend has accelerated since the 2000s with China entering the industry and huge increases in production. In the 2010s, the core of the petrochemical industry is taking a dramatic shift away from the West and towards Asia and the Middle East. Accordingly, Western companies have been successively dropping out of the industry since the 1990s. However, unlike their counterparts in the West, Japanese petrochemical companies took a different path. Japan is now not only planning for greater functionalization within the petrochemical industry, but also developing fields of functional chemistry outside of the conventional scope of petrochemistry, even incorporating polymer molding technology. There have also been changes within the conventional scope of petrochemistry, such as significant growth in the demand for propylene in contrast to ethylene. In response to these changes in business environment, new trends have been observed in petrochemical technology since the 1990s. Petrochemistry may change significantly in the next decade or two.

 Profile Contents Keizo Tajima Introduction Chief Survey Officer, Center of the History of 1 ...... 3 Overview of petrochemistry Japanese Industrial Technology, National Museum of 2 ...... 6 Petrochemical product categories Nature and Science 3 ...... 22 Industrial organic chemicals and polymers 4 predating petrochemistry 1967: Graduated from Tokyo Metropolitan Ueno ...... 56 History of the petrochemical industry High School 5 ...... 94 Technological system and systematization of 1972: Graduated from the Department of 6 petrochemistry Synthetic Chemistry, Faculty of ...... 134 Conclusion Engineering, The University of Tokyo 7 ...... 194 1974: Completed Master’s degree at the Graduate Location Confirmation of Historical Technology School of Engineering, The University of Resource Items from the Petrochemical Industry Tokyo ...... 196 Joined the Ministry of International Trade A list of abbreviations for the product names used and Industry (administrative post) in this document ...... 199 1987: Joined Mitsui Toatsu Chemicals Co., Ltd.

1997: Transferred to Mitsui Chemicals, Inc. by

merger 2008: Retired from Mitsui Chemicals, Inc. Subsequently involved in writing, editing, translating and lecturing 2015: Chief Survey Officer, Center of the History of Japanese Industrial Technology, National Museum of Nature and Science Introduction 1

Let us begin by defining petrochemistry chemical industry producing basic and clarifying the scope of what is covered in petrochemical products, industrial organic this survey report. chemicals and polymers using petroleum or natural gas as the raw material.” The 1.1 Definition of petrochemistry petrochemical industry spans a number of industries in the Japan Standard Industrial The petrochemical industry is often Classifications, namely: basic petrochemicals, defined as “a chemical industry with aliphatic intermediates, cyclic intermediates, petroleum as its raw material.” Certainly, plastics, synthetic rubber and surface-active petroleum is the main raw material used in agents (surfactants). This definition is slightly the Japanese petrochemical industry. broader than what is generally termed as However, globally speaking, there are vast petrochemistry, and includes industrial petrochemical industries in the United States organic chemicals made from methane, and Middle East that use natural gas and engineering plastics and functional polymers, associated petroleum gas as raw materials; it which have recently been developed into a is therefore inaccurate to use a definition that number of different products. only applies to the Japanese petrochemical However, since the petrochemical industry. Furthermore, the above definition industry often refers to products with only qualifies the raw material used in an significantly high production and demand industry without determining to what extent volumes, this report focuses on products the products produced in that industry can be within this broader definition that have high products of the petrochemical industry. production and demand volumes. Current chemical industries are structured as shown in Fig. 1.1. The petrochemical 1.2 Focus of the survey report industry forms a core industry providing raw materials to low-molecular organic chemical Present-day petrochemical products end-product industries (pharmaceuticals, include vinyl chloride, polyvinyl chloride pesticides etc.) and high-molecular chemical (PVC), synthetic surfactants, coating resins end-product industries (plastic molding, and adhesive resins. Some of these have been chemical fibers, coatings, etc.). touched on in other technology systemization As shown in Table 1.1, the chemical survey reports, such as the reports on vinyl industries here are the chemical and allied chloride (March 2001, March 2002), soaps product industries as defined by the Japan and synthetic detergents (March 2007), Standard Industrial Classifications, as well as coating (March 2010) and adhesives (August plastic products, rubber products and 2012). The petrochemical industry has chemical fibers (rayon, acetate, synthetic produced a great number of products and fibers). Although the chemical fiber industry product groups with an equally impressive was classified as a chemical industry up until production scale, history and technology the 2002 revision of the Japan Standard system, including methanol and its Industrial Classification, since then it has derivatives, olefins (including dienes), been classified as a textile industry. Out of aromatics, alcohols, organic solvents, consideration for continuity of statistics, plasticizers, acetic acid, polyvinyl acetate and production history and technical details, it has its derivatives, ethylene oxide and its been included as a chemical industry for the derivatives, acrylonitrile and its derivatives, purposes of this report. acrylic acid and its derivatives, methyl In light of the current structure of the methacrylate and polymethyl methacrylate, chemical industries, the petrochemical polyethylene, polypropylene, styrene and industry is defined in this report as “a styrenic polymers, phenol and its derivatives,

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phenol resin and amino resin, polyurethane its raw materials, engineering plastics, and its raw materials, epoxy resin, generic synthetic rubbers, special synthetic unsaturated polyester resin, polyethylene rubbers, thermoplastic elastomers, silicon terephthalate (PET) resin and its raw resin and fluorine-based industrial organic materials, polyamide resin (nylon resin) and chemicals and resins.

Fig. 1.1 Chemical industry and petrochemical industry.

Table 1.1 Definition of chemical industry

Supposing that olefins, vinyl chloride or systematization reports that have already been the like were single trees, then petrochemistry done would be impossible, not only in terms would be an entire forest. Accordingly, of the sheer number of hours and pages surveying petrochemistry to the same depth required, but also in terms of the capabilities as vinyl chloride or other technology of a single survey officer. It would also not be

4 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) enough to simply focus on some of the as yet have been included in this report because unreported areas of petrochemistry, such as there would be few other opportunities to olefins, phenol and its derivatives, or include them in other technology polyethylene, as then the overall picture of systematization survey reports. petrochemistry would be lost. Consequently, The petrochemical industry was founded this survey report does not focus in on any in the United States of America in the 1920s particular area, instead providing a and developed from there. Industries were wide-angle view of the overall field of established in Europe and Japan following a petrochemistry and discussing the wider worldwide increase in Middle Eastern oil trends of the entire forest. Readers should be exports from the 1950s onwards. Since the advised that this report will not go into the 1970s, petrochemical industries have same level of detail on the individual trees, so continued to expand all around the world. to speak, as has been done in other survey The raw materials, products and technologies reports. of the petrochemical industry have been As a lead-up to the history of traded the world over since the 1950s. petrochemistry, this report does provide a Accordingly, the development of the relatively detailed outline of the industrial petrochemical industry in Japan must be organic chemical and polymer industries that viewed in the context of global trends; this existed prior to the establishment of the survey report focuses the worldwide petrochemical industry, using raw materials petrochemical industry as much as possible, other than petroleum or natural gas, such as rather than just Japan. the coal chemical industry. These industries Please note that since this report is have now come under pressure from the intended for the general public, the use of petrochemistry industry and have diminished chemical structural formulas has been significantly. However, they are essential to provided only for reference and the use of any consideration of the history of chemical reaction formulas has been avoided petrochemical industry technology. They as much as possible.

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Overview of petrochemistry 2

This chapter provides an overview of hydrocarbons. Aromatic hydrocarbons are petrochemistry. What are petrochemical hydrocarbons with a relatively stable carbon products? What are they used for? How does ring (aromatic ring) [Footnote 2]. Typical the petrochemical industry relate to society products include benzene (C6), toluene (C7) and to other industries? What are the and xylene (C8). Olefins are hydrocarbons distinguishing characteristics of the with double bonds and no aromatic ring. production technology? What other Typical products include ethylene (C2, one technologies have been based on double bond), propylene (C3, one double petrochemical technology and what related bond), butylene (C4, one double bond), technologies undergird petrochemistry? butadiene (C4, two double bonds), isoprene These are the points that shall be addressed. (C5, two double bonds) and cyclopentadiene (C5, cyclic structure, two double bonds) 2.1 Uses of petrochemical products [Footnote 3]. The molecular structures of some typical basic petrochemical products are Petrochemical products can be divided shown in Fig. 2.2 for reference. into three major categories, as shown in Fig. 2.1. These are basic petrochemicals, industrial organic chemicals and polymers. Figure 2.1 also shows some of the main products in each of these categories. However, there are actually far more products than those given here.

Fig. 2.1 Current raw materials and principal products of the petrochemical industry.

2.1.1 Uses of basic petrochemicals The main use for basic petrochemicals with a one carbon atom (C1) (syngas, carbon monoxide, phosgene, hydrogen cyanide, chloromethane) is as the raw materials for industrial organic chemicals. A small amount different hydrocarbons. Hydrocarbons with one or more double bonds are called olefins. Hydrocarbons with only one double bond is used as organic solvents and also as a raw are also called alkenes. Double bonds are more reactive than single material for industrial inorganic chemicals. bonds [Footnote 2] Typical examples are benzene rings, with six carbons Basic petrochemicals with two or more joined in a ring, and naphthalene rings. Aromatic rings themselves carbon atoms can be divided into two broad are very stable and do not break easily. Atoms or functional groups attached to the edge of an aromatic ring are more susceptible than to categories: olefins [Footnote 1] and aromatic substitution reactions or oxidation reactions than the carbon-carbon bonds forming the aromatic ring. [Footnote 3] Other than cyclopentadiene, the typical olefins-based [Footnote 1] A compound comprising only carbon and hydrogen is products mentioned have a linear carbon structure (and are capable called a hydrocarbon. As the number of carbon bonds and bonding of branching). Cyclopentadiene has five carbon atoms in a cyclic methods can vary greatly, there are an almost unlimited number of structure. See Fig. 2.2 for the chemical structural formula.

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provide the raw material for industrial organic chemicals. Other than industrial organic chemicals, another major application for these is in solvents. Benzene, toluene and mixed xylene (xylene isomer mixture) are used in solvents.

Fig. 2.2 Molecular structures of typical basic petrochemicals. 2.1.2 Uses of industrial organic chemicals Industrial organic chemicals are made by In principle, there are many other reacting basic petrochemical products hydrocarbons besides these with eight or less together, or by reacting them with inorganic carbon atoms. This also includes some chemicals, such as air, oxygen, hydrogen, substances produced by steam cracking of water, ammonia, chlorine, sulfuric acid or naphtha, as shall be mentioned later. nitric acid. Unlike basic petrochemical However, these are seldom used as basic products, there is an extremely diverse range petrochemical products as they do not have of industrial organic chemicals with various any widespread applications and the chemical and physical properties. The separation and purification process is a products shown in Table 2.1 are just a very difficult one. few examples of industrial organic chemical Thus, even including isomers products with particularly high production [Footnote 4], there are no more than around a volumes. dozen basic petrochemical products at most To a certain extent, industrial organic that are being put to use in large quantities. chemicals can be broadly categorized by The only use for basic petrochemical functional group [Footnote 6]. Table 2.1 products is to provide the raw materials for shows examples of types and products of industrial organic chemicals and polymers. typical industrial organic chemicals Olefins are often consumed as raw materials categorized by functional group. Fig. 2.3 also (monomers) for polymers without being made shows examples of typical functional groups into industrial organic chemicals. Of all of the along with chemical structural formulas of petrochemical products produced worldwide, typical products. Since the chemical around 60% of ethylene is estimated to be properties of industrial organic chemicals consumed as polyethylene, 60% of propylene largely depend on the functional group, these goes into polypropylene (PP) and synthetic categorizations can provide a general idea of ethylene-propylene rubber (EPR), at least their application and method of production. 90% of butadiene goes into styrene-butadiene For example, many alcohols are used directly rubber (SBR), butadiene rubber (BR), as solvents and have esters or ethers as their acrylonitrile-butadiene rubber (NBR) and feedstock. As epoxides have very reactive other synthetic rubbers, as well as three-membered rings containing oxygen, acrylonitrile-butadiene-styrene resin (ABS they are used to produce other industrial resin) [Footnote 5]. The remaining 40% of organic chemicals or in polymerization ethylene and propylene goes into a very wide reactions. In many cases, a single industrial variety of industrial organic chemicals. organic chemical has multiple applications, Meanwhile, aromatic hydrocarbons are being used as an organic solvent as well as an almost never used in polymers directly; they organic intermediate.

[Footnote 4] Some substances have different chemical and physical properties despite having the same molecular formula, due to having different chemical structures. The substances are called isomers. For example, there are four isomers of butylene with four carbon atoms [Footnote 6] An atom or group of atoms that determines the and three isomers of xylene with eight carbon atoms, as shown in properties of an organic compound is called a functional group. For Fig. 2.2. Including the similarly-structured ehtylbenzene, there are example, the alkyl group, which is composed of only carbon and four such isomers. hydrogen, carries the properties of being hydrophobic and having [Footnote 5] Since the Japanese petrochemical industry supplies a relatively low reactivity. The hydroxyl group, composed of oxygen diverse range of products, around 40% of ethylene and propylene is and hydrogen, carries the property of being hydrophilic. The chloro consumed only as polyethylene and PP. group carries the property of being flame retardant.

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Table 2.1 Typical industrial organic chemical types and products

Fig. 2.3 Examples of typical functional groups and molecular structures of industrial organic chemicals.

As shown in Table 2.2, the main uses for (1) Monomers (feedstocks for polymers) industrial organic chemicals are monomers Quantitatively, the most common (feedstocks for polymers), organic solvents, application by far for industrial organic refrigerants, heat transfer medium, chemicals is monomers. There are four types plasticizers, surfactants, organic intermediates of monomers, as shown in Table 2.2. and other uses. Carbon-carbon double-bonded monomers form polymers through a reaction whereby

8 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) the double bond becomes a single bond, and linkage on a molecule, a hydroxyl group and the monomers join together. Cyclic a carboxyl group form at the ends of the monomers form polymers through the molecule, and the EG and PTA can react opening of the ring. Monomers with multiple further. The same thing happens even when functional groups within one molecule form larger molecules produced react together. polymers through a reaction between Thus, the molecule grows and forms a functional groups that creates new bonds. For polymer. Monomers with multiple reactive example, ethylene glycol (EG) is a type of sites act the same way as monomers with alcohol and has two hydroxyl groups. multiple functional groups, with reactive sites High-purity terephthalic acid (PTA) is a reacting to form new bonds and creating a carboxylic acid and has two carboxyl groups. polymer. For example, phenol has three The hydroxyl groups and carboxyl groups reactive sites, and formaldehyde has two react, releasing water and forming an ester reactive sites. linkage. When EG and PTA form an ester

Table 2.2 Typical industrial organic chemical applications and example products

(2) Organic solvents, refrigerants, heat lithium-ion secondary batteries. Plasticizers transfer mediums, plasticizers are liquid organic chemical products with Not only are organic solvents used in the high boiling points; these are used to soften chemical industry (reaction solvents, polymers and to improve moldability. synthetic fiber spinning solvents, extraction solvents, etc.), they are also used in large (3) Surfactants quantities in the machinery industry A large amount of surfactants are used in (degreasing agents for machine parts synthetic detergents. They also have a wide processing, and cleaners for semiconductor range of other applications, such as fabric manufacturing, refrigerants and heat transfer softeners, concrete water-reducing agents, mediums, etc.) and the laundry industry (dry disinfectants, foaming and antifoaming agents cleaning) as well. They are also used as and solubilizers and emulsifiers for cosmetics components in chemical products, such as and pesticides. coatings, adhesives, printing inks, aromas, cosmetics and pesticides. Furthermore, they (4) Organic intermediates have also recently started being used as a Organic intermediates are solely used as component (electrolyte solution) in feedstocks for other industrial organic

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chemicals, such as ethylbenzene, feedstock products. for styrenes, cyclohexane, feedstock for caprolactam and adipic acid and ethylene (1) Plastic molding products dichloride, feedstock for vinyl chloride and While the term plastic can refer to any chlorinated solvents. These form a material that can be molded into a desired substantially high volume of products. Some shape (any material with plasticity), organic intermediates are also used as nowadays it is generally only used to describe feedstocks in chemical industries outside of polymers. Plastics can be grouped into the petrochemical industry, pharmaceuticals, thermoplastics and thermoset plastics. pesticides and dyes. There are numerous Thermoplastics are polymers that soften or different types of these organic intermediates, fluidize when heated. These are molded while although the individual types are not very hot and form the finished product once cooled. substantial in volume. If the finished product is heated again, it softens or melts. Conversely, thermoset (5) Other uses plastic finished products no longer soften or Other applications that use high volumes melt, even when heated again. Thermoset of industrial organic chemicals are gasoline plastics are molded at the raw material stage feedstocks and petroleum additives, such as while the molecular weight is low and the alkylates [Footnote 7] and methyl tertiary material has some fluidity, or at a butyl ether (MTBE). Alkylates are produced semi-polymer stage when the molecular by oil refineries and are often self-consumed. weight has increased to a certain extent. After molding, the product is then heated to 2.1.3 Uses of polymers complete the reaction further, resulting in the Substances with a molecular weight of finished product. The reaction that takes place around 1,000 or higher are called polymers. through heating after molding links the Since polymers are formed by monomers, polymers together in three dimensions substances with a low molecular weight, (crosslinking). going through a very large number of

reactions, their molecular structure is made up of a very long series of repeated units. The reaction that produces polymers is called polymerization. There are a very high number of different types of polymers, although they are not as numerous as industrial organic chemicals. Polymers can be classified in various ways, such as by molecular structure, by polymerization method or by application. For reference, Fig. 2.4 shows the molecular structures of some typical polymers. Table 2.3 shows a classification of polymers by application. Polymer applications can be categorized into molding products, coatings, adhesives and binders and high performance products. In this report we shall only cover molding products, since these account for the highest volume by far. Molding products can be divided into three broad categories: plastic molding products, synthetic fibers and rubber molding

[Footnote 7] Gasoline base materials that are multi-branch chain saturated hydrocarbon mixtures made by reacting isobutene with propylene, butylene or other olefins.

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Fig. 2.4 Typical polymer chemical structures.

Table 2.3 Polymer applications and example products

Since the molding stage generally allows used as a thermoplastic; however, in some thermoplastics to have a far greater cases it is used as a thermoset plastic, being productivity than thermoset plastics, crosslinked to form a three-dimensional thermoplastics have far higher production structure after molding, such as for volumes. These categorizations are not high-voltage cables and for water supply and absolute, as the same polymer can be made hot water piping. Polyurethane is also often into a thermoplastic or a thermoset plastic, used as a thermoset plastic, and the depending on the molecular design of the polyurethane foam used in cushions is a polymer structure and on how the thermoset plastic product. However, polymerization and molding are achieved. thermoplastics with one-dimensional For example, polyethylene is very commonly molecular structures are used for synthetic

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fibers. history of the petrochemical industry in Japan as an example. (2) Synthetic fibers Synthetic fibers are made from polymers 2.2.1 The polymer revolution with one-dimensional structures that are The petrochemical industry became easily crystallized. After forming the fiber industrialized in Japan in the late 1950s, shape, they are stretched to increase the mainly through introduced technology from degree of crystallinity, which significantly the West. By the end of 1960s, the industry increases the tensile strength of the fiber. was supplying large volumes of new products, Synthetic fibers can be treated as a type of such as polyethylene, polystyrene, thermoplastic molding product. polypropylene (PP), polyester fiber, acrylic fiber and SBR. (3) Synthetic rubber molding products On top of this, changes in raw materials Synthetic rubbers are materials with and manufacturing methods in the 1960s saw so-called rubber elasticity. Rubber molecules the petrochemical industry take up and have a far looser molecular structure at room significantly develop new product categories temperature than plastic molecules. Therefore, that had been previously supplied by other when stretched, their tensile strength chemical industries, such as nylon fiber, decreases considerably and they expand polyvinyl chloride, vinylon fiber, acetates and significantly. Since the rubber molecules are plasticizers. The petrochemical industry crosslinked to each other and the molecular expanded by thus supplying large quantities chain does not shift, when the stretching force of polymers to society, having a significant is released, the rubber immediately returns to impact both on society and on other industries. its former shape. Thus, rubbers differ Polymers had steadily spread across the significantly from plastics in terms of their United States throughout the 1930s–1950s physical properties. Synthetic rubbers are and took Japan by storm in the late 1950s molded in a softened state. At that stage, with the introduction of the petrochemical sulfur and crosslinking agents are kneaded in. industry, sparking a polymer revolution in After molding, a vulcanization reaction Japanese society. In addition, petrochemical occurs upon heating. This is the same as the industry production volumes skyrocketed crosslinking reaction in thermoset plastics. from the late 1950s to the 1960s; this required The sulfur and crosslinking agents link the large-scale capital investments to fund it, and rubber molecules together and the elastic played a hand in spurring Japan’s rapid properties emerge. economic growth. From the 1970s onwards, By contrast, like thermoplastics, this pattern repeated again and again with the thermoplastic elastomers melt when heated establishment of petrochemical industries in and can be molded. Once cooled, this forms a Korea, Taiwan, the ASEAN nations and even molding product with elastic properties. China. There is also no need to add sulfur and Polymers advanced into new territories crosslinking agents or to induce a that had previously been the domains of wood, vulcanization reaction by heating. These paper, natural fiber, natural rubber, glass, synthetic rubbers are high in productivity due ceramics and metals. Polymers had the to the molding process. advantages of being lightweight, moldable, water resistant and corrosion resistant. They 2.2 Interaction between the were initially used in a number of petrochemical industry and other applications, including fibers, industries and society packaging/containers, daily necessaries, agricultural film, tires and wire coating. Later, The petrochemical industry has had they also came to be used in applications various interactions with other chemical requiring higher strength and durability, such industries, other industries and also wider as construction, civil engineering, machine society. The following is a brief outline of the parts, fishing vessels, large-scale tanks and

12 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) optical fibers. Currently, they are even being other chemical industries that had used coal used in aircraft fuselages. Thus, polymers chemical products and natural products as have made a significant contribution to raw materials likewise transitioned to using energy conservation, product longevity and petrochemical products as raw materials. cost reduction in many industries, including manufacturing, distribution, transport and 2.2.3 Location changes in the chemical communications and the information industry industry. The Japanese petrochemical industry was established using naphtha (a petroleum distillate with a boiling point between 30– 2.2.2 Structural changes in the chemical ° industry 200 C) as a feedstock; the naphtha was While the Japanese petrochemical supplied by oil refineries refining and industry was achieving considerable growth separating crude oil imported mainly from the within the first two decades of its Middle East. The steam cracking of naphtha establishment, the wider Japanese produced a number of liquid and gas basic petrochemical industry was also undergoing petrochemical co-products. Costs were significant structural changes, in which the reduced by piping these products to adjacent petrochemical industry came to take a leading industrial organic chemical plants and role. The coal chemical industry (the polymer plants. At that time, it was important acetylene chemical industry and coal tar that all of the basic petrochemical chemical industry) and the fermentation co-products were used up. Accordingly, the chemical industry (ethanol fermentation Japanese petrochemical industry took the industry and acetone-butanol fermentation form of a coastal industrial complex or industry), suddenly went into decline at the kombinat, incorporating multiple chemical end of the 1960s, despite both having plants on an expansive site, right from the predated the establishment of the outset. petrochemical industry. The celluloid Until then, the chemical industries in Japan had used coal, electricity (mainly industry, which had been one of Japan’s hydroelectric) and agricultural produce as raw leading chemical industries since the 1910s, materials, and had developed separately in using cellulose (natural polymer) from different inland areas where those raw wood/pulp as a raw material, and the materials could be obtained [Footnote 8]. rayon/acetate industry went into decline in These existing chemical industries were the 1960s under pressure from the new forced to move to coastal industrial plastics and synthetic fibers that were being complexes by the petrochemical industry at produced by the petrochemical industry. the point where the raw materials were By contrast, polymer molding industries, converted into petrochemistry. Many such as plastic molding, rubber molding and high-producing inorganic chemical industries, synthetic fibers, were expanding dramatically such as ammonia, industrial gas (oxygen, due to the high-volume supply of low-cost nitrogen, etc.) and salt electrolysis (chlorine, plastics, synthetic rubbers and synthetic sodium hydroxide), have a far longer history fibers. than the petrochemical industry. Since the Even the soap industry, which used petrochemical industry requires large natural fat as a raw material, went into amounts of ammonia, oxygen, nitrogen and decline due to pressure from the synthetic chlorine, as well as the carbon source, many detergent industry, which used synthetic of these inorganic chemical industries also surfactants supplied by the petrochemical started relocating to coastal industrial industry as its main raw material. The paint complexes as the petrochemical industry industry, which had similarly used natural began to grow in scale. Thus, the fats and oils as raw materials, also transitioned to synthetic polymers as raw materials. Synthetic dyes, synthetic [Footnote 8] Some of the coal chemical industries and electrochemical industries also had factories in the form of industrial pharmaceuticals, cosmetics, pesticides and complexes to maintain their product chains.

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petrochemical industry effected significant 2.3 Undergirding technologies for the structural changes in the geographic mapping petrochemical industry of Japan’s chemical industries, with industries centering on the petrochemical Petrochemistry is said to have had the industrial complexes. United States as a mother, and Germany as a father. This refers to the fact that petroleum 2.2.4 Pollution/environmental issues and refining technology was developed in the responses United States, and that industrial Meanwhile, as the petrochemical industry organic/industrial inorganic chemicals and developed, expanded in scale and centralized, large-scale synthesis technology for synthetic its negative impacts on society also began to oil were developed in Germany, as well as emerge. These included industrial pollution referring to polymer synthesis technology, issues, plastic waste issues, chemical such as the industrialization of synthetic pollution issues and global environmental rubber, which also started in Germany. These issues. To manage these, Japan carried out technologies laid the foundation for the intensive emergency-response anti-pollution establishment of the petrochemical industry. measures within a short period in the 1970s. The technologies that formed the basis for the From the 1980s onwards, these were followed establishment and development of by technology developments to revolutionize petrochemistry can be broadly grouped into the chemical reaction processes from the four main areas, as shown in Fig. 2.5. ground up and to develop substitute products. Essentially, petrochemistry is an organic The problem of plastic waste has been chemical industry; accordingly, organic difficult to resolve, but the cooperation of chemistry technology plays the most society (such segregated collection and waste significant role in undergirding it. However, power generation) and other industries (such this goes without saying and can be as the cement and steel industries) has now overlooked here. finally led to some progress towards a resolution, mainly through thermal recycling and material recycling.

2.2.5 Contribution to energy conservation The two oil crises of the 1970s significantly impacted the petrochemical industry, not only in Japan, but all over the world. This prompted the development of energy-conserving technologies within the Fig. 2.5 Undergirding technologies for the petrochemical industry, such as gas phase petrochemical industry. linear low-density polyethylene (L-LDPE) 2.3.1 Petroleum cracking technology and production technology. Meanwhile, petroleum reforming technology lightweight plastics were becoming Petroleum cracking technology and widespread throughout the automotive and petroleum reforming technology were aircraft industries, thereby improving the developed in the United States as a means of energy efficiency of cars and airplanes. obtaining as much good-quality gasoline as Plastics with superior thermal insulation possible from crude oil. These are related to performance were being promoted as steam cracking technology and aromatic insulation in refrigerators, buildings and hydrocarbon production technology, and form residential facilities. Thus, the petrochemical the core technologies for producing basic industry made a major contribution to social petrochemical products. and industrial energy conservation through its

products. 2.3.2 Cryogenic distillation technology

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German company Linde AG completed Meanwhile, continuous operation an industrial air liquefaction equipment in technology for successively reacting and also 1895. This was followed by initiatives to separating and purifying large volumes of develop cryogenic distillation technology, gases and liquids can be traced back to 1867, with devices developed for pure oxygen in with the Solvay process (ammonia-soda 1902, pure nitrogen in 1903 and a process). However, it was technologies two-column device for both pure oxygen and developed for ammonia synthesis, methanol pure nitrogen in 1910. At the time, pure synthesis and synthetic oil that laid the oxygen was used for welding and cutting; in immediate foundation for the continuous the middle part of the 20th century, it started processes widely used in petrochemistry. being used in large quantities in converter furnaces. Pure nitrogen was used to produce 2.3.4 Polymer synthesis technology nitrolime, and also in ammonia synthesis. For the first couple of decades of its Cryogenic distillation technology was later establishment in the United States, used to separate hydrogen from syngas and petrochemistry was mainly used for products water gas; the hydrogen was used in the such as solvents, petroleum additives and hydrogenation of fats and oils and as a raw antifreeze. However, a push for the material in ammonia synthesis. production of synthetic rubber in the United This kind of cryogenic distillation States in the 1940s formed the first links of technology was essential in petrochemistry. the polymer industry with petrochemistry, In particular, accurate separation of different and significant development began on the gases was very important in the steam petrochemical industry in the United States. cracking of naphtha. Distillative separation of Even today, as mentioned previously, ethane from natural gas, as well as precise polymers make up for an overwhelmingly distillation separation of ethane and ethylene, high proportion of basic petrochemical and propane and propylene, is the most product consumption and industrial organic prominent example of how cryogenic chemical consumption. By linking with distillation technology underpins polymers, petrochemistry has transformed petrochemistry. into a materials-supply industry, and a large-scale industry at that. Most of the 2.3.3 Industrial catalyst technology, polymer synthesis technology already high-pressure technology and achieved by the 1940s involved monomers continuous operation technology produced by the coal chemical industry or the Industrial catalyst technology and fermentation chemical industry. These high-pressure technology, starting with technologies were incorporated into ammonia synthesis in the 1910s, have come petrochemistry and became fundamental increasingly into play in petrochemical technologies of the petrochemical industry. In technology. Across the history of the 1950s, Europe also entered the petrochemistry, nearly all new products and petrochemical era, with large quantities of processes have come about due to the olefin being supplied. Ziegler-Natta catalysts development of new industrial catalysts. At were discovered in Europe at that same time, the same time, high-pressure technology laid and this new polymer synthesis technology a significant milestone in petrochemistry with became the first polymer technology in high-pressure low-density polyethylene petrochemistry. This technology later resulted production technology in the 1930s. in a great leap forward in petrochemistry. Reactions under high pressure have been established as one of the fundamental 2.4 Related technologies that support petrochemical technologies, although not to petrochemistry such a high pressure as this. Petrochemical equipment often used in high-pressure As mentioned several times previously, chemistry is extremely compact and highly petrochemical technology was introduced to productive. Japan in the late 1950s. A lot of related

Systematic Survey on Petrochemical Technology 15

supporting technology was also introduced to the education curriculum. By the end of the Japan at the same time. There were four main 1920s, unit operation had a greater amount of technologies, as shown in Fig. 2.6. This was substance, such as the completion of also a time of breakthrough in these distillation theory, and it began to be utilized technologies that were essential to by the American oil refining industry and also petrochemistry. In that sense, petrochemistry the petrochemical industry as well. Further became industrialized in Japan with very developments were also taking place in good timing. process engineering, which examines the oil refining process and chemical processes overall, and reaction engineering, which focuses on the core reaction part of the process. Chemical engineering became an essential technology, not only in terms of designing, procurement, managing construction and operation of individual petrochemical facilities, but also for planning and designing complete factories and overall Fig. 2.6 Related technologies that support industrial complexes. petrochemistry. German-style industrial chemistry and applied chemistry had also been taught in However, not all chemical companies Japan since the start. However, this was adopted these related technologies. If we look fundamentally different from the at the history of various chemical companies, systems-engineering nature of chemical we see that in the early 1950s many of them engineering. Although organizations such as investigated the American petrochemical Kanazawa Higher School of Technology industry and petrochemical technology and (now Kanazawa University), Kyoto considered whether or not to enter the market. University and Tokyo Institute of Technology At that time, there was often a strong sense of had established chemical machinery and resistance to petrochemical technology and chemical engineering departments by around also related technologies among chemical 1940, chemical engineering was not yet companies experienced in batch reactions, widely known about in the Japanese chemical such as synthetic dyes. This was due to industry. In the 1950s, petrochemical differences between science-type chemical technology and chemical engineering were corporate culture and engineering-type both adopted by the Japanese chemical chemical corporate culture. In many cases, industry, and the idea of chemical these differences in corporate culture resulted engineering was welcomed with new wonder. in companies failing or lagging behind in Today, chemical engineering has taken hold introducing petrochemistry. in many fields of the chemical industry besides petrochemistry and is becoming a key 2.4.1 Chemical engineering technology right across the chemical industry. Chemical engineering was developed in the 1910s by the American oil refining 2.4.2 Instrumentation and control industry. It developed as an academic technology discipline focused on physical operations that Instrumentation and control is technology are utilized across the oil refining and to operate a plant using three factors: chemical industries, such as flow (fluid measurements by measuring instrumentation, transport, filtration), thermal conductivity and automated feedback control and automatic mass transfer (gas absorption, distillation, valves. When petrochemistry was introduced extraction, drying, adsorption). Arthur D to Japan, instrumentation and control Little from the United States advocated the technology was transitioning from pneumatic idea of unit operation; chemical engineering control to electronic control, and the was established once it was incorporated into technology was becoming more compact and more long-range. Accordingly, Japan’s new

16 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) petrochemical plants built central control automotive industry, such as for car tires. rooms for monitoring and control. This Natural rubber molding in Japan started in method of operation, called process 1886, when Tsuchiya Rubber Factory automation, had not been available to the commenced operations using vulcanization existing chemical industries in Japan. The methods. The tire industry became petrochemical industry and the oil refining established in Japan in the 1920s, and by industry were the first to implement 1931 Bridgestone had commenced production automated production processes. of a purely Japanese-produced tire. Meanwhile, celluloid, a thermoplastic 2.4.3 Instrumental analysis polymer, was industrialized in the late 19th The late 1950s, when petrochemistry was century and was being used in molding introduced to Japan, was the time in which products. Natural rubber molding technology technologies to support petrochemistry were was applied to celluloid molding. In the just coming into full swing; instrumental 1910s, phenol resin, a thermosetting resin, analysis technology was no exception. Gas was industrialized. The molding method was chromatography and infrared spectroscopy compression molding, an extension of press are often used in petrochemistry. In gas molding. By the 1930s, polyvinyl chloride, chromatography, analysis is made by polystyrene, polyethylene and other polymers separating out gaseous components and had been industrialized in Europe. While the easily-vaporized liquid components; in molding of these polymers did not extend infrared spectroscopy, organic compounds are beyond applying rubber molding technology, analyzed by functional group. The world’s the screw extruder soon emerged as what first gas chromatograph was introduced in could be called an archetype for modern 1955; by 1957, Japan had developed its own extruders. By 1939, hard PVC pipes were mass-produced gas chromatograph equipment. being manufactured in Europe. By 1958, the process gas chromatograph was Highly productive molding technologies being developed. By 1957, a high-resolution for thermoplastics include extrusion molding, infrared spectrophotometer had also been blow molding and injection molding. developed. Injection molding had been developed in the While these analysis devices were West before the Second World War, but only initially expensive, prices eventually dropped for very small products at very slow speeds. significantly and they came to be widely used In the 1950s, Japan made significant in the petrochemical industry, not only for advances in PVC, polyvinyl acetate (PVA) research and development and quality control, and urea resins through coal chemistry. Japan but also for process management. was also importing polyethylene and polystyrene. Molding fabricators and molding 2.4.4 Polymer molding technology machine companies started out by importing Natural rubber molding technology as a molding machines from the West and starting polymer molding technology developed from to produce molding products. Right around the mid-19th century onwards. Vulcanization this time there were some rapid developments was discovered in 1839. The development of in extrusion molding and injection molding, rubber processing machinery and making it possible to produce larger products vulcanization techniques (1849) by Thomas faster. Accordingly, in the late 1950s, just as Hancock in the United Kingdom significantly the petrochemical industry was being advanced rubber molding technology. established in Japan, a foundation was being Although natural rubber is a difficult material laid for new plastic molding. After that, to process, molding was achieved with petrochemistry and plastic molding calender molding technology using rollers, technology started developing through mutual and through press molding technology. In the interaction, a trend that has continued to the 20th century, rubber molding technology had present day. become a large-scale industry before the A similar thing occurred with synthetic Second World War, with many rubber fibers. The rayon industry, which had seen molding products being used in the

Systematic Survey on Petrochemical Technology 17

major developments in Japan since the 1920s, used a wet spinning method in which the polymers were dissolved in a solvent and then spun. This was because cellulose, the feedstock for rayon, is not a thermoplastic polymer. By contrast, nylon, industrialized in the United States at the end of the 1930s, used a process called melt spinning, since it is a thermoplastic polymer. Even Japan started small-scale production of nylon during the Fig. 2.7 Petrochemical technology Second World War using domestic characteristics. technology, and was able to produce it using melt spinning. Melt spinning was applied to One significant characteristic of polyester fiber as well in the late 1950s, petrochemistry is not only using petroleum as leading to a series of technological a feedstock, but also using it in fluid form as innovations from the 1970s onwards, such as much as possible at each stage of continuous polymerization and spinning, and petrochemical product production. Basic integration of high-speed spinning, drawing petrochemicals and many industrial organic and false-twist texturing. chemicals exist in gas or liquid form at normal temperatures. Therefore, they are often transported within factories by pumps 2.5 Petrochemical technology and pipes, and often stored in tanks. One of characteristics the biggest reasons for amalgamating

petrochemical factories together and forming While there are of course many petrochemical industrial complexes is that exceptions, a comparison with this makes it easier to handle fluid substances. mass-producing chemical industries that Long-haul transportation between factories is predated petrochemistry and present-day also often done on a large scale by tank trucks, non-petrochemistry chemical industries railroad tank cars or tankers, thereby making reveals the five major distinguishing best use of the fluid properties. characteristics of petrochemical technology By contrast, polymers are often solid shown in Fig. 2.7. products, although some are liquids, such as

solvents and emulsions. However, these 2.5.1 Part of energy revolution solids are often handled in grain form, such as In the 1950s, oil from the Middle East powders or pellets. started being supplied in large volumes to

Japan and Europe, and the main source of Kombinats energy switched to petroleum from coal, 2.5.2 or industrial complexes In petrochemistry, several basic which had been in constant use since the petrochemical products are co-produced, and Industrial Revolution of the 18th century. then used to produce industrial organic This era was known as energy revolution. chemicals and polymer products. As Chemical industries that used coal and mentioned above, basic petrochemical agricultural produce for feedstocks also products and many industrial organic started switching to petroleum as a feedstock. chemicals are fluids. Therefore, the factories This was part of energy revolution. are converged together and connected with pipes for transporting products or raw materials, thus forming kombinats or industrial complexes [Footnote 9]. In many cases in Japan, industrial

[Footnote 9] As mentioned in Footnote 8, there were instances of industrial complexes forming in coal chemistry and electrochemistry. However, it is standard practice in petrochemistry to form industrial complexes; petrochemical industrial complexes are also far larger in scale.

18 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) complexes have formed as industrial organic temperature and atmospheric pressure. chemical plants and polymer plants have However, the use of moderately high pressure gathered around naphtha steam-cracking has made a significant contribution to plants. Most industrial complexes are not equipment productivity, and is also a means connected to each other and instances of of achieving optimal reaction conditions. versatility between basic petrochemical Reactions at room temperature and products such as ethylene or propylene atmospheric pressure are not necessarily through pipes are rare. Although the situation categorically superior. in Europe is essentially similar to Japan, there Petrochemical technology can also be are long-distance ethylene pipelines across categorized by heavy catalyst use, the continent, and some industrial complexes particularly solid catalysts. Advances and even link to other industrial organic chemical improvements in catalysts have been crucial plants and polymer plants. The United States to competition among petrochemical has a long-distance pipeline network for companies. Ironically, ethane and naphtha ethylene and other products; many ethane or steam-cracking have the largest plants in naphtha steam-cracking plants are connected petrochemistry and also serve as the into this network. Many industrial organic foundation for the supply of basic chemical plants and polymer plants are also petrochemical products, but are non-catalytic connected into this network. This situation is reactions. referred to as a “spaghetti bowl.” 2.5.4 Large-scale 2.5.3 Continuous, high-pressure, Even in the late 1950s, when catalytic petrochemical technology was only just Factory layout and operational methods introduced to Japan from the West, in the chemical industries vary significantly petrochemical facilities and factories were far depending on whether a chemical reaction larger in scale than those found in coal takes places continuously or in batches. Many chemistry and other mass-producing chemical reactions in petrochemistry are continuous, industries. The amount of capital needed to with distillation and other processes also build these large-scale facilities and factories carried out continuously. Operations are also was far more than made sense to any of the carried out continuously. Under the other chemical industries. Also, since many provisions of the old High Pressure Gas of the products were unknown to the Japanese Control Act and other such laws, naphtha market, there were huge risks for companies steam-cracking plants in Japan would close aspiring to get into petrochemistry. This was once a year for maintenance, but operate one reason for promoting the formation of continuously at all other times. At the present corporate groups. time, the regulations have eased up, and Up-scaling rapidly progressed from the plants can now operate continuously for 1950s to the 1960s. With the price of oil several years at a time. Many industrial dropping, the petrochemical industry proved organic chemical plants and polymer plants to have good economy of scale. Naphtha also operate continuously and carry out steam-cracking plants that had been built in continuous reactions. the late 1950s with 20,000-ton annual Many petrochemical reactions are also ethylene production capabilities rapidly carried out under high pressure, unlike some expanded to 50,000-ton capabilities in the of the other chemical industries that predate early 1960s, to 100,000-ton capabilities in the petrochemistry, such as coal tar chemistry, mid-1960s, and to 300,000-ton capabilities by acetylene chemistry and fermentation the end of the 1960s. The speed of expansion chemistry. The use of high pressure has often slowed after the oil crises; currently, four come under criticism from the perspective of decades since the 1970s, new ethylene plants energy conservation and been deemed as too are built with annual production capabilities much of a contrast from natural conditions, in of around 0.6–1.2 million tons (or 1–1.5 which reactions are carried out at room million tons for ethane steam-cracking plants,

Systematic Survey on Petrochemical Technology 19

which require less investment expenditure). Japan,” Iwanami Shoten, 1st edition Industrial organic chemical plants and 1957, 2nd edition 1961; Y. Hayashi and polymer plants are also increasing in scale. T. Watanabe, “Chemical industries of Thus, one of the major distinguishing Japan,” Iwanami Shoten, 3rd edition characteristics of petrochemistry is being far 1968, 4th edition 1974. greater in scale than other chemical [2] T. Watanabe, “The petrochemical industries. industry,” Iwanami Shoten, 1st edition 1966, 2nd edition 1972; “The 2.5.5 Internationality petrochemical industry at a turning Since expanding to Europe and Japan point,” Iwanami Shoten, 1984. from the United States in the 1950s, [3] “Ten-year history of the petrochemical petrochemistry has been international in its industry,” Japan Petrochemical Industry technology, feedstocks and product trading. Association, ed., Japan Petrochemical Neither the synthetic dye industry, which Industry Association, 1971. developed in the late 19th century, nor the [4] “A technical survey of process control coal chemical industry, which developed in systems,” Survey Report on the the 20th century, has had this level of Systematization of Technologies, no. 11, internationality; they have shown strong National Museum of Nature and cartel-like tendencies, rejecting newcomers Science, March 2008. and trying to hold a monopoly. Technology [5] “Analytical instruments/scientific was an effective means to that end. By equipment heritage catalog (2014),” contrast, since petrochemistry came after the Japan Analytical Instruments Second World War amidst a world-wide Manufacturers’ Association and Japan proliferation of antitrust policies, it has been Scientific Instruments Association, eds., difficult for anybody to gain a worldwide September 2014. production monopoly by concealing new [6] Y. Yasuda, “Plastic centenary special: petrochemical technologies. The patent history of molding methods and agreement between DuPont in the United machines,” Plastics, Japan Plastics States and ICI in the United Kingdom was Industry Federation, 2007. abolished in 1952 due to violation of antitrust [7] H. Koyama, “The history of Japan’s laws. In the 1950s, concerned that the plastic industry,” Kogyo Chosakai, dominant American petrochemical companies 1967. would expand into Japan and Europe, the [8] “A 10-year history of injection molding Japanese government and various European in Japan,” Japan Injection Molding governments placed strict regulations on Industry Association, 1963. capital expansion. This is thought to be [9] “Injection molding,” Japan Patent another reason that facilitated the Office, ed., Patent Map by Technical internationalization of the technology. Instead Field, 1997. of being unable to be leveraged, new [10] “Plastic extrusion,” Japan Patent Office, technology was licensed to start recovering ed., Patent Map by Technical Field, the expenses of development as soon as 1998. possible. British company ICI sent an enquiry [11] “An outline of the development of poly commission to Japan in the 1950s specifically vinyl chloride technology in Japan, to promote the high-pressure polyethylene inclusing a description of historical technology it had developed in the 1930s. materials (2),” Survey Report on the From such beginnings, petrochemical Systematization of Technologies, no. 2, technology continued to become even more National Museum of Nature and internationalized from the 1970s onwards as Science, March 2002. plant engineering companies expanded. [12] “Systematic review of tyre technology,” Survey Report on the Systematization of Bibliography Technologies, no. 16, National Museum [1] Y. Hayashi, “Chemical industries of of Nature and Science, March 2011.

20 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

[13] “History of polyester fiber technologies Technologies, no. 7, National Museum used for making textiles,” Survey of Nature and Science, March 2007. Report on the Systematization of

Systematic Survey on Petrochemical Technology 21

Petrochemical product categories

3 The previous chapter provided a petrochemical products produced will be bird’s-eye view of the forest that is olefins with C2 to C4. If the raw material is petrochemistry. Since this does little to reveal naphtha, gas oil or other petroleum product any detail, let us now enter that forest. In (hydrocarbon mixtures with five or more other words, this chapter discusses carbon atoms), then the basic petrochemical petrochemical product categories and how products produced will be olefins and these products are made. aromatic hydrocarbons. While petrochemical products can be The size and complexity of petrochemical broadly grouped into three categories: basic products are determined by the number of petrochemical products, industrial organic carbon atoms in the raw material. The main chemicals and polymers, they are not petrochemical product line patterns around necessarily always produced in this order. In the world can be broadly categorized into five many cases, polymers are made from basic groups, as shown in Table 3.1. petrochemical products without first being Pattern (1) is the petrochemistry to made into industrial organic chemicals. Since produce methanol from syngas using natural industrial organic chemical products and methane gas as a raw material. At the present polymer products are generally made time, over 1 million tons of methanol is separately according to the number of carbon produced annually at large-scale plants. atoms in the basic petrochemical product, Although there are several derivative here we shall discuss industrial organic products made from methanol, as shall be chemicals and polymers together in order of mentioned later, very few derivative products the number of carbon atoms in the basic are produced on a large scale at methanol petrochemical product. production sites. In many cases, methanol is For those who are unfamiliar to chemistry, exported in its manufactured form. this chapter may seem to be complicated and Accordingly, it is no overstatement to say that confusing. It should suffice to look at only the Pattern (1) is methanol-plant petrochemistry. figures and tables, and to note the Pattern (2) is the petrochemistry to magnificence and intricacy of modern produce ethylene products from ethylene petrochemical industries. using ethane from natural gas and associated petroleum gas as raw materials. At present, 3.1 Global petrochemical industries by plants have been built with annual ethylene product categories production capabilities of over 1 million tons; these are in the form of industrial complexes Since petrochemical product categories that produce several different types of are complex and there is every chance that we ethylene-based products using ethylene as a would lose sight of the overall forest if were raw material. Pattern (3) is the petrochemistry looked too closely at the individual trees, let to produce a lot of different industrial organic us first examine the patterns in major chemicals and polymers from a wide variety petrochemical product categories around the of olefins and aromatic hydrocarbons using world, thereby revealing the broader naphtha, gas oil and other liquid petroleum categories in the forest that is petrochemistry. products as raw materials. Since plants are Basic petrochemical product categories presently being built with ethylene production largely depend on the raw material used. If capabilities of over 500,000 tons (over 1.5 the raw material is methane, with C1, then million tons of basic petrochemical products only basic petrochemical products with C1 in total), these are taking the form of can be produced. If the raw material is ethane, industrial complexes surrounded by a number with C2, then the only basic petrochemical of derivative product plants. While Patterns product that can be produced is ethylene, with (2) and (3) are in competition on the global C2. If the raw material is propane or butane, ethylene-based products market, with C3 or C4, then the main basic

22 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) non-ethylene-based products are mainly generally produces no non-ethylene-based provided through Pattern (3), as Pattern (2) products.

Table 3.1 Global petrochemical industries by products

Pattern (4) is the petrochemistry to discuss the raw materials in petrochemistry. produce propylene-based and butylene-based products from propylene and butylene from 3.2.1 Oil/natural gas producing areas byproduct waste gas emitted when producing and location of petrochemical the gasoline fraction using heavy oil as a raw industries material. Pattern (5) is the petrochemistry to The raw materials for petrochemistry are produce aromatic-based products by petroleum and natural gas, as previously extracting aromatic hydrocarbons from mentioned. Both are made up of reformate. Patterns (4) and (5) only take place hydrocarbons, and both are extremely useful in countries and regions where gasoline is as sources of fuel (energy). In terms of the produced from heavy oil, or where overall consumption of petroleum and natural high-octane gasoline is produced in large gas, only a very small amount is used as raw volumes. Since the main aim is to produce materials for petrochemistry. Where natural gasoline, and basic petrochemical products gas is used as a fuel (energy) source, it is are byproducts, these complement Patterns transported long distances in its natural state (2) and (3). In the United States, Pattern (2) is through pipelines, or converted into liquefied common while Pattern (3) is rare; meanwhile, natural gas (LNG) and transported by LNG since there is a high supply from Patterns (4) tankers. Long-distance transportation can be and (5), these are the main source of supply adequately covered by a fixed cost, since far for non-ethylene-based products. higher quantities of gas are used for fuel than for petrochemical raw materials. However, 3.2 Raw materials for petrochemistry where natural gas is used as a petrochemical raw material, it is consumed near the Different petrochemical industries in production site rather than being transported different countries around the world produce long distances. By contrast, petroleum is different product categories, due to the often transported near to the area of different raw materials available. Since raw consumption, since crude oil and even materials are the greatest determining factor naphtha, the main petrochemical raw material, for the petrochemical industry, let us first can be transported long distances in large

Systematic Survey on Petrochemical Technology 23

tankers. 3.2.3 Associated petroleum gas Consequently, in areas with natural gas, Gaseous hydrocarbons dissolve into petrochemical industries tend to be located crude oil at high pressure underground, but near production sites. In areas without natural they naturally separate out again at gas, imported crude oil, naphtha and other atmospheric pressure when the crude oil is petroleum products are used as raw materials, mined. This is called associated petroleum and petrochemical industries have developed gas. Associated petroleum gas often contains near areas of consumption. ethane, propane and butane, as well as methane. Once the ethane is separated and 3.2.2 Natural gas recovered, it is used as a raw material for Most of the natural gas mined in the ethylene. The petrochemical industries that North Sea, Russia, Asia and the Pacific, have developed in the Middle East on a large including the small amount mined in Japan, is scale since the 1980s used associated made up of only methane. Methane is the petroleum gas as a raw material, where simplest saturated hydrocarbon with C1 previously it had not been used for anything. [Footnote 1]. In Japan, methane is imported Associated petroleum gas also contains long-haul in large quantities in LNG form; it hydrocarbons that liquefy at atmospheric is solely used as fuel for thermal power pressure, corresponding to the naphtha generation and city gas supplies. Since it can fraction. This is called gas condensate, or be expensive, it is rarely used as a natural gasoline. With simple distillation, gas petrochemical raw material. Petrochemical condensate makes an extremely good and ammonia/fertilizer industries that use petrochemical raw material, which is methane as a raw material are often located marketed as naphtha, like that distilled from near methane production sites. Many of the crude oil. world’s natural gas fields are in remote locations that are of little use, as the methane 3.2.4 Crude oil and petroleum products cannot be transported anywhere. Hydrocarbons with five or more carbon While natural gas mined in the United atoms exist in liquid form at atmospheric States, Canada and the Middle East is mainly pressure. Crude oil comes in various forms, made up of methane, it can also contain a depending on where it is produced; some percentage of ethane, a saturated hydrocarbon forms are mainly made up of saturated with C2, as well as a small proportion of hydrocarbons, while some forms contain high propane and butane, saturated hydrocarbons amounts of alicyclic hydrocarbons with C3 or C4. The same is true of shale gas [Footnote 2] or aromatic hydrocarbons. Crude mined in the United States, a recent topic of oil also contains sulfur, nitrogen or other discussion. Ethane, propane and butane can organic compounds. Oil refining industries be cracked and used as raw materials for distill and refine crude oil, separating out olefins. As propane and butane are easily different products according to their boiling liquefied, they are often made into liquefied points: the naphtha/gasoline fraction petroleum gas (LPG) and transported long [Footnote 3], the kerosene/jet fuel fraction, distances to be sold for fuel. Since ethane is the diesel oil fraction and the heavy oil not as easily liquefied as propane and butane, fraction. Oil refineries also produce various it is used almost solely as a petrochemical types of complementary petroleum products raw material near production sites, like in the required quantities through various methane. If there are no nearby petrochemical physical treatments and chemical processes, facilities, ethane can also be used in fuel such as vacuum distillation, hydrocracking, without being separated from methane.

[Footnote 2] Hydrocarbons that are made up of only single bonds and have a cyclic structure are called alicyclic hydrocarbons. Also [Footnote 1] Hydrocarbons made up of carbon chains with only called naphthenes or cycloparaffins. single bonds are called saturated hydrocarbons. They are also known [Footnote 3] The oil fraction with a boiling point between 30–180˚C as paraffins or alkanes. Their molecular formula can be represented (or 200˚C) is called naphtha. Naphtha, also called crude gasoline, is as CnH2n+2. Methane CH4 has the lowest number of carbon atoms of mainly made up of hydrocarbons with C5–C12. Gasoline is a type of any saturated hydrocarbon. Saturated hydrocarbons are the least naphtha used as automotive fuel, with its octane number, sulfur reactive of the hydrocarbons. content and benzene content adjusted to particular standards.

24 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) thermal cracking, catalytic cracking, catalytic reforming, alkylation, dehydrogenation, hydrotreating, isomerization and caulking processes. In Japan and other parts of Asia, only naphtha is used as a petrochemical raw material. In Europe, both naphtha and gas oil [Footnote 4] are used as petrochemical raw materials. Oil refineries produce large amounts of Fig. 3.1 Basic petrochemicals from methane. petroleum waste gas during catalytic cracking and other chemical processing. These waste Syngas is a mixture of carbon monoxide gases are made up of propylene, butylene and and hydrogen. It can be made from coal, other olefins. These olefins can be used as natural gas and petroleum and also from raw materials for petrochemistry as necessary. carbohydrates, though in small quantities. In Catalytic reforming is a type of chemical the petrochemical industry, it is entirely made processing to raise the octane number from natural gas (methane). Syngas thus [Footnote 5] of gasoline. Since catalytic obtained is further chemically treated to reformate contains high quantities of aromatic change the carbon monoxide/hydrogen ratio hydrocarbons, these can be extracted as depending on the expected use and is used for necessary to produce basic petrochemical synthesis of methanol and production of products. Thus, oil refineries often produce carbon monoxide. As a raw material for oxo and supply basic petrochemicals. Further process (hydroformylation), syngas is also details on petroleum refining technology have used for production of oxoaldehyde and not been included in this report. oxoalcohol. In industries other than petrochemistry, it is used for production of 3.3 Product categories of basic hydrogen and synthesis of ammonia and petrochemicals artificial petroleum. Syngas is manufactured from methane by Main basic petrochemicals include C1 steam reforming. Methane is reacted with syngas, C2–C5 olefins and C6–C8 aromatic water to give syngas composed of carbon hydrocarbons. The product categories of monoxide and hydrogen that is 3 times the basic petrochemicals are given below for volume of carbon monoxide. each raw material and production technique. C1 basic petrochemicals other than 3.3.1 C1 basic petrochemicals syngas are described below. Carbon Figure 1 shows the product categories of monoxide is produced from syngas. Phosgene C1 basic petrochemicals made from methane. (COCl2) is made by the reaction of carbon The main C1 basic petrochemical is syngas. monoxide and chlorine. According to the Andrussow process, hydrogen cyanide is Carbon monoxide (CO), phosgene (COCl2), hydrogen cyanide (HCN) and synthesized from methane, ammonia and air chroromethanes are also C1 basic at 1,000°C. Water is obtained as a byproduct. petrochemicals. According to a modification of the Andrussow process, hydrogen cyanide and hydrogen are only made from ammonia and methane at 1,400°C in the absence of air. Because hydrogen cyanide is produced in large quantities as a byproduct when acrylonitrile is made by ammoxidation of [Footnote 4] Gas oil is generally the same thing as diesel oil. However, in some cases, gas oil refers to both kerosene and diesel propylene, this process has been used to oil. supply of hydrogen cyanide at a low price [Footnote 5] Octane number is an index that indicates the anti-knocking capacity of gasoline engine fuels. The reference since the 1960s. However, owing to criteria range from 0 to 100, with iso-octane having an octane improvement of catalysts for ammoxidation number of 100, and n-heptane having an octane number of 0.

Systematic Survey on Petrochemical Technology 25

in recent years, the production of hydrogen hydrocarbons are steam-cracked to give cyanide as a byproduct has been markedly mixtures of olefins and aromatic decreasing. hydrocarbons as co-products. Chloromethane is made by direct chlorination of methane. It is classified into (1) Steam cracking technique four types, which are methyl chloride, Hydrocarbon is cracked when naphtha or dichloromethane (methylene chloride), gas oil is mixed with superheated steam and chloroform and carbon tetrachloride, is then passed for a few milliseconds through depending on the number of chlorine atoms. a pipe that is heated above 1,000°C from the If another manufacturing process is used, outside. The cracked gas is quenched to methyl chloride is made from methanol and approximately 300°C in a heat exchanger hydrogen chloride by dehydration, and is then (quench cooler). As the reaction temperature chlorinated to produce chloromethanes with of steam cracking is 800–900°C, heat can be more chlorine atoms. If this process is used, recovered as high-pressure steam using the the necessary products can easily be obtained quench cooler. The cracked gas is then with a higher yield. sprayed with oil (mainly cracked gasoline, The commercial value of carbon mentioned below) in the quench tower and tetrachloride was lost in the 1990s when it then with water in the next quench tower. As was specified as an ozone layer depleting a result, the steam mixed at the time of substance and its production and consumption reaction changes to water, and the C5–C9 were regulated by the Montreal Protocol. The fractions of the cracked products are commercial values of fluorocarbons (such as condensed/separated and collected as a liquid hydrogen-free chlorofluoromethanes) and (cracked gasoline). Further separation and halons (such as hydrogen-free purification of the cracked product are bromofluoromethanes) made from described in the next section. chloromethanes have also been lost, because Steam cracking described here is not a these substances were also classified as ozone reaction of hydrocarbons with steam as was layer depleting substances. Fluorocarbon mentioned in the preceding section on substitutes made from chloroform, etc. are manufacture of syngas (steam reforming). also being regulated one by one to prevent Steam only lowers the partial pressure of global warming. gaseous hydrocarbons. Steam cracking achieved by thermal cracking in the absence 3.3.2 Basic petrochemicals from steam of a catalyst is markedly endothermic. cracking of gaseous hydrocarbons Cutting of carbon chains, isomerization, Ethylene and hydrogen are only produced cyclization and dehydrogenation of by steam cracking of ethane that is separated hydrocarbons occur during the reaction. If the from natural gas, crude oil associated gas, etc. retention time of hydrocarbons is too long, Other olefins or aromatic hydrocarbons are thermal cracking will progress further, rarely produced. In the United States, steam ultimately resulting in cracking into carbon cracking of a mixture of ethane and propane and hydrogen. Therefore, the retention time is or a mixture of propane and butane is also shortened to avoid this problem, but carbon performed, though on a small scale. In this as a byproduct of hydrocarbon thermal case, not only ethylene but also olefins such cracking still accumulates in the pipes during as propylene and butylene are obtained. The operation. Since steam cracking devices are production of aromatic hydrocarbons is low. composed of up to a dozen furnaces, the As the steam cracking technique for gaseous furnace in which the carbon accumulates in hydrocarbons is the same as that for naphtha the pipes is separated after the supply of raw and gas oil, it is described in the following materials is stopped, and then air is supplied section. to remove the carbon by combustion. After 3.3.3 Basic petrochemicals from steam this decoking operation, the furnace is put cracking of liquid hydrocarbons into operation again.

As shown in Fig. 3.2, liquid

26 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.2 Major basic petrochemicals obtained from steam cracking of naphtha or gas oil.

The production of olefins is higher when (2) Separation and purification of olefins the cracking temperature is higher, retention and aromatic hydrocarbons time is shorter, and partial pressure of Since many olefins and hydrocarbons are hydrocarbons is lower (mixed with more produced simultaneously during steam steam). Recently, because the main suppliers cracking of naphtha and gas oil, the of aromatic hydrocarbons as a basic techniques for separating and purifying them petrochemical have also transitioned to oil have progressed. Several refiners (catalytic reformate) in Japan, steam separation/purification processes have been cracking devices for naphtha tend to be developed depending on the order of product operated in such a way to obtain more olefins. separation. Detailed description of each The yields of basic petrochemicals process is avoided here, and how to separate produced by steam cracking differ greatly and purify co-products is described below by depending on the raw material and conditions showing an example. for cracking. If the raw material is ethane as At first, the cracked product cooled to mentioned in the preceding section, the yields room temperature in the water quench tower of ethylene and hydrogen/methane are is divided three ways, namely, water, a gas approximately 80% and 14%, respectively. If component and a component that occurs as a the raw material is butane as mentioned in the liquid at room temperature (cracked preceding section, the yields of ethylene, gasoline). propylene, butylene/butadiene and The gas component is washed with a hydrogen/methane are approximately 38%, solution of sodium hydroxide to remove 15%, 10% and 25%, respectively. In contrast, carbon dioxide and traces of sulfur if the raw material is naphtha, the yields of compounds. After drying, the gas is cooled ethylene, propylene, butylene/butadiene, under compression. Hydrogen, the C1 basic petrochemicals with five or more fraction and the C2, C3 and C4 fractions are carbon atoms (including aromatic separated one by one while the gas is being hydrocarbons) and hydrogen/methane are passed sequentially through the distillation approximately 30–35%, 15–17%, 9–12%, columns for demethanization, deethanization, 25% and 14–16%, respectively. depropanization, debutanization, etc. The C2 fraction is further separated into ethylene and

Systematic Survey on Petrochemical Technology 27

ethane in the ethylene column to give On the other hand, the C5 fraction is ethylene. Ethane is charged again as a raw separated first from cracked gasoline which material into the cracking furnace. The C3 has been separated from the gas component fraction is separated into propane and and water in the water quench tower as propylene in the propylene column to give mentioned at the beginning of this section. propylene. As it is very difficult to separate Various hydrocarbons are contained in the propane and propylene by distillation, a C5 fraction. However, because it is difficult distillation column with a large number of to separate all of them, only isoprene and plates is needed. To synthesize industrial cyclopentadiene are separated due to organic chemicals, propylene is often purified demand. When the C5 fraction is heated at to a chemical grade of approximately 94%. 150°C under pressure, cyclopentadiene is To produce PP, its purity must be further dimerized to give C10 dicyclopentadiene increased to a polymer grade of 99.5% or (DCPD) which can be separated by more. distillation. When C10 dicyclopentadiene is Separation of the C4 fraction is heated at 350°C after separation, time-consuming, because it contains many cyclopentadiene is reproduced. The C5 components. As shown in Fig. 3.3, butadiene fraction from which cyclopentadiene has is separated first by extractive distillation been separated is subjected to extractive using a polar solvent. Because three kinds of distillation with acetonitrile or N-methyl n-butylene [Footnote 6] and isobutylene are pyrrolidone to separate isoprene. The contained in raffinate I from which butadiene remaining C5 fraction is not separated has been removed, isobutylene with the further, but is polymerized and used as highest reactivity is changed to tert-butyl petroleum resin. alcohol by hydration in the presence of a Aromatic and non-aromatic hydrocarbons solid acid catalyst and separated. Tert-butyl are then separated first from the six or more alcohol is returned to isobutylene by carbon atoms fractions. For this purpose, dehydration. If it is necessary to separate solvent extraction is often performed using a 1-butylene from the remaining raffinate II, it solvent such as N-methyl pyrrolidone, can be separated by extractive distillation or N-formylmorpholine or by using a porous solid adsorbent. Raffinate N,N-dimethylformamide (DMF). III from which 1-butylene has been removed Aromatic hydrocarbons are further is a mixture of cis- and trans-2-butylene. This separated by distillation into benzene, toluene mixture is usually used, without further and mixed xylene. Mixed xylene (the C8 separation, for manufacture of alkylate aromatic hydrocarbon fraction) is a mixture gasoline or synthesis of sec-butyl alcohol. of ethylbenzene, o-xylene, m-xylene and p-xylene. Since these chemicals cannot be separated by distillation due to having similar boiling points, various methods of separating them have been developed. As the demand for p-xylene is much greater, its separation is the most important. At present, the Parex process developed by Universal Oil Products (UOP) in 1971 is widely used (see Section 6.1.1 (6)).

Fig. 3.3 Separation of the C4 fractions. 3.3.4 Basic petrochemicals from catalytic cracking and catalytic reforming In the oil refinery industry, catalytic cracking of the heavy oil fraction is performed to obtain more gasoline fraction as [Footnote 6] Molecules with a straight carbon chain are called linear well as the fraction contained in crude oil, molecules, and n is attached. In the case of butylene, 1-butylene, cis-2-butylene and trans-2-butylene shown in Fig. 2.2 are linear resulting in the formation of large quantities molecules.

28 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) of waste gas. Since olefins such as propylene aromatic hydrocarbons can be supplied from and butylene are contained in the waste gas, it cracked gasoline. However, because the is possible to separate/purify and use them as demand for aromatic hydrocarbons has necessary. However, this process is not increased, the main supply source of aromatic efficient, because the concentrations of hydrocarbons in Japan has also changed from propylene and butylene in waste gas are cracked gasoline to catalytic reformates. lower for catalytic cracking of heavy oil than for steam cracking of naphtha. In countries 3.3.5 Disproportionation and where steam cracking of naphtha is actively isomerization of aromatic carried out, there is low dependence on hydrocarbons propylene and butylene separated from waste Production of benzene and xylene by gas from catalytic cracking, because the disproportionation of toluene and production production of propylene and of butylene from of mixed xylene by isomerization of steam cracking of naphtha correspond to m-xylene are included in the techniques of approximately one-half and one-third of the manufacturing basic petrochemicals (see production of ethylene, respectively. On the Section 6.1.1 (6)). other hand, in the United States, catalytic cracking of petroleum is performed on a large 3.4 Product categories of industrial scale (Section 3.1). When the C3 fraction organic chemicals and polymers from catalytic cracked gas is used for synthesis of alkylate gasoline, etc. in the oil In the petrochemical industry, industrial refinery industry, it is not distilled precisely organic chemicals and polymers are made but to a refinery grade (approximately 70% from basic petrochemicals according to the propylene purity) (the main impurity is number of carbons, and different industrial propane with low reactivity). When it is used organic chemicals and polymers are made for production of industrial organic chemicals from individual industrial organic chemicals. and polymers, it must be purified to a Therefore, in this section, the product chemical or polymer grade as mentioned categories of industrial organic chemicals and above. polymers are described for each carbon In the oil refining industry, catalytic number found among basic petrochemicals. reforming of naphtha/gasoline fractions is There are usually several competitive performed to enhance the octane number of routes and techniques for manufacture of gasoline. It is enhanced because hydrocarbon industrial organic chemicals. Moreover, molecules are branced, cyclized and historically, they have often shown profound aromatized by catalytic reforming. As a result, changes. In this section, typical routes and aromatic hydrocarbons are contained in techniques are described to provide further catalytic reformates. However, because insight on the product categories of current concentrations of aromatic hydrocarbons are petrochemistry. Competitive routes and lower for catalytic reformates than for historical changes are explained later. cracked gasoline, various solvent extraction As there are much more industrial methods have been developed. Old organic chemicals and polymers than basic well-known methods are the Udex process petrochemicals in the petrochemical industry, (extracting solvent: ethylene glycols/water) it is impossible to describe all of them. Since developed by UOP-Dow Chemical in 1952 the purpose of this report is to take a general and the sulfolane process developed by view of petrochemical manufacturing Shell-UOP in 1959. On the other hand, new techniques and to consider the processes using new solvents have also been systematization of such techniques, only the developed one after another. Catalytic typical products manufactured in large reformates are the main supply source of quantities worldwide or in Japan are aromatic hydrocarbons in the United States In described below. places like Europe and Japan, where steam cracking of naphtha is actively carried out, 3.4.1 Product categories from the C1

Systematic Survey on Petrochemical Technology 29

fraction (dihydric alcohol) are made by aldol C1 basic petrochemicals include syngas, condensation and reduction reaction of carbon monoxide, phosgene, hydrogen formaldehyde with various aldehydes. These cyanide and chloromethanes. Figure 3.4 alcohols are used as raw materials for shows the categories of main industrial unsaturated polyester and alkyd resin and as organic chemicals and polymers raw materials for polyether polyol used in manufactured from each of them. polyurethane. Formaldehyde is also used for synthesizing 4,4-diaminodiphenyl methane as a raw material for methylene diphenyl diisocyanate (MDI). At present, acetic acid is manufactured mainly from methanol and carbon monoxide. This process is explained under (3) in this section.

(2) Oxoaldehyde and oxoalcohol Aldehydes are synthesized by the oxo process (hydroformylation) in which olefins, Fig. 3.4 Major product categories from basic etc. are reacted with carbon monoxide and petrochemicals with C1. hydrogen. Aldehydes thus obtained have one more carbon atom than the original olefins. (1) Methanol Synthesis of n-butyraldehyde and The production of methanol from syngas isobutyraldehyde from propylene is the is greater than that of any other C1 greatest use of the oxo process. This reaction petrochemicals. Methanol is made by the is also used for synthesis of propionaldehyde reaction of syngas as a mixture of carbon from ethylene and for synthesis of monoxide and hydrogen at a gas volume ratio β-hydroxypropionaldehyde from ethylene of 1:2. . Methanol is used not only as a oxide. Propionaldehyde and solvent but also in large quantities for β-hydroxypropionaldehyde are reduced with synthesizing industrial organic chemicals. It hydrogen to give n-propylalcohol and is used for manufacture of various methyl 1,3-propanediol, respectively. Linear higher esters as well as formaldehyde and acetic acid. alcohols are made by the oxo process of In recent years, methanol has also been used α-olefins. Such a series of aldehydes in large quantities for synthesizing fuels and produced by the oxo process are called fuel additives, such as biodiesel oil from fats oxoaldehydes, while alcohols formed by and oils [Footnote 7] and dimethyl ether. reduction of these oxoaldehydes are called Formaldehyde is made by oxo alcohols. dehydrogenation or oxidative

dehydrogenation of methanol. Many (3) Industrial organic chemicals from industrialized processes are available. carbon monoxide Formaldehyde is also used for production of The most significant industrial organic phenol, urea and melamine resins. It is used chemical from carbon monoxide is acetic acid. for producing polyacetal as one of the It is produced by the reaction of methanol and engineering plastics. It is also used as an carbon monoxide. The most important use of organic intermediate for making various acetic acid is vinyl acetate. Acetic acid is also organic compounds. Pentaerythritol used as a solvent for manufacture of (tetrahydric alcohol), trimethylol propane terephthalic acid. Acetic acid is also used for (trihydric alcohol) and neopentyl glycol other purposes such as the production of acetate, acetic anhydride and chloroacetic [Footnote 7] Biodiesel oil is a higher fatty acid methyl ester. Higher fatty acid methyl esters and glycerin are produced by acid. transesterification between oils/fats (triglycerides as higher fatty Ube Industries has industrialized a acids) and methanol. As the oils and fats, palm oil, rape seed oil and sunflower oil are often used. Biodiesel oil can also be made from method of co-producing dimethyl carbonate used edible oil, though in very small quantities.

30 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) and dimethyl oxalate by the reaction of pharmaceuticals, pesticides, etc. carbon monoxide with methyl nitrite in the Hydrogen cyanide used to be obtained in presence of a platinum-group metal catalyst large quantities as a byproduct of acrylonitrile. (nitrite process). Methyl nitrite is synthesized At that time, it was reacted with acetone and from nitrogen monoxide, methanol and butadiene to give methyl metacrylate and oxygen. Oxalic acid is obtained from adiponitrile, respectively. However, in recent dimethyl oxalate. Ethylene glycol (EG) is years, because the production of hydrogen obtained by hydrogen reduction of dimethyl cyanide as a cheap byproduct has decreased, oxalate. Accordingly, C2 industrial organic its large-scale uses have also decreased. chemicals (oxalic acid and EG) can be obtained from C1 petrochemicals such as (6) Products from chloromethanes carbon monoxide and methanol by the nitrite As industrial organic chemicals from process (see Section 6.2.3). chloromethanes have become regulated as ozone depleting substances or greenhouse (4) Products from phosgene gases, the production of these substances has Phosgene is a highly reactive gas and is recently decreased to a large extent. However, used in large quantities for the manufacture of some important petrochemicals are still being diisocyanate as raw materials of polyurethane manufactured from chloromethanes. and polycarbonate. As a solvent/detergent, dichloromethane Isocyanate is synthesized by the reaction (methylene chloride) is widely used not only of amine with phosgene. Aromatic in the chemical industry but also in the diisocyanates (MDI and toluene diisocyanate machine industry. Methyl chloride is reacted [TDI]) are produced on a large scale. Of the with silicon to give chlorosilanes. aliphatic diisocyanates, hexamethylene Chlorosilanes are important raw materials of diisocyanate, isophorone diisocyanate, etc. silicone oil, silicone rubber and silicone resin. are not produced on such a large scale, but Chlorodifluoromethane (HCFC-22) are essential for the manufacture of obtained by the reaction of chloroform with non-yellowing polyurethane foam. anhydrous hydrofluoric acid is thermally Phosgene is reacted with compounds cracked to give C2 tetrafluoroethylene. having hydroxy groups to give carbonic acid Polytetrafluoroethylene is obtained by radical esters (carbonates). Of these, bisphenol A polymerization of tetrafluoroethylene (BPA) is reacted with phosgene to give large according to the suspension polymerization quantities of polycarbonate as an engineering method. Polytetrafluoroethylene (PTFE) is a plastic. typical fluororesin (Teflon). Phosgene is also reacted with carboxylic acid to give acid chlorides. As 3.4.2 Products from the C2 fraction monoisocyanate and acid chlorides are highly (ethylene-based products) reactive industrial organic chemicals, they are The C2 basic petrochemical is ethylene. used as organic intermediates for the Figure 3.5 shows the categories of main manufacture of pesticides, pharmaceuticals products from ethylene. Of the four major and surfactants. general-purpose resins which are produced in exceptionally large quantities compared with (5) Industrial organic chemicals from other polymers, polyethylene, polystyrene hydrogen cyanide and vinyl polychloride are made from Alkali salts (sodium cyanide and ethylene. Furthermore, because ethylene is potassium cyanide) of hydrogen cyanide often used as a comonomer of propylene (hydrocyanic acid) are used in the metal [Footnote 8], it may be said that the products refining, plating and inorganic chemical from ethylene including PP play the most industries. These substances are also used for [Footnote 8] Polymers in which only one type of molecule introducing a cyano group in organic (monomer) is polymerized are called homopolymers. Polymers in synthetic reactions and as organic which different types of molecule are polymerized (copolymerized) are called copolymers. Of more than one monomer involved in intermediates for dyes, feed additives, copolymerization, the monomers other than the main monomer are called comonomers.

Systematic Survey on Petrochemical Technology 31

important role in the petrochemical industry. reaction to double bonds (see Section 6.1.2 The reaction of ethylene is mostly addition (1)).

Fig. 3.5 Major product categories from ethylene.

(1) Polyethylene Ethylene is polymerized to give polyethylene. Polyethylene is the greatest use of ethylene and is a typical petrochemical that is produced i larger quantities than any other polymers. Since the molecular structure of ethylene is CH2=CH2, the basic molecular structure of polyethylene is -(CH2)-, and

thousands to hundreds of thousands of Fig. 3.6 Type of typical polyethylenes. -(CH2)- are connected. The molecular chain of polyethylene may be almost High-pressure low-density polyethylene one-dimensional/straight or branched. (LDPE) is polyethylene that was synthesized Furthermore, in addition to ethylene, a for the first time in 1933. LDPE is made by comonomer is used in small quantities to radical polymerization [Footnote 9] at 200°C change the performance of polyethylene by and 2,000 atm using a trace of oxygen or slightly modifying the structure of its peroxide as a polymerization initiator molecular chain. Thus, as shown in Fig. 3.6, [Footnote 10]. The autoclave (vessel) and polyethylene is roughly classified into 4 tubular processes are available depending on types: low-density polyethylene (LDPE), the type of reactor, but both of them are based ethylene-vinyl acetate copolymer (EVA), on the bulk polymerization process high-density polyethylene (HDPE) and [Footnote 11]. Because the molecular chain L-LDPE. of LDPE is branched substantially,

[Footnote 9 ] Chemicals that generate radicals on heating, etc., thus making radical polymerization start are called polymerization initiators. Catalysts do not remain on the molecular chains of polymers, while some of the polymerization initiators become part of molecular chains. [Footnote 10 ] Radical polymerization is one of the polymerization reactions. In this reaction, the molecular chain that grows when the polymer chain grows due to the reaction of the monomer is a radical. In contrast, the reaction in which the growing molecular chain is an ion is called ionic polymerization. (See Section 6.1.3 (1) 2), 3)) [Footnote 11 ] See Secton 6.1.3 (1) for these polymerization method.

32 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) crystallization hardly occurs and as a result, it owing to the development of highly active has low density (0.915–0.925) compared with catalysts, production by gas phase other types of polyethylene. As a transparent polymerization [Footnote 11] using a flexible film, LDPE is used in large quantities fluidized bed reactor started in the 1980s and for packaging bags, garbage bags, mulch has subsequently become widely used. films for agriculture, etc. It is also used for HDPE is often injection- or blow-molded molded products such as blow-molded bottles and used for convenience goods, containers, and extrusion-molded pipes. Crosslinked automotive gasoline tanks, kerosene tanks LDPE is used as an insulating material for and bottles. HDPE with high molecular high-voltage transmission line cables. weight is extrusion-molded to give an However, because expensive extremely thin but strong film, which is used superhigh-pressure facilities are required for for disposable shopping bags and packaging LDPE, LDPE has recently tended to be bags at supermarkets. As a synthetic fiber, replaced by L-LDPE mentioned below and as HDPE is used for fishing nets, ropes, filter a result, there are few new LDPE plants under cloth and insect proof nets. The film is split construction. and extended to give flat yarn and split yarn, Ethylene-vinyl acetate (EVA) resin is a which are used for blue sheets, flexible copolymer obtained by copolymerization of containers, strings for packing, etc. ethylene and vinyl acetate. Due to its L-LDPE has low density, while keeping excellent adhesiveness, it is laminated with the advantages of HDPE, i.e., low equipment other types of polymer film and used as a and operational energy costs. When ethylene multilayer film. It is also used as an adhesive is copolymerized with a several-percent lower (hot-melt adhesive) for paper bags, etc. and as α-olefin such as 1-butylene, 1-hexene or a foamed product for shoes and sandals. EVA 1-octene [Footnote 12], C2–C6 side chains of resin can be produced using the same alkyl groups occur at random in the molecular manufacturing equipment as for LDPE. chain. Due to such side chains, unlike HDPE, High-density polyethylene (HDPE) is the linear main chain of L-LDPE cannot be made by ionic polymerization of ethylene changed to crystals, demonstrating [Footnote 10] at room temperature to 250°C characteristics similar to those of LDPE and atmospheric pressure to 150 atm. (density, transparency, flexibleness, etc.). Catalysts are needed for polymerization. By Moreover, because highly active catalysts can using the Phillips process or Standard Oil of be used for L-LDPE as well as for HDPE, Indiana process depending on the catalyst, L-LDPE can also be manufactured by gas polymerization is carried out at a medium phase polymerization with higher pressure of several tens to 150 atm. On the productivity. Slurry polymerization is also other hand, if a Ziegler or metallocene applicable. catalyst is used, polymerization of ethylene In addition to the four polyethylenes can be performed under moderate conditions mentioned above, many special polyethylenes (atmospheric pressure and less than 90°C). and reformed polyethylenes are being Linear polyethylene without branching can be manufactured. The molecular weights of the obtained by both of the medium pressure and typical polyethylenes mentioned above are atmospheric pressure processes. Since such a approximately 20,000 to 250,000. molecular chain tends to be folded to produce Polyethylenes of more than 1 million crystals, slightly higher density (0.955–0.965) molecular weight are called ultrahigh translucent polyethylene can be obtained. molecular weight polyethylenes. It is difficult HDPE does not require the to mold them, but because of excellent superhigh-pressure manufacturing facilities abrasion resistance and shock resistance, that are essential for LDPE and consumes these polyethylenes are used as engineering much less energy to manufacture than LDPE. plastics. Polyethylene can be crosslinked by HDPE has been manufactured by solution polymerization [Footnote 11] and slurry [Footnote 12] Olefins in which the double bond is at the end of the carbon-carbon bonds are called α-olefins. Both lower α-olefins with polymerization [Footnote 11]. However, a small number of carbon atoms and higher α-olefins with a large number of carbon atoms are available.

Systematic Survey on Petrochemical Technology 33

exposure to radiation or blending with an Ethylene oxide is manufactured by organic peroxide during or after molding. directly adding oxygen to ethylene in the Crosslinked polyethylene is clearly more presence of a silver catalyst. Because carbon excellent with respect to heat resistance, dioxide is produced if ethylene is oxidized strength and weather resistance. Various excessively, selectivity [Footnote 14] is polyethylene copolymers in which ethylene is important. To improve selectivity, various copolymerized with vinyl compounds are attempts have long been made, such as the available. Kuraray’s EVALTM is a copolymer addition of a small quantity of alkali metal of ethylene and vinyl alcohol. Due to its salt as a promoter. As a result, selectivity has excellent gas barrier properties [Footnote 13], improved from around 60% in the 1930s to it is used for lamination of packing containers over 90% at present. and automotive gasoline tanks. Polyethylene Ethylene oxide is a very reactive gas. It is reacted with chlorine gas, etc. to give may be used as it is for disinfecting medical chlorinated polyethylene. Since chlorinated apparatus. However, it is usually used for polyethylene has the characteristics of both synthesis of industrial organic chemicals and plastic and rubber, it is used as an impact polymers, as shown in Fig. 3.7. modifier for polyvinyl chloride. As The greatest use of ethylene oxide is chlorinated polyethylene is resistant to flame ethylene glycol (EG) from a reaction with owing to the chlorine group, it is also used as water. EG is used as an antifreeze for car a flame retardant for polyethylene and PP. engines. It is also used in large quantities for Ethylene is used for copolymerization the synthesis of polyester (PET resin, with propylene and also for copolymerization polyester fiber and unsaturated polyester resin, of propylene and dicyclopentadiene (DCPD), etc.). During production of EG, EG obtained as shall be described later. is reacted with ethylene oxide to give diethylene glycol, which is then reacted with (2) Ethylene oxide ethylene oxide to give triethylene glycol. The greatest use of ethylene after These byproducts are used for solvents and polyethylene differs by country. Ethylene extractive distillation. When more ethylene oxide, ethylbenzene/styrene and ethylene oxide molecules are polymerized, dichloride/vinyl chloride are almost polyoxyethylene is obtained. comparable with respect to the use of Polyoxyethylene with the structure of ethylene. polymerized EG is also known as polyethylene glycol. Polyoxyethylene is used as a raw material for polyurethane, etc. Since it is nontoxic, it also has prospectice uses in medical devices such as drug delivery systems.

[Footnote 13] Difficulty in passage by gas. Like rubber balloons that deflate on the following day, many polymers tend to let gas pass [Footnote 14] In chemical reactions, an unexpected substance is through when pressurized to a certain extent. Gas barrier property is often obtained as a byproduct in addition to an expected product. important performance in food packaging, because difficulty in The percentage of reaction producing the expected product is called passage by vapor and oxygen is often required. selectivity.

34 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.7 Major product categories from ethylene oxide.

Ethylene oxide is reacted with various polar solvent, recently attacting attention as lower alcohols to form glycol ethers. Esters an electrolyte for lithium ion secondary with acetic acid are also made by using the batteries. It is also used for the manufacture hydroxy groups of glycol ethers. Glycol of polycarbonate in the absence of phosgene. ethers and glycol ether esters are used as Carbon monoxide and hydrogen are oxo solvents for coatings and cleaners. reacted with ethylene oxide to give Since ethylene oxide is reactive to the 1,3-propanediol in one step via hydroxy and carboxy groups, it is reacted β-hydroxypropionaldehyde (see Section 3.4.1 with linear higher alcohols [Footnote 15], (2)). Shell industrialized this process in 1999. higher fatty acids and alkyl phenol to form a It has gained attention as a new series of compounds to which the manufacturing process in contrast with the polyoxyethylene group -(CH2CH2O)n- is previous manufacturing process using added (these products are also known as acrolein (see Section 3.4.3 (8)). ethoxylates). Ethoxylates are used for Furthermore, ethylene oxide is non-ionic surfactants. The polyoxyethylene copolymerized with formaldehyde to give group is hydrophilic, although it does not polyacetal and also with epichlorohydrin to dissociate into ions. On the other hand, give epichlorohydrin rubber. However, because the higher alkyl group is lipophilic, because ethylene oxide is not a main ethoxylates are made to nonionic surfactants. monomer, these polymers are small-scale Ethylene oxide is successively reacted uses of ethylene oxide. with the hydrogen atoms of ammonia to give monoethanolamine, diethanolamine and (3) Ethylbenzene/styrene triethanolamine. As organic intermediates, Ethylene is reacted with benzene to give ethanolamines are used as raw materials of ethylbenzene. For this reaction, various acid pesticides and pharmaceutical products, as catalysts and liquid- and gas phase solvents and pH controllers for synthetic manufacturing processes have been detergents and cosmetics and as carbon developed. At present, the gas phase process dioxide absorbents. using a zeolite catalyst is usually used in Although carbon dioxide is a consideration of corrosiveness of facilities, low-reactivity gas, ethylene oxide is also disposal of waste catalysts, recovery of heat, reacted with carbon dioxide to form ethylene etc. (see Section 6.1.2 (1) 4)). Ethylbenzene is carbonate. Ethylene carbonate is used as a also obtained as one of the C8-fraction

chemicals from cracked gasoline produced by [Footnote 15] In organic chemistry, “higher” means that the number steam cracking of naphtha and also from of carbon atoms is large, being more than 10, while “lower” means that the number of carbon atoms is small, being 1 to several. catalytic reformate of petroleum. However,

Systematic Survey on Petrochemical Technology 35

because of the difficulty in computers. Polystyrene, HIPS, AS resin, ABS separation/purification from xylene, resin, etc. are generally known as styrenic ethylbenzene is mainly synthesized from polymers. ethylene and benzene. Another great use of styrene is synthetic Ethylbenzene is mostly used for the rubber from copolymerization with butadiene. manufacture of styrene. It is a typical organic Styrene-butadiene rubber (SBR) is a typical intermediate. Styrene is mainly manufactured synthetic rubber and is used in large by the dehydrogenation of ethylbenzene. quantities for tires. The Since this reaction is endothermic, like steam styrene-butadiene-styrene block copolymer cracking of naphtha and ethane, it is (SBS) is a typical thermoplastic elastomer. performed at 500–600°C while carbonization Since various styrene-based polymers are is prevented by adding high temperature available as mentioned above, bulk steam to lower the partial pressure. Steam polymerization, solution polymerization, cracking of naphtha and ethane is thermal suspension polymerization and emulsion cracking in the absence of a catalyst, while polymerization are used on a case-by-case dehydrogenation of ethylbenzene uses a basis. Styrene is also used as a crosslinking catalyst. The co-production process of agent for processing/molding unsaturated propylene oxide and styrene is also an polyesters. important route for the supply of styrene (see Section 3.4.3 (4)) (4) Ethylene dichloride and vinyl chloride As shown in Fig. 3.8, styrene is Ethylene dichloride (EDC) is obtained by exclusively used as a raw material for adding chlorine to ethylene. It is then cracked polymers. into vinyl chloride and hydrogen chloride by non-catalytic thermal cracking. The reactants are quenched with cold EDC spray. Hydrogen chloride gas is removed, and vinyl chloride is separated by distillation. This process is very similar to the reactant-quenching process after steam cracking of naphtha. Hydrogen chloride gas is collected and used for ethylene oxychlorination. Ethylene, hydrogen chloride and oxygen or air are reacted by oxychlorination in the presence of a copper Fig. 3.8 Major product categories from chloride catalyst to give EDC and water. styrene. Vinyl chloride is mostly polymerized and used for the production of vinyl polychloride Polystyrene as a homopolymer is a hard, (polyvinyl chloride). Initially, production of transparent polymer. It is made into molded vinyl polychloride by radical polymerization products, sheets and foamed products and was performed by emulsion polymerization used for daily necessaries, electrical using water. However, it was subsequently appliances, containers, food trays, buffers and replaced by suspension polymerization with heat insulators. To improve the poor impact characteristically good product quality. resistance of polystyrene, high impact As shown in Fig. 3.9, not only polyvinyl polystyrene (HIPS) in which rubber is chloride but also many industrial organic modified, acrylonitrile-styrene resin (AS resin chemicals are obtained from EDC or vinyl or styrene acrylonitrile [SAN]) in which chloride. Vinylidene chloride is obtained acrylonitrile is copolymerized, and ABS resin when 1,1,2-trichloroethane obtained by in which butadiene and acrylonitrile is chlorination of vinyl chloride is copolymerized have been developed. ABS dehydrochlorinated using an alkali. resin is not transparent. As colored resin, it is Vinylidene chloride is subjected to radical often used for casings of electrical products polymerization to give vinyliden polychloride. such as television sets and personal Because vinylidene polychloride is excellent

36 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) in gas barrier property and adhesiveness, it is EDC is reacted with aqueous ammonia used as food cling films in daily life. under pressure to give ethylenediamine. EDC and chlorine as a raw material gives Ethylenediamine is used as an organic a mixture of trichloroethylene and intermediate for the manufacture of tetrachloroethylene. The production ratio of pharmaceutical products and rubber tetrachloroethylene to trichloroethylene can chemicals. It is also reacted with be adjusted by changing the charge-in ratio of monochloroacetic acid to give EDC to chlorine. ethylenediamine tetraacetate (EDTA, edetic acid), which is used as a complex-forming agent.

(5) Acetaldehyde and vinyl acetate The production scales of other products from ethylene shown in Fig. 3.5 are far smaller than polyethylene, ethylene oxide, ethylbenzene and EDC. However, a great many products are included in this category. Acetaldehyde as well as vinyl chloride Fig. 3.9 Major product categories from used to be a core industrial organic chemical ethylene dichloride, vinyl chloride. made from acetylene. Acetaldehyde became a petrochemical product in the latter half of the Trichloroethylene is used for solvents and 1950s when the Hoechst-Wacker process was extractive solvents. Tetrachloroethylene, also industrialized (see Section 6.1.2 (2) 1)).. In known as perchloroethylene, is used as a the presence of a similar catalyst, ethylene, solvent for dry cleaning and a degreasing acetic acid and oxygen are reacted to give agent for metal processing. These vinyl acetate. chlorine-based solvents have the advantage of Acetaldehyde was mainly used for the being flame retardant. However, it is also synthesis of acetic acid, butanol (butyl feared that they could have adverse health alcohol) and octyl alcohol. However, in the and environmental effects. 1970s, carbonylation of methanol, mentioned 1,1,1-Trichloroethane as well as previously, was industrialized as a new tetrachloroethylene, manufactured from vinyl method of manufacturing acetic acid and was chloride was used in large quantities as a subsequently widely used worldwide. chlorine-based solvent until the early 1990s. Moreover, the oxo process However, because it was classified as an (hydroformylation) using propylene as a ozone depleting substance and its use was starting material was widely used for regulated by the Montreal Protocol, its manufacture of butanol and octyl alcohol. As production was discontinued in the a result, acetaldehyde lost its main uses and mid-1990s. its production rapidly decreased worldwide In vinyl fluoride, chlorine of vinyl from the 1980s onwards. At present, it is only chloride is replaced by fluorine. Hydrogen used for the manufacture of small-scale fluoride is added to vinyl chloride under products such as pentaerythritol. pressure in the absence of a catalyst to give Showa Denko developed a method of 1-chloro-1-fluoroethane, which is then manufacturing acetic acid by direct oxidation dehydrochlorinated at approximately 500°C of ethylene without going through to give vinyl fluoride. Vinyl fluoride is acetaldehyde and industrialized it in the late exclusively made into vinyl polyfluoride and the 1990s. However, this method has not been used as a coating material. It is an industrial widely enough used to replace carbonylation organic chemical similar to of methanol on a worldwide scale. tetrafluoroethylene obtained from the C1 Vinyl acetate is polymerized to give fraction, although there are clear differences polyvinyl acetate (adhesives, coatings and in raw materials and manufacturing processes fiber-finishing agents). Polyvinyl acetate is between the two chemicals. saponified and used for polyvinyl alcohol

Systematic Survey on Petrochemical Technology 37

(paste, coating agents and raw material of syngas and then reduced with hydrogen, polyvinyl butyral). Vinyl acetate is also used higher alcohols of odd carbon numbers as a comonomer for ethylene and vinyl having one more carbon atom can be chloride. obtained. There is another modification in which (6) Ethanol the disadvantage of oligomerization of Ethanol (also known as ethyl alcohol) is ethylene by trialkylaluminium has been made by adding water to ethylene in the gas improved to obtain the C6 to C14 olefins that phase in the presence of an acid catalyst are in great demand. This method has the (phosphoric acid/silica carrier, etc.). Ethanol disadvantage of an increased number of is widely used as a solvent and is also used as branched chains and internal olefins. The a raw material for ethyl esters such as ethyl SHOP process developed by Shell and acetate. The ethanol market was developed industrialized in 2003 is used for the using the fermentation process before the manufacture of C10 to C14 α-olefins and C11 petrochemical industry was established. to C15 higher alcohols with a terminal Afterwards, the petrochemical industry took hydroxy group. α-Olefins with other lengths over the market completely. Therefore, are reutilized during the reaction. ethanol was the main product of ethylene in the 1950s when the petrochemical industry 3.4.3 Products from the C3 fraction began to develop rapidly. This was because (propylene-based products) acetaldehyde could be produced by oxidizing The C3 basic petrochemical is propylene. ethanol. However, as it became possible to Figure 3.10 shows the main product make acetaldehyde by the Hoechst-Wacker categories made from propylene. For some process without first creating ethanol, the time after petroleum chemistry entered full commercial value of ethanol began to decline. swing in the 1950s, the basic petrochemicals ethylene, butadiene and benzene were in good (7) α-Olefins and linear higher alcohols demand, while production of propylene was C4 to C20 hydrocarbons with the greater than its consumption. This was terminal double bond (at the α-position) are because it was not easy to develop methods known generally as α-olefins. Among them, of synthesizing C3 industrial organic C10 to C14 linear α-olefins are particularly chemicals (acrylonitrile, acrylic acid, glycerin, important as raw materials for surfactants and etc.) from propylene, although these products lubricants and are being produced industrially. had been manufactured in the fields of coal Meanwhile, there has been a growing recent chemistry and oleochemistry since before the demand for C4 to C8 lower α-olefins for the establishment of petrochemistry. However, a manufacture of various L-LDPEs. number of industrial organic chemicals were According to one method of later developed from propylene. Furthermore, manufacturing α-olefins by oligomerization PP was developed and its production of ethylene, trialkylaluminium is reacted with increased rapidly, resulting in an increase in ethylene (Ziegler process). This process has the consumption of propylene. Propylene been modified and is used even now. demonstrates two types of reaction, i.e., However, it has a disadvantage in that the addition reaction to the double bond, as is number of carbon atoms of the resulting observed with ethylene (see Section 6.1.2 (1)), α-olefin varies considerably from 4 to 24. and reaction of the methyl group while Linear trialkylammonium is reacted with leaving the double bond (see Section 6.1.2 oxygen and then hydrolyzed to give higher (2)). Acrylonitrile, acrolein and allyl chloride alcohols. When α-olefins are oxo reacted with are manufactured using the latter reaction.

38 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.10 Major product categories from propylene.

(1) Polypropylene with a solvent to remove low crystalline Unlike ethylene, propylene could not polymer and low molecular weight polymer easily be radically or ionically polymerized to after the reaction. As catalysts have improved obtain an industrial material. It was not until subsequently, slurry polymerization and mass the Ziegler-Natta catalysts were developed in polymerization (polymerization in liquefied 1957 that polypropylene (PP) could be propylene, also known as bulk produced for the first time. Unlike polymerization) have been developed, polyethylene, PP has side-chain methyl making washing and decalcification groups on the main chain of the polymer and unnecessary, resulting in a marked reduction therefore in order to obtain an industrial in equipment and energy costs. The polymer material with good physical technology that has dramatically promoted properties, propylene must be polymerized in the improvement of catalysts was developed such a way that the side chains are arranged by Mitsui Petrochemical Industries (now to face a fixed direction. Even the direction of Mitsui Chemicals). Japan can boast this side chains is regulated in stereospecific polymer synthesizing technoloogy to the polymerization, and polymers thus obtained world (see Section 5.6.3 (1), Section 6.1.3 (1) are called stereoregular polymers. All side 4)). chains are arranged to face a fixed direction Meanwhile, a metallocene catalyst that in isotactic polymerization, while in was found as an epoch-making catalyst for syndiotactic polymerization the side chains polyethylene in the 1980s has also been are arranged to alternately face different applied to the polymerization of propylene. directions. The side chains are not arranged Isotactic PP has been the only stereoregular regularly in atactic polymerization. PP that has been produced in the presence of Since the Ziegler-Natta catalysts are the Ziegler-Natta catalyst. If the metallocen available as fine crystals, polypropylene was catalyst is used, syndiotactic PP can also be initially produced by solution polymerization produced. In 2011, Mitsui Chemicals in which the catalyst was dispersed in a industrialized this process. solvent such as hexane and then propylene As shown in Fig. 3.11, PP is classified as was passed through the solution. As the either homopolymer, in which only propylene activity of the catalyst and the is polymerized, and copolymer, in which stereoregularity of the resulting polymer were propylene is copolymerized with ethylene. both low, it required decalcification with methanol to remove the catalyst and washing

Systematic Survey on Petrochemical Technology 39

Homopolymer [Footnote 16]. EPR is also known as ethylene propylene diene rubber (EPDM) because it is Polypropylene PP composed of ethylene, propylene and a diene Random PP monomer. EPR that can be vulcanized with Copolymer sulfur is used as synthetic rubber. Most of the Block PP conjugated diene-based synthetic rubbers have double bonds in the main chain of the Fig. 3.11 Types of typical polypropylenes. polymer with unsaturated bonds still remaining in the main chain even after it is The copolymer is further classified into partially involved in vulcanization (see random copolymer, in which ethylene is Section 3.4.4 (1)). This is the primary cause irregularly copolymerized with the propylene of the deterioration of rubber on exposure to sequence by adding a small amount of oxygen/ozone and light. In contrast, the ethylene (5% or less), and block copolymer bonds in the main chain of EPR are all (also known as the impact copolymer), in saturated, while unsaturated bonds are all in which the propylene homopolymer portion, the side chains. Since EPR is outstanding in the random copolymer portion of ethylene resistance to weather, heat and chemicals, it is and propylene, and the propylene widely used for automotive parts such as tires homopolymer portion are connected in that and tubes. order. The homopolymer is highly crystalline, hard and strong. It demonstrates higher heat (3) Cumene, acetone and phenol resistance than polyethylene and PP random Like ethylbenzene, cumene is copolymers, and is used for films, sheets, manufactured by the reaction of propylene injection-molded products, fibers, unwoven and benzene. In the same way that styrene is cloth and bands (binding for packaging). produced by the dehydrogenation of Since the crystallinity of the random ethylbenzene, α-methylstyrene can be copolymer is low, its heat-resistance is also produced by the dehydrogenation of cumene. low (although it is still higher than the heat α-Methylstyrene is a small-scale industrial resistance of polyethylene). As it can be made organic chemical that is used in small transparent and is heat-sealable, it is useful quantities as a comonomer for improving the for films and sheets. The film is categorized heat resistance of ABS resin. Since into nonoriented cast polypropylene (CPP) α-methylstyrene is obtained as a byproduct of film and biaxially oriented polypropylene the co-production of phenol and acetone from (OPP) film. The random copolymer is also cumene as mentioned below, this process is used for injection-molded articles, such as actually the main source of supply of this transparent clothes cases and transparent food compound. containers, and blow-molded articles, such as The main use of cumene is the shampoo bottles. The block copolymer is an co-production of acetone and phenol. impact-resistant material characterized by Cumene is oxidized with air to give cumene both the hardness and strength of the hydroperoxide. Treated with sulfuric acid, the homopolymer and the flexibility of the peroxide is cleaved to give phenol and random copolymer. It is used for automobiles acetone. Since one mol each of acetone and (car bumpers) and large home electric phenol are produced simultaneously from 1 appliances, having played the most important mol of cumene, the balance of demand role in expanding the demand for PP since the between acetone and phenol is important. In 1980s. the past, there was a great demand for acetone, while the supply of phenol tended to be (2) Synthetic rubber (EPR) excessive. In that case, acetone could be EPR is a polymer in which ethylene, propylene and an unconjugated diene such as [Footnote 16] Olefines with two double bonds are called dienes. Dienes sandwiching a single bond between two double bonds are dicyclopentadiene or ethylidene norbornene called conjugated dienes, while dienes sandwiching two or more as the third component are copolymerized in single bonds between two double bonds are non-conjugated. Two double bonds react irrespectively of each other in the case of the presence of the Ziegler-Natta catalyst non-conjugated dienes.

40 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) supplied by dehydrogenation or oxidative supply of hydrogen is needed, the process is dehydrogenation of isopropyl alcohol, as more costly than it would be in the event of mentioned below. Conversely, in recent years, an acetone shortage. there has been a great demand for phenol, As benzene-derived phenol is explained while the supply of acetone has tended to be in the “Benzene” section (see Section 3.4.5), excessive. Using a recently industrialized only propylene-derived acetone is described method, acetone is reduced with hydrogen to in this section. Acetone is important not only give isopropyl alcohol, which is then as a solvent but also as an organic dehydrated to propylene and returned into a intermediate, as shown in Fig. 3.12. raw material of cumene. However, because a

Fig. 3.12 Major product categories from acetone.

At present, the greatest synthetic use of high boiling point solvent but also as an acetone is BPA obtained by reaction with organic intermediate. Isophorone phenol. This substance is also described in diisocyanate is an important organic chemical the “Benzene” section. The next most induced from isophorone. As aliphatic important use is methyl methacrylate (MMA) diisocyanate, it is used for the production of that is synthesized via reaction with hydrogen polyurethane. cyanide. Although for a long time this reaction was the main process of (4) Propylene oxide manufacturing MMA, it has rapidly Figure 3.13 shows the products from decreased in importance recently. One of the propylene oxide. Compared with Fig. 3.7 reasons is that the supply of cheap hydrogen showing the product categories from ethylene cyanide as a byproduct of acrylonitrile has oxide, the product line-up from propylene markedly decreased. Another reason is that oxide is very poor, comprising only methods of manufacturing MMA by using C4 propylene glycol, polypropylene glycol and isobutylene and tert-butyl alcohol as starting propylene glycol ether, corresponding to EG, materials have been developed and widely polyethylene glycol and glycol ether. used. C6 methylisobutyl ketone is obtained by aldol condensation of 2 molecules of acetone followed by several steps of reaction. This compound is used as a solvent. Isophorone is obtained by aldol condensation of 3 acetone molecules. Isophorone is used not only as a

Systematic Survey on Petrochemical Technology 41

Fig. 3.13 Major product categories from the oxidation of propylene with a peroxide to propylene oxide. give propylene oxide. If the product obtained after the reaction of the peroxide is useful, the Propylene oxide is entirely used for process can be industrialized as a method of polypropylene glycol as a raw material for manufacturing the product and propylene polyurethane. Polypropylene glycol, in which oxide simultaneously. However, it is difficult polyhydric alcohol is polymerized with to manage co-production, because it is propylene oxide, is called polyether polyol. It influenced by the supply-demand balances is used as a raw material for thermosetting and markets for the two products. Table 3.2 polyurethane. shows the main industrialized peroxides Propylene glycol is used for polyether together with their raw materials and polyol and unsaturated polyesters. However, products. it is just one of the polyhydric alcohols such Of these methods of manufacturing as EG, glycerin and pentaerythritol. Its propylene oxide, process (1) was convenient product scale is much smaller than EG. while MTBE required large quantities of Various propylene glycol ethers made tert-butyl alcohol. However, after the use of from propylene oxide and lower alcohols are MTBE for gasoline was prohibited, there was solvents that compete with various glycol no demand for tert-butyl alcohol. Process (2) ethers (cellosolves) made from ethylene oxide has become a promising route to supply and lower alcohols. However, they are not as styrene. According to process (3), because large-scale. cumene and then cumene hydroperoxide can In the structure of propylene oxide as be produced from cumyl alcohol, the product well as ethylene oxide, oxygen is directly from the peroxide is returned to the original added to the double bond. The direct addition raw material. Thus the disadvantages of of oxygen to ethylene was achieved in the co-production can be avoided. Since 1930s, while the direct addition of oxygen to hydrogen peroxide has recently been propylene has not yet been achieved. The produced on a large scale and supplied chlorohydrin process as a very old method of cheaply, process (4) using hydrogen peroxide synthesizing ethylene oxide is still used as a peroxide has been industrialized. As only commonly for the production of propylene propylene oxide and water are produced in oxide. As this process is very wasteful, many this process, the problems of co-production other manufacturing methods have been can be completely solved. investigated. A method that has been industrialized is

42 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Table 3.2 Typical propylene oxide production process by peroxide

(5) Isopropyl alcohol solvents, but n-butanol with higher solubility In the same way that ethanol is produced is more popular as a solvent in coatings. In by adding water to ethylene, isopropyl this way, n-butyraldehyde has a greater alcohol (IPA) is produced by adding water to demand than isobutyraldehyde propylene. Isopropyl alcohol is used as a (7) Acrylonitrile cheap alternative solvent to ethanol. It used to Propylene is reacted with ammonia and be an important raw material of acetone. oxygen to give acrylonitrile. This reaction, However, as mentioned above, a significant known as ammoxidation, is one of the amount of demand for it was lost due to the epoch-making reactions in the technological fact that acetone became excessive in the history of petrochemistry. This reaction is co-production of acetone and phenol. also called the “Sohio process” after the company that invented it. It is significant in (6) n-Butyraldehyde and isobutyraldehyde that it is not the double bond but the methyl n-Butyraldehyde and isobutyraldehyde group of propylene is reactive. This reaction having one more carbon atom are produced was discovered in the latter half of the 1950s. by the oxo process of propylene (see Section In the 1960s, it replaced many existing 3.4.1 (2)). Figure 3.14 shows the main methods of manufacturing acrylonitrile, such products from n-butyraldehyde and as the hydrogen cyanide process to give isobutyraldehyde. acetylene. Initially, because the the reaction n-Butyraldehyde is condensed with aldol had low selectivity, large quantities of in the presence of an alkali catalyst, hydrogen cyanide and acetonitrile were dehydrated, and reduced with hydrogen to produced as byproducts. Hydrogen cyanide give 2-ethylhexanol (an octanol). was used for many purposes such as methyl 2-Ethylhexanol is reacted with phthalic methacrylate. Initially, the use of acetonitrile anhydride to give dioctyl phthalate (DOP). It was limited, but the demand for this is also reacted with adipic acid or phosphoric compound as polar and extracting solvents acid to give esters with a 2-ethylhexyl group. subsequently gradually expanded. However, These esters from 2-ethylhexanol are used in due to progressive improvements in catalysts large quantities as plasticizers for polyvinyl in recent years, the production of these chloride. n-Butyraldehyde is reduced with byproducts has decreased. Alternative hydrogen to give n-butanol. Acrylic acid methods are available for manufacture of esters of n-butanol and 2-ethylhexanol are hydrogen cyanide, but some measures must used as raw materials for coatings. be taken for acetonitrile, as it has long been Meanwhile, isobutyraldehyde is reduced with manufactured only as a byproduct of hydrogen to give isobutyl alcohol. Both acrylonitrile. n-butanol and isobutyl alcohol are used as

Systematic Survey on Petrochemical Technology 43

Fig. 3.14 Major product categories from butyraldehyde, isobutyraldehyde.

As shown in Fig. 3.15, acrylonitrile is manufacture of AS resin, ABS resin and used for many purposes. synthetic rubber (NBR). Acrylonitrile is dimerized by electrolysis to give C6 adiponitrile, which is then reduced with hydrogen to give hexamethylenediamine. This process is one of the methods of manufacturing hexamethylenediamine as a raw material for 6,6-nylon. The nitrile group of acrylonitrile is hydrolyzed to give acrylamide. A copper catalyst has been used for hydrolysis. However, in 1985, Nitto Kagaku Kogyo (now Mitsubishi Rayon) industrialized a biological Fig. 3.15 Major product categories from method using acrylamide-producing acrylonitrile. organisms. Subsequently, biological methods

Acrylonitrile is polymerized to give using enzymes characterized by high heat polyacrylonitrile (PAN). PAN is used for resistance and good productivity have been acrylic fiber. As a plastic with an excellent developed. These are unique petrochemical gas barrier property, it is also used for techniques created in Japan. Acrylamide is packaging containers. PAN-based carbon polymerized to give polyacrylamide. fiber made by carbonizing acrylic filament is Polyacrylamide is used as a flocculant for very strong. Toray and other Japanese wastewater treatment, as a mud-solidifying companies have used it for manufacturing stabilizer for drilling oil wells, and in the fishing poles, golf shafts, tennis rackets, etc. paper industry as a yield-improving agent, a since the 1970s. Since carbon fiber is light, it filtering agent and a paper-strengthening has been used for aircraft parts since the late agent. Since polyacrylamide as a 1980s. It has also been used in the main water-soluble polymer increases the viscosity wings and bodies of aircrafts, attracting of water, it is also used as a thickener for attention since the late 2000s. Since it is also enhanced oil recovery (EOR) [Footnote 17]. expected to be used for automotive parts and Compounds with reactive hydrogen such bodies, the demand for carbon fiber could as amine, alcohol and aldehyde are added to expand dramatically in the future. As a comonomer, acrylonitrile is used for [Footnote 17] A method of increasing the production of crude oil by injecting water and gas into oil wells that are running dry.

44 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) the double bond of acrylonitrile to cause as a builder for synthetic detergents. However, cyanoethylation. Amine is obtained by the in Japan, zeolite is used exclusively as a reduction of cyanoethyl compounds with builder, while polyacrylic acid is rarely used hydrogen, while carboxylic acid is obtained for this purpose. When acrylic acid and by the hydrolysis of these compounds. These acrylic acid sodium are copolymerized in the processes are important reactions for presence of a polyhydric alcohol ester of producing cationic surfactants and acrylic acid as a crosslinking agent, amphoteric surfactants. As mentioned above, superabsorbent resin is obtained. While acrylonitrile is used not only as a monomer starch-based superabsorbent resins, etc. are but also as an organic intermediate. also available, acrylic acid-based is the most widely used. Copolymers of acrylic acid (8) Acrolein, acrylic acid and acrylic acid esters with metacrylic acid esters, vinyl esters acetate, etc. are used as acrylic coatings. A There have been several methods used for great variety of coatings such as aqueous, manufacturing acrylic acid. However, at thermoplastic and ultraviolet curable coatings present, acrylic acid is mainly produced by can be made by using various ester groups. oxidizing the methyl group of propylene and Figure 3.16 shows the uses of acrolein. then oxidizing the resulting acrolein (see The greatest use is acrylic acid. However, Section 6.1.2 (2) 4)). This process was because acrolein is a very reactive aldehyde, developed by Nippon Shokubai and it is also used as an organic intermediate for Mitsubishi Chemical. Acrylic acid is reacted methionine as an essential amino acid (amino with various alcohols to give acrylic acid acid pharmaceuticals and feed additives), esters. glutaraldehyde (sterilizing disinfectants, Acrylic acid undergoes radical leather tanning agents and fiber treating polymerization to give polyacrylic acid as a agents) and 1,3-propanediol. water-soluble polymer. As polyacrylic acid catches calcium ions, etc. in water, it is used

Fig. 3.16 Major product categories from acrolein.

(9) Allyl chloride and epichlorohydrin water (hypochlorous acid) is allowed to act When propylene is reacted with chlorine on allyl chloride and is then at 500°C, allyl chloride is produced by highly dehydrochlorinated with an alkali. This selective chlorination of the methyl group manufacturing process is the same as for rather than an addition reaction to the double propylene oxide. Since epichlorohydrin has bond. A major use of allyl chloride is the two functional groups, i.e., epoxy and manufacture of epichlorohydrin. chlorine groups, it is used as a monomer for Epichlorohydrin is obtained when chlorine the production of epoxy resin. Epoxy resin is used for adhesives and semiconductor sealing

Systematic Survey on Petrochemical Technology 45

materials. There has also been a growing recent demand for epoxy resin as a matrix (1) Polymers from butadiene resin (impregnation resin) for carbon fiber. Synthetic rubber called diene-based Glycerin can be synthesized from either rubber is produced by the polymerization and allyl chloride or epichlorohydrin, and these copolymerization of butadiene. processes were industrialized. However, Styrene-butadiene rubber (SBR) obtained by synthesis of glycerin declined from the 2000s, the copolymerization of butadiene and because biodiesel oil began to be produced in styrene and butadiene rubber (BR) obtained large quantities from fats and oils such as by polymerization of butadiene alone are palm oil, resulting in the production of high termed as general purpose rubber. The amounts of glycerin as a byproduct. consumption of general purpose rubber is high, being comparable to that of natural 3.4.4 Products from the C4 and C5 rubber and isoprene rubber (IR), mentioned fractions below. Both SBR and BR are used in large C4 olefins produced by steam cracking of quantities for tires and are also widely used naphtha include butadiene and four kinds of for rubber shoes, industrial parts, butylene, which are separated and purified as rubber-coated cloth, paper coatings, etc. BR necessary. Of these, butadiene is the most is used for golf ball cores and high impact important. Figure 3.17 shows the main polystyrene (HIPS). product categories from butadiene.

Fig. 3.17 Major product categories from butadiene.

Nitrile rubber (NBR) is formed by the The reaction used for the manufacture of copolymerization of butadiene and synthetic rubber from conjugated diene is 1,4 acrylonitrile. Hydrogenated nitrile rubber polymerization [Footnote 18], which makes (HNBR), in which the double bond of NBR is use of the characteristics of conjugated hydrogenated almost completely, is improved double bonds. As a result of this reaction, the with respect to weather resistance. Both NBR double bonds at positions 1 and 3 of and HNBR are special rubbers that have outstanding oil resistance. These are used for [Footnote 18] When the double bond of conjugated diene oil-resistant hoses, tank lining and packing. (CH2=CH-CHR=CH2) is polymerized alone by addition reaction to Chloroprene is obtained by reaction with make the polymerization chain -CH2-CH (CHR=CH2)-, the reaction is called 1,2 polymerization, while when the two double bonds are chlorine and butadiene. Chloroprene is allowed to act concertedly to make the polymerization chain polymerized to give chloroprene rubber (CR). -CH2-CH=CHR-CH2-, the reaction is called 1,4 polymerization. The double bond is left on the side chain in 1,2 polymerization, while it CR is used for belts, hoses, adhesives, wire is left on the main chain in 1,4 polymerization. The binding direction coating, etc. of the main chain around the double bond (cis or trans) may be in disorder or regulated.

46 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) conjugated diene move to position 2 and undergoes ring-opening polymerization to remain there. In the vulcanization of rubber, give polytetramethylene glycol (PTMG). this double bond is partially reacted with PTMG is copolymerized with MDI to give sulfur to make the rubber elastic. For polyurethane elastic fiber. polymerization and copolymerization from When hydrogen cyanide is added in 2 conjugated diene, radical polymerization and steps to the double bond of butadiene, ionic polymerization are used depending on adiponitrile that is a C6 industrial organic the expected product. Radical polymerization chemical is obtained (see Section 3.4.1 (5)). is further classified into radical Sulfolene is obtained by 1,4-addition of polymerization, using an ordinary sulfur dioxide to butadiene, while sulfolane is polymerization initiator, and redox obtained by the hydrogenation of sulfolene. polymerization, in the presence of a redox Sulfolane is used as a solvent for extractive system at low temperature. In ionic distillation and gas purification. polymerization, alkali metals, organic metals, the Ziegler-Natta catalyst, etc. are used on a (3) Industrial organic chemicals and case-by-case basis. Polymerization is polymers from isobutylene performed as emulsion polymerization or Isobutylene is the next most important C4 solution polymerization depending on the basic chemical to butadiene. Figure 3.18 type of rubber. Polymerized products are also shows the product categories made from classified as solid products that are isobutylene. coagulated so as to be used as raw materials Isobutylene is readily reacted with water for rubber-molded products, and latex, which to give tert-butyl alcohol in the presence of an is left emulsified. acid catalyst. As mentioned above, this Thermoplastic elastomers SBS reaction is also used for separating (styrene-butadiene-styrene block copolymer) isobutylene (see Section 3.3.3 (2)). tert-Butyl are obtained by the block copolymerization of alcohol is dehydrated to give isobutylene. butadiene and styrene. SBS is a block Methyl methacrylate (MMA) is made copolymer that is composed of a polystyrene from isobutylene or tert-butyl alcohol as a portion as a hard segment and a BR portion as starting material. This process is similar to a soft segment. ABS resin is obtained by the the reaction for producing acrolein and then copolymerization of butadiene, styrene and acrylic acid by oxidizing the side-chain acrylonitrile. methyl group while retaining the double bond of propylene. (2) Industrial organic chemicals from Isobutylene is copolymerized with small butadiene quantities of isoprene to give butyl rubber Butadiene that is used as a raw material (isobutylene isoprene rubber [IIR]). Butyl of polymers is also used for the manufacture rubber has specific physical properties, of industrial organic chemicals. because most of the bonds in the main chain 1,4-Diacetoxy-2-butene is obtained by are saturated. It is outstanding in aging 1,4-addition of acetic acid to butadiene. resistance and ozone resistance and is 1,4-Diacetoxy-2-butene is reduced with characterized by very low gas permeability. hydrogen and then hydrolyzed to give Due to these merits, it is used for tire tubes, 1,4-butanediol and acetic acid. The acetic inliners for tires, roofing, etc. acid is reutilized. 1,4-Butanediol is Isobutylene is directly reacted with copolymerized with terephthalic acid to give methanol to give methyl tert-butyl ether polybutylene terephthalate (PBT), a general (MTBE). MTBE was used as gasoline purpose engineering plastic. Tetrahydrofuran additives, but its use was later prohibited. (THF) is produced from 1,4-butanediol by This course of events is outlined in Section dehydration. THF is used as a solvent and 5.5.2 (3) 3).

Systematic Survey on Petrochemical Technology 47

Fig. 3.18 Major product categories from butylenes.

(4) Industrial organic chemicals and purified are reacted with isobutane in the polymers from n-butylene presence of a fluoric acid catalyst to give C8 Figure 3.18 shows the industrial organic branched paraffins. Petroleum waste gas chemicals and polymers made from containing propylene and butylene is n-butylene (normal butylene) (a mixture of sometimes used as it is for reaction with 1-butylene, cis-2-butylene and isobutane to give C7 to C8 branched paraffins. trans-2-butylene). n-Butylene was often used These branched paraffins, also called without separation for the production of alkylates, are gasoline-based materials (see industrial organic chemicals. However, the Section 2.1.2 (5)). importance of 1-butylene has increased rapidly since the use of L-LDPE spread (5) Main industrial organic chemicals and worldwide in the 1980s, and it has since been polymers from the C5 fraction separated and purified. Figure 3.19 shows the product categories n-Butylene is oxidized with air to give produced from the C5 fraction. Important maleic anhydride. However, since the method basic petrochemicals that are separated and of manufacturing maleic anhydride by purified from the C5 fraction include oxidation with n-butane was developed, cyclopentadiene and isoprene (see Section production of maleic anhydride via 3.3.3 (2)). The methods of separating these n-butylene has decreased in significance. chemicals have already been mentioned. The When water is added to n-butylene as a resulting residue after separating these mixture in the presence of an acid catalyst, substances and the C5 fraction is polymerized sec-butyl alcohol is obtained. sec-Butyl to give petroleum resin, a cheap polymer that alcohol is oxidized to give methyl ethyl is used for coatings for white street markings ketone (MEK), which is widely used as a and adhesives. solvent. Butylenes that are not separated or

48 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.19 Major product categories from products with C5.

Dicycylopentadiene is the important third made from oligomers of isoprene. component for producing EPR by copolymerization with ethylene and 3.4.5 Products from the C6 fraction propylene (see Section 3.4.3 (2)). When The main C6 basic petrochemical is not heated, dicyclopentadiene is cracked to give an olefin but benzene, an aromatic cyclopentadiene. Cyclopentadiene or hydrocarbon. Figure 3.20 shows the main dicyclopentadiene undergoes ring-opening industrial organic chemicals and polymers metathesis polymerization or made from benzene. In the same way that an copolymerization with ethylene followed by addition reaction is the core reaction in reduction to give various kinds of COP olefins, a substitution reaction plays the most (cycloolefin polymers) and copolymers. COP important role in benzene reactions. In Fig. is used as an optical material, because it is 3.20, all the reactions of benzene except noncrystalline, very transparent, and not hydrogenation to give cyclohexane are hygroscopic. substitution reactions. A significant use of isoprene is the manufacture of synthetic rubber (isoprene (1) Ethylbenzene, cumene and linear rubber, IR). Isoprene undergoes alkylbenzene stereospecific polymerization in the presence The formation of ethylbenzene by the of a Ziegler-Natta catalyst to give reaction with ethylene and benzene and the cis-1,4-polyisoprene. The structure of this formation of styrene by dehydrogenation polymer is the same as that of natural rubber. have already been mentioned in the “Ethylene” Isoprene is added in small quantities for section (see Section 3.4.2 (3)). copolymerization with isobutylene to give The formation of cumene by the reaction synthetic rubber (isobutylene isoprene rubber, with propylene and benzene and the IIR). Due to the addition of isoprene, IIR is a formation of phenol and acetone by oxidizing sulfur-vulcanizable rubber. A block cumene to a peroxide and then cleaving it copolymer with a with an acid have already been mentioned in polystyrene-polyisoprene-polystyrene the “Propylene” section (see Section 3.4.3 structure like SBS is obtained. It is a (3)) Since phenol is an important industrial thermoplastic elastomer called organic chemical, it is described in another styrene-isoprene-styrene block copolymer section. (SIS). In addition, many synthetic perfumes Linear alkylbenzene is also made from are produced by the dimerization of isoprene α-olefin and benzene. The hydrogen in the followed by oxidation. Raw materials for aromatic ring of linear alkylbenzene is cosmetics such as squalane, pharmaceutical replaced by a sulfonic acid group using products and intermediates for pesticides are sulfuric acid anhydride to give linear

Systematic Survey on Petrochemical Technology 49

alkylbenzene sulfonate. Linear alkylbenzene and epoxy resin, respectively. Polycarbonate sulfonate is an important anionic surfactant, is a polymer with superior transparency, which is used in large quantities for synthetic impact resistance and flame resistance. It is detergents. widely used in consumer electrical appliances, automobiles, building materials, etc. A (2) Phenol common example is its in the transparent As shown in Fig. 3.21, many industrial substrates of CDs and DVDs. The production organic chemicals and polymers are made of polycarbonate has increased since the from phenol. 1990s and it has grown into a large-scale Phenol undergoes addition condensation product. Epoxy resin has already been with formaldehyde to give phenol resin (see mentioned in the “Epichlorohydrin” section Section 6.1.3 (2)). (see Section 3.4.3 (9)). Other small-scale Bisphenol A is obtained from acetone and polymers such as polysulfone and phenol by reaction similar to the reaction of polyetherimide are obtained from bisphenol formaldehyde and phenol. As bisphenol A is A. Polysulfone is often used for filters in an industrial organic chemical with 2 hydroxy artificial kidneys. Polyetherimide is a super groups (-OH) of phenol, it is widely used as a engineering plastic in which improves the monomer. It is polymerized with phosgene molding processability of polyimide. and epichlorohydrin to give polycarbonate

Fig. 3.20 Major product categories from benzene.

50 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 3.21 Major product categories from phenol.

Similar to the reaction between benzene The method of manufacturing caprolactam by and ethylene or propylene mentioned in the hydrogenation of benzene is described later in preceding section, alkylphenol is obtained by the “Cyclohexane” section. a reaction between α-olefin and phenol. Ethylene oxide is reacted with the hydroxy (3) Nitrobenzene and aniline group of alkylphenol to give polyoxyethylene Benzene is treated with a mixture of alkylphenyl ether. It is used as a nonionic concentrated nitric acid and concentrated surfactant. sulfuric acid to give nitrobenzene (Fig. 3.20). The hydrogen atoms at positions 2 and 6 Nitrobenzene is reduced with hydrogen to of phenol are replaced by methyl groups give aniline. Aniline is an important organic using methanol to give 2,6-xyrenol. When intermediate for synthetic dyes, and is also 2,6-xyrenol undergoes oxidative used in large quantities as a raw material for polymerization (oxidative coupling) in the MDI (4,4’-diphenylmethane diisocyanate) in presence of a copper catalyst, only the para the petrochemical industry. Aniline is reacted position (position 4) of phenol reacts, giving with formaldehyde in the presence of an polyphenylene ether in which aromatic rings alkali to give 4,4’-diaminodiphenyl methane. and oxygen are connected linearly. The This reaction is similar to the reaction to processability of polyphenylene ether is poor. obtain bisphenol A from phenol and acetone, However, because it mixes well with mentioned previously. Hydrogen at the para polystyrene to give a marked improvement in position of the aromatic ring is replaced by a processability, it is usually used as a mixture methylene group derived from aldehyde, and with such a polymer (called a polymer alloy). aniline is connected. When Polyphenylene ether is also known as 4,4’-diaminodiphenyl methane is reacted with modified polyphenylene ether (PPE). phosgene, the amino group changes to an Phenol is reacted with chlorine to replace isocyanate group to give MDI. MDI is some of the hydrogen atoms in the aromatic reacted with polyether polyol to give ring with chlorine groups to give polyurethane. chlorophenol. Chlorophenol is used as an intermediate for pesticides. (4) Chlorobenzene The method of manufacturing Benzene is reacted with chlorine to give caprolactam by hydrogenation of phenol via chlorobenzene, in which some of the cyclohexanone is an old process. However, it hydrogen atoms in the aromatic ring are is often used even now and is an important replaced by chlorine (Fig. 3.20). use of phenol in the United States and Europe. Monochlorobenzene is reacted with

Systematic Survey on Petrochemical Technology 51

trichloroacetaldehyde to produce an insecticide (1) Industrial organic chemicals from (didchlorodiphenyl-trichloroethane [DDT]). toluene DDT used to be a significant chemical in As a solvent, toluene is often used for terms of public health and agriculture, coatings, adhesives, etc. TDI, shown in Fig. although its production is now prohibited. 3.22, is one of the main industrial organic Monochlorobenzene is mainly used as a chemicals obtained from toluene. In the same solvent, for instance, in the reaction of way that aniline is made from benzene, 4,4’-diaminodiphenyl methane and phosgene, toluene is initially nitrated with concentrated mentioned in the preceding section. nitric acid and concentrated sulfuric acid to Paradichlorobenzene is used for give dinitrotoluene. This process is a insecticides and deodorants. It is polymerized substitution reaction in which the hydrogen in with sodium sulfide to give polyphenylene the aromatic ring is substituted by nitro sulfide (PPS). Due to its outstanding heat groups. The dinitrotoluene is then reduced resistance and mechanical strength, PPS is with hydrogen to give diaminotoluene, which used as an engineering plastic. is then reacted with phosgene to give TDI. TDI, as well as MDI, is a diisocyanate (5) Cyclohexane, adipic acid and that is produced in large quantities. TDI is caprolactam reacted with polyether polyol to give The reaction in which the aromatic ring polyurethane. Polyurethane is mainly used in of benzene is destroyed by hydrogenation to the manufacture of flexible polyurethane give cyclohexane is very unique, because foam and is also used for polyurethane benzene usually undergoes substitution coatings, polyurethane adhesives and reactions. Cyclohexane is also contained in polyurethane rubber. catalytic reformates and cracked gasoline. However, apart from TDI, there are no However, due to the difficulty in separation large-scale industrial organic chemicals and purification, it is exclusively produced by produced from toluene. Consequently, , the the hydrogenation of benzene. It is used as a demand for toluene in the petrochemical solvent, and also oxidized to give industry is small in proportion to the amount cyclohexanone and cyclohexanol, and of toluene produced alongside benzene and subsequently adipic acid and caprolactam xylene when extracting aromatic (see Section 6.1.2 (4)). Adipic acid is reacted hydrocarbons from cracked gasoline and with hexamethylenediamine by condensation catalytic reformates, resulting in excessive polymerization to give 6,6-nylon. amounts of toluene being produced. At Caprolactam undergoes ring-opening petrochemical plants, this excessive toluene is polymerization to give 6-nylon. Nylon made into benzene and xylene by a (polyamide) is used for synthetic fibers and disproportionation reaction. engineering plastics. (2) Industrial organic chemicals from xylene 3.4.6 Products from the C7 and C8 Xylene has three types of isomer (ortho, fractions metha and para). The main industrial organic Like main C6 basic petrochemicals, main chemical produced from xylene is carboxylic C7 and C8 basic petrochemicals are not acid obtained by the oxidation of both methyl olefins, but rather aromatic hydrocarbons, groups (see Section 6.1.2 (3) 1)). This namely toluene and xylene. Ethylbenzene, a reaction is not a substitution reaction, as is C8 aromatic hydrocarbon, is also obtained characteristic of aromatic hydrocarbons, but from cracked gasoline. However, because it is is similar to the reaction in which the methyl usually synthesized from ethylene and group of propylene is oxidized to give acrylic benzene, it has already been described as an acid. However, because the mechanism of ethylene product. Figure 3.22 shows the main reaction is quite different, these reactions are product categories made from toluene and only similar in style. xylene.

52 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Phthalic anhydride is made from o-xylene It is also reacted with polyhydric alcohol and by oxidation. Phthalic anhydride is reacted maleic anhydride by condensation with 2-ethylhexanol to give a plasticizer polymerization to give unsaturated polyester (DOP). The plasticizer is used together with resin. As a glass fiber-reinforced plastic, polyvinyl chloride to produce flexible unsaturated polyester resin is used for the polyvinyl chloride products (films, hoses, manufacture of large molded articles such as leather, wire coating, etc.). Phthalic anhydride fishing boats, tanks and bathtubs. It has also is also reacted with various alcohols such as long been used as a raw material for alkyd isodecyl alcohol and used as a raw material resin. for various phthalate ester-based plasticizers.

Fig. 3.22 Major product categories from toluene, xylene.

m-Xylene is oxidized to give isophthalic is also reacted with 1,4-butanediol by acid. Isophthalic acid is used for unsaturated condensation polymerization to give PBT. polyester resin. However, unlike phthalic PBT is widely used as an engineering plastic. anhydride, it is not used as a main monomer, Terephthalic acid is changed to acid chloride only for reforming. When isophthalic acid and is then reacted with changes into a highly reactive acid chloride, paraphenylenediamine by condensation then reacted with m-phenylenediamine by polymerization to give para-aramid. As a very condensation polymerization, it gives strong fiber, para-aramid is used for tire cords, meta-aramid (wholly aromatic polyamide). bulletproof vests, safety globes, etc. As Since meta-aramid has outstanding heat mentioned above, terephthalic acid is a resistance and flame resistance, it is used for large-scale industrial organic chemical having space suits, firefighting uniforms, curtains, a much greater demand than not only etc., albeit in small quantities. isophthalic acid but also phthalic anhydride. p-Xylene is oxidized to give terephthalic Compared with o-xylene and p-xylene, acid. Terephthalic acid is reacted with EG by m-xylene has a much smaller demand. condensation polymerization to give PET. Meanwhile, the isomer ratio of xylene Polyester fiber has dominated nylon and obtained from catalytic reformates and acrylic fibers and is currently considered to cracked gasoline is almost constant. be the most important synthetic fiber. In the Therefore, surplus m-xylene has been form of PET resin, terephthalic acid is used in isomerized in the presence of an acid catalyst large quantities for bottles, films, tapes, etc. It to give a mixture of o-, m- and p-xylene and

Systematic Survey on Petrochemical Technology 53

then o- and p-xylene have been separated and of linear n-paraffin from kerosene as a purified (see Section 6.1.1 (6)). petroleum fraction having more carbon atoms than naphtha (Fig. 3.23 [1]). n-Olefin is 3.4.7 Products from the ten or more obtained by the thermal cracking of fractions n-paraffin. The molecule of n-olefin is a Industrial organic chemicals from the ten straight carbon chain with a double bond at or more carbon atoms include many the end or inside. The second route is the important surfactants. The greatest use of production of α-olefin from ethylene as a surfactants is synthetic detergents. To prevent starting material (Fig. 3.23 [2]), as mentioned environmental contamination with foam, in Section 3.4.2 (7). In the third route, fats synthetic detergents must be promptly and oils are used as raw materials rather than degraded by microorganisms after discharge petroleum or natural gas (Fig. 3.23 [3]). For into the environment. To achieve this, the this reason, this route is considered to conflict carbon chains must be straight. However, with the definition of petrochemistry. basic petrochemical products with more than Nevertheless, petrochemical techniques can C10 that can be used as raw materials of be applied to the manufacture for surfactants ssurfactants cannot be produced by steam from the raw materials of fats and oils. Fats cracking of naphtha. As shown in Fig. 3.23, and oils are higher fatty acid triglycerides. there are three starting materials. Triglycerides composing fats and oils are One of the three routes is the extraction mostly C12 to C18 linear carboxylic acids.

Fig. 3.23 System of product from C10.

(1) Industrial organic chemicals from When α-olefin is sulfonated by reaction olefins with ten or more carbon atoms with sulfuric acid anhydride and then Linear alkylbenzene is obtained by a hydrolyzed, the double bond shifts internally reaction between the n-olefins (including during the reaction. This results in α-olefin α-olefin) shown in Fig. 3.23 [1], [2] and sulfonic acid being obtained, although the benzene. Sulfonic acid is then introduced into position of the double bond is different in this the aromatic ring using sulfuric acid mixture. It is neutralized with an alkali to anhydride and neutralized with an alkali to give α-olefin sulfonate. This is used as an give linear alkylbenzene sulfonate. Linear anionic surfactant (α-Olefin sulfonate [AOS]) alkylbenzene sulfonate is a linear anionic with outstanding biodegradability. surfactant (linear alkylbenzene sulfonate After the oligomerization of ethylene, [LAS]) with outstanding cleaning properties. linear higher alcohols are obtained by It is used in large quantities for detergents. oxidation and hydrolysis. Linear higher

54 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) alcohols having one more carbon atom than subjected to ester exchange with methanol to the original olefin can also be obtained by the give a higher fatty acid methyl ester, which is oxo process of α-olefin. The uses of linear then hydrocracked. Higher alcohol is higher alcohols are described in the next esterified with chlorosulfuric acid or section. anhydrous sulfuric acid and then neutralized with an alkali to give a higher alcohol sulfuric (2) Industrial organic chemicals from fats acid ester salt. This is an anionic surfactant and oils (alkyl sulfuric acid ester salt [AS]) used as a Higher fatty acid (C12–C18) obtained by neutral detergent with stable quality. Higher the high-pressure hydrolysis of fats and oils alcohol is polymerized with ethylene oxide to (Fig. 3.23 [3]) is neutralized with an alkali to give polyoxyethylene alkyl ether. This is a give soap and metallic soap. Soap that is a nonionic surfactant (AE). It is further sodium salt of higher fatty acids has long changed into a sulfate ester salt to give been produced as a detergent and also as an polyoxyethylene alkyl ether sulfate. This is an anionic surfactant. Calcium salt, magnesium anionic surfactant polyoxyethylene alkyl salt, barium salt, zinc salt, etc. of higher fatty sulfate (AES). Higher alcohol is reacted with acids are termed as metallic soap. Metallic dimethylamine to give tertiary aliphatic soap is used for plastic stabilizers and amine. lubricants/mold release agents. Higher fatty acids react with ethylene Bibliography oxide to give a polyethylene glycol fatty acid [1] “An outline of the development of poly ester that is used for nonionic surfactants. vinyl chloride technology in Japan, Higher fatty acids also react with ammonium including a description of historical to give amide, which is then dehydrated to materials,” Survey Report on the give fatty acid nitrile. Fatty acid nitrile is Systematization of Technologies, no. 1, reduced to give primary to tertiary fatty National Museum of Nature and amine, which is then reacted with methyl Science, March 2001. chloride to give a quaternary fatty acid [2] “Systematic survey of technological ammonium salt. This substance is used as a development in laundry soaps and cationic surfactant. Acrylonitrile is added to detergents,” Survey report on the primary fatty acid amine (cyanoethylation) systematization of technologies, no. 9, and then the nitrile group is hydrolyzed and National Museum of Nature and neutralized to give an alkylamino fatty acid Science, March 2007. salt. Since this substance has both amino and [3] K. Weissermel, H. J. Arpe, “Industrial carboxy groups within the molecule and also organic chemistry,” Tokyo has a long-chain alkyl group, it is used as an Kagaku-dojin Publishing Company, amphoteric surfactant. Inc., 5th edition, 2004. Higher fatty acid of fats and oils are also [4] H. A. Wittcoff, B. G. Reuben, J. S. reduced by high-pressure hydrogene to give Plotkin, “Industrial organic chemicals,” fatty alcohol (linear higher alcohol). In fact, Wiley, 3rd edition, New York, 2013. to accelerate the reaction, fats and oils are

Systematic Survey on Petrochemical Technology 55

4 Industrial organic chemicals and polymers predating petrochemistry

Even before the establishment of the forests that thrived more than the forest of petrochemical industry, there had been petrochemistry. However, that forest grew fully-fledged industrial organic chemical rapidly within a short space of time in the industries and polymer industries based on 1950s and the 1960s, in the United States, in wood, carbohydrates (fermentation), fats and Europe and also in Japan. It either absorbed oils and coal since the late 19th century. Of or overshadowed the pre-existing forests of course, industrial organic chemicals and industry that had developed alongside it. polymers were being produced before that, Accordingly, many of the petrochemical such as highly-concentrated ethanol from products discussed in the previous chapter alcohol distillation, vinegar (acetic acid were developed in industries predating aqueous solution) from acetic acid petrochemistry. This chapter discusses the fermentation of alcohol, soap made by boiling rise and decline of these chemical industries fats and oils with alkalis, coatings from that predated petrochemistry, citing examples unsaturated oils and lacquers and adhesives from Japan. from glue or starch paste. However, these were by no means modern chemic al 4.1 Industrial organic chemicals and industries. Accordingly, this chapter polymers from wood discusses the industrial organic chemical and polymer industries that existed from the late There are two broad forests of chemistry 19th century onwards. using wood as a raw material, as shown in These industrial organic chemical and Fig. 4.1. One is industrial organic chemicals polymer industries developed in significantly made from byproducts produced during wood different ways in various different regions, carbonization, practiced since before the depending on the availability of raw materials modern chemical industry began. The other is and the different product demands. These the use of cellulose, a natural polymer that is industries were individually taking shape in the main component in wood. the forest of petrochemstry, as mentioned in Industrial organic chemical industries the previous chapter. As shall be mentioned using wood carbonization came to an end in later, two forests sprang up from wood, and the 1930s due to the rise of the carbide and three from coal. In terms of technology, acetylene industries, as shall be mentioned Germany, the United States and the United later. This took place at almost exactly the Kingdom were the developed nations. same time in Japan, the United States and However, even Japan developed fully-fledged Europe. Prior to the Second World War, the industrial organic chemical and polymer cellulose industries in Japan started producing industries from the 1930s onwards, using a few chemical products that reached various different raw materials. This laid the world-class production volumes (celluloid, foundation for Japan’s quick uptake and rapid rayon). In the late 1950s, as the development of petrochemical technology petrochemistry became industrialized, the from the late 1950s onwards. cellulose industry forest dwindled into Petrochemistry originated in the United decline as it came under pressure from the States in the 1920s, and existed alongside petrochemistry forest. However, some other pre-existing industrial organic chemical cellulose products have still survived to this and polymer industries in the United States day, namely fine chemical products and up until the 1940s. The forest of functional products. petrochemistry stayed small for the first three decades of its existence in its native habitat, 4.1.1 The wood carbonization industry the United States. There were many other When wood is carbonized to produce

56 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) charcoal, wood tar, pyroligneous acid and acetic acid and its salts and esters, as well as wood gas are produced as byproducts. producing acetone if dry distilled. Crude Pyroligneous acid produces acetate of lime methanol produces refined methanol, which and crude methanol. Acetate of lime produces in turn produces formalin.

Fig. 4.1 Major product categories of wood as raw material.

Wood carbonization has been carried out and Ōkawa Heizaburō. In 1907, The Nippon since the 18th century in forest-resource-rich Acetic Acid Manufacturing Company countries and regions such as Austria, increased its capital to ¥300,000. The Hungary, Northern Europe and the United company newly imported acetic acid States, while Germany and the United manufacturing equipment (steam-heated, Kingdom developed acetic acid refining diminished-pressure crude acetic acid industries, importing acetate of lime and manufacturing equipment, acetic acid using it to produce acetic acid. concentrated distillation apparatus, acetic acid The wood carbonization industry in Japan rectification equipment) from the German began in 1893 with the establishment of a company Mayer. A new plant was completed wood carbonization plant in Tochigi by in 1908, and production of glacial acetic acid Shōichirō Katō, the wealthy founder of Kato (100% acetic acid) commenced. To be more Chemicals in Nikko. Later, the demand for self-sufficient in raw materials, The Nippon acetic acid for dyeing grew, and the wood Acetic Acid Manufacturing Company carbonization industry developed, with an increased its capital to ¥600,000 and increasing number of small-scale established a new plant in Shiobara, Tochigi, manufacturers affiliated to charcoal-making importing a suite of transportable wood facilities. However, such small-scale carbonization equipment from Mayer for the production could not meet the increasing new plant. This ushered in a new era of demand for acetic acid. In 1902, Shōichirō modern wood carbonization plants, well Katō established The Nippon Acetic Acid beyond the reach of small-scale charcoal Manufacturing Company (capital ¥100,000) byproduct processing. The wood was in Honjo, Tokyo. This took over Kato carbonized in a transportable retort or furnace Chemicals and relocated its facilities to begin (wood processing capacity of 1,000 cubic large-scale acetic acid production, using shaku or 27.83 m3) and pyroligneous acid mainly imported acetate of lime. This move was produced by removing the wood tar from was endorsed by the major players in the the volatile component. The pyroligneous business world at the time, including Magoshi acid was then neutralized with milk of lime in Kyōhei, Shibusawa Eiichi, Ōkura Kihachirō a neutralization tank. The neutralized solution

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was heated to evaporate the methanol, then the early 1930s. distilled to produce crude methanol. The residual liquid from the evaporation was 4.1.2 Nitrocellulose concentrated in a double-effect evaporator to Another forest sourced from wood is the produce a concentrated lime acetate solution. cellulose chemistry industry. Cellulose is a This was then dried in a cylindrical natural polymer and is the main component in dehydrator. Annual production of 80% wood and grasses. It has been used since acetate of lime was 900 tons; annual ancient times in the form of hemp fiber, production of 80% crude methanol was 250 cotton and paper. However, cellulose does tons; these products were then sent to the not melt or soften when heated, and also does Honjo plant in Tokyo for refining. not dissolve in solvent. Accordingly, Later, a number of manufacturers started naturally-available, short-fibered cellulose entering the wood carbonization industry as materials had to be utilized through physical the First World War disrupted the import of manipulation such as spinning or acetate of lime, and the market soared. paper-making. Chemical manipulation of Incidentally, during the war, Germany cellulose began in the late 19th century, when industrialized synthetic acetic acid made from it was discovered that it could be partially carbide and acetylene, which was imported nitrated in concentrated nitric/sulfuric acid by many countries, including Japan, after the mixture to produce nitrocellulose, which war. This was followed by a sudden increase could be dissolved in solvent, and had some in acetate of lime imports from the American plastic properties when mixed with camphor. wood carbonization industry, sending a succession of Japanese wood carbonization (1) Celluloid manufacturers into bankruptcy or mergers. In An early cellulose product was collodion 1925, four surviving companies, including (liquid bandages) made by dissolving The Nippon Acetic Acid Manufacturing nitrocellulose in a mixture of ether and Company, formed the Dai Nippon Acetic ethanol. This was followed by celluloid, Acid Manufacturers’ Association, and tried to made from nitrocellulose and camphor in the restrict production in order to achieve market United States in the 1870s. In modern terms, stability. However, the appearance of camphor served as a plasticizer. While synthetic acetic acid meant there was no celluloid was arguably also industrialized in future for the wood carbonization industry, the United Kingdom in the 1850s, it was not and the association turned its attention to until after it was industrialized in the United domestic production of synthetic acetic acid. States that it became properly widespread. The course of events that followed is Celluloid was the first plastic. Initially used discussed in the section on carbide and in daily necessaries and toys, it was also put acetylene. With the domestic production of to use in photographic film by Eastman synthetic acetic acid, the wood carbonization Kodak in 1889, revolutionizing the industry rapidly declined, and completely photosensitive materials industry. disappeared by 1939, as shown in Fig. 4.2. Japan started importing celluloid sheets in the late 1870s, not long after it was first invented. By the mid-1880s, celluloid sheet imports were in full swing; it was being processed to produce faux coral beads, combs, hairpins and collars. In the 1890s, a number of celluloid product manufacturers, inventors, and entrepreneurs started planning to produce celluloid sheets domestically. Despite repeated failures, including some explosion incidents, small-scale production of celluloid Fig. 4.2 Switchover from acetic acid from sheets was achieved. By the late 1900s, wood carbonization to synthetic acetic acid in Mitsui, Mitsubishi, Suzuki Shoten, Iwai

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Shoten and other large-capital enterprises had celluloid. With the successive emergence of started production of celluloid sheets; celluloid-substitute thermoplastics, the main Japanese celluloid sheet production rapidly drawback with celluloid – its combustibility – increased around the time of the First World was a major factor in its losing much of its War. Eight of these celluloid manufacturers demand in the market for toys and daily combined to form Dainippon Celluloid (now necessaries. After that, celluloid production in Daicel) in 1919. Japan started to wane, stopping altogether in After the First Sino-Japanese War, Japan 1996. annexed Taiwan and promoted camphor production there. By the early 1900s, Taiwan (2) Lacquer was leading the world in camphor supply. A butyl acetate solution of nitrocellulose This gave the Japanese celluloid industry a was also used in coatings. This was called competitive edge, and by 1937 Japan was nitrocellulose lacquer. Quicker to dry than producing the highest quantity of celluloid in existing coatings made from unsaturated fats the world (12,760 tons). This accounted for and oils, nitrocellulose lacquer revolutionized 45% of the world’s celluloid; Japan was the automotive coating industry. One exporting 7,500 tons of celluloid sheets. well-known brand was Duco coating, Figure 4.3 shows the trends in celluloid produced by DuPont in 1923. Nitrocellulose production volumes in Japan. Celluloid lacquer is still used for coating leather, production peaked between 1937 and 1940. synthetic leather, wooden articles, furniture, By the late 1930s, nearly 70 companies were etc., due to its luster, durability and quick producing phenol resin, which had been drying speed. domestically produced since 1915. Together, phenol resin and celluloid dominated the (3) Rayon fiber from soluble nitrocellulose plastics market. As a thermoplastic, celluloid Ether and ethanol solutions of had an advantage over thermosetting phenol nitrocellulose could also be made into fibers resin, making for a formidable rival in the by extruding them through a glass tube. market. Frenchman Hilaire de Chardonnet started industrial production of artificial fiber (rayon fiber from soluble nitrocellulose) in 1892. Because silk had been the only long-fiber material available before that, this artificial long-fiber material was known as artificial silk. As nitrocellulose had the drawback of being highly flammable, de Chardonnet denitrated the fibers by soaking them in sodium sulfide. Swiss German chemist Matthias Schweizer had discovered in 1857 that cellulose dissolved in a cuprammonium Fig. 4.3 Change of production volume of solution. Cuprammonium rayon fibers were celluloid. also produced by spinning this solution in a sulfuric acid bath. By the start of the 20th The celluloid industry resumed century, this fiber was proving to be fierce production soon after the Second World War, competition for soluble nitrocellulose rayon exporting toys and daily necessaries. By the fiber in Europe. Soluble nitrocellulose rayon late 1950s, however, it started to come under was never industrialized in Japan. pressure from polyvinyl chloride in the rising acetylene industry; once the petrochemical industry started domestic production with a 4.1.3 Viscose succession of new polymers (mostly The cellulose-based industries were thermoplastics such as polyethylene, significantly transformed by the invention of polystyrene, etc.), the sun began to set on viscose. Once viscose rayon fiber was industrialized in 1904 by British company

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Courtaulds, this method quickly dominated world’s leading rayon-producing country rayon production in the 1910s, having lower (245,000 tons), overtaking the United States, production costs and better product quality by 1938. This was also aided by the fact that than the soluble nitrocellulose method or the the core of the American chemical fiber cuprammonium method. The cellulose is industry had shifted from viscose rayon to treated with a sodium hydroxide solution, and acetate, as shall be discussed in the following then has carbon disulfide added to dissolve it section. into sodium cellulose xanthate, in turn Figure 4.4 shows the trends in production producing a viscous liquid (viscose). When volumes for rayon fiber (including spun in sulfuric acid, the cellulose regenerates, cuprammonium rayon, which started being producing viscose rayon fiber. The viscose produced in small quantities in Japan from can also be extruded through a film-shaped 1931), acetate fiber and synthetic fiber. The slit to form cellophane. prewar peak production volume of rayon fiber was around 20 times higher than the (1) Rayon fiber prewar peak production volume of celluloid. Industrialization of rayon fiber in Japan This figure shows how much smaller in scale began with the viscose method rather than the the plastics market was before the Second soluble nitrocellulose method or the World War. Chemical utilization of polymer cuprammonium method. Mitsubishi, Iwai materials started with fibers rather than with Shoten and Suzuki Shoten, mentioned in the plastics. previous section, were involved in the industry; Japan Celluloid Artificial Silk (now Daicel) was established in 1908 and its factory in Aboshi started operating in 1911. However, contrary to what the name implies, the company did not actually produce artificial silk, but solely produced celluloid sheets. Since there was fierce competition in Europe between the soluble nitrocellulose method, the cuprammonium method and the Fig. 4.4 Change of production volume of viscose method, European companies were rayon fiber, acetate fber and synthetic fiber. not readily exporting technology or

equipment, which meant that Japan Celluloid Rayon fiber revived relatively quickly Artificial Silk was unable to acquire or after the Second World War, topping its industrialize any artificial silk technology. prewar peak in the late 1950s, as shown in Meanwhile, Itsuzō Hata of Yonezawa Fig. 4.4, and reaching 1.8 times its prewar Higher Technical School (now Yamagata peak in 1957. Right at this time, full-scale University Faculty of Engineering), with the production of vinylon, nylon and other support of Suzuki Shoten, independently synthetic fibers began. However, unlike developed a viscose rayon method using celluloid, rayon fiber did not cede defeat to literature from Europe. This technology was synthetic fiber, and did not fall into rapid industrialized, and the Imperial Artificial Silk decline. Although its growth later markedly Company (now Teijin) was established in slowed, production reached a record peak in Yonezawa in 1918. After the First World War, 1967 (479,000 tons). This is thought to be German companies started to actively supply because although rayon was not as strong as technology, and many Japanese companies synthetic fiber, it was still more absorbent entered the viscose rayon industry using and also did not have any fatal flaws, such as introduced technology. Short-fiber rayon was celluloid’s flammability. However, ongoing developed in 1931, and the Japanese rayon improvements were made to synthetic fibers, industry joined forces with the Japanese mainly polyester, and rayon production spinning industry, the strongest in the world volumes decreased from the 1970s onwards, at the time. This enabled Japan to become the as shown in Fig. 4.5.

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cellophane/polyethylene film laminate product (called Polycello) had been achieved in 1954, and by leveraging the respective strengths of both products (the flexibility and transparency of cellophane combined with the moisture resistance and heat sealing-properties of polyethylene), the two were able to develop alongside each other, mainly for packaging food products. This was an unexpected development. While it is Fig. 4.5 Change of production volume of difficult to estimate the weight of cellophane rayon fiber after the production peak and its due to its being a film, cellophane industry being surpassed by acetate fiber. statistics estimate that production increased by 23 times in 20 years from 1950 to 1970, The overall Japanese textile industry reaching a volume of 100,000 tons. (synthetic fiber, spinning, fabric, knitting, However, domestic production of dyeing, sewing) decreased in scale, and is bi-axially oriented polypropylene (OPP) film presently estimated to have a production began in 1963. OPP film could compete head volume of only several tens of thousands of on with cellophane film in terms of its tons. By the 2000s, rayon no longer appeared transparency and flexibility. While OPP film in the statistics on its own, due to decreases in initially made little headway due to its lack of company numbers. Rayon is currently heat sealing properties and other factors estimated to account for only several percent inhibiting its compatibility with packaging of the overall chemical fiber production machines, by laminating it with cast volume, consisting of rayon fiber, acetate polypropylene (CPP) or polyethylene film fiber and synthetic fiber combined. and with the improved heat sealing properties, the market for it rapidly grew from the late (2) Cellophane 1960s onwards. As a result, cellophane Cellophane was invented in 1908 by production volumes peaked in the late 1960s Swiss chemist Jacques Brandenberger. It was and rapidly declined in the 1970s. In 1974, industrialized in 1912 by French company La OPP film production overtook cellophane, Cellophane. It was industrialized in the and the gap increasingly widened from then United States in 1914 by DuPont. DuPont on. In 1980, cellophane production had developed nitrocellulose-coated, dropped to around 50,000 tons, less than half moisture-proof cellophane in 1927, and that of OPP film. Although cellophane demand grew significantly. production has continued to decline, there are The Japanese cellophane industry started still applications for it, and it is still being later than the rayon industry, with Kōshinsha produced. More recently, cellophane has starting production 1926. Like rayon, postwar gained some attention for its biodegradability. production reached a peak around 1937, with an article in the Manchuria Daily News (July 4.1.4 Acetate 21, 1938) estimating a production volume of Acetate, which is produced by reacting around 6,000 tons. Cellophane production cellulose with acetic anhydride, was rapidly recovered after the war, topping its developed during the First World War as an prewar peak in the early 1950s. Meanwhile, aircraft coating resin. British company LDPE imports began in 1951, and production Celanese started industrial production of began the same year on highly productive acetate fiber in 1924 by dissolving acetate in inflation film. This cheap polyethylene film acetone and using a dry spinning method. was thought to be a strong competitor against French company Rhône-Poulenc developed cellophane. With domestic production of similar technology and established LDPE starting in 1958, cellophane was Rhodiaceta in 1922 to start industrial expected to go into decline. However, a production of acetate fiber. Acetate also

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began to be used for cinematographic film in triacetate film. Domestic production of particular, and was not as flammable as triacetate film in Japan started in 1953. As nitrocellulose. Acetate fiber could not easily early as the 1960s, a petrochemical product be dyed with normal cotton dyes, and so made an entry into this field in the form of special synthetic dyes were developed for it. PET film. However, PET film only went as These disperse dyes were also later used for far as X ray films, with triacetate film dyeing synthetic fibers. The production and continuing to be used for ordinary utilization of acetate fiber necessitated the photographic film. With the popularization of development of industrial organic chemical digital cameras from the late 1990s, industries such as acetic anhydride and production of ordinary photographic roll film acetone, and also required far more advanced rapidly declined in the 2000s, and the demand technology than viscose rayon, such as for triacetate photographic film decreased. monoacetylation control technology, dry However, from the 1990s onwards, triacetate spinning, solvent recovery and dyeing with film began to gain attention as a polarizing disperse dyes. Many of these technologies film for liquid crystal displays. Acetate film carried over into synthetic fibers. has thus survived as a new functional product. (1) Acetate fiber Since Japan had not significantly 4.1.5 Fine chemical products from developed industrial organic chemicals prior cellulose to the Second World War, a number of As cellulose polymers interact strongly companies prototyped acetate fiber in the through their hydroxyl groups, cellulose does 1930s and took it no further. Full-scale not break down in water or organic solvents. industrialization came in 1949. However, as If part of the hydroxyl group is esterized or this overlapped with the period of full-scale etherized, the interaction between the industrialization of synthetic fiber, acetate polymers weakens, and they can break down fiber was completely overshadowed by the in water or organic solvent. Various development of synthetic fiber in Japan, and derivatives have been produced and used as remained dormant, as shown in Fig. 4.4. fine chemicals. There are two main products However, in the 1960s, acetate fiber was of this type in particular, as follows. adopted as a raw material for cigarette filters, Sodium carboxymethyl cellulose (CMC) which were in widespread use in Japan. The is a polymer made by reacting cellulose demand for cigarette filters expanded in both treated with sodium hydroxide with the domestic market and the export market, monochloroacetic acid so the hydroxyl and this industry, rather than clothing, groups in the cellulose form carboxymethyl remains the main use for acetate fiber. Unlike ether. The etherization makes the cellulose celluloid or rayon, acetate fiber has its own water soluble. CMC solutions are viscous, area of use that is not in competition with any and form protective colloids. Once applied as petrochemical products, and its production a coating and dried, this forms a transparent volumes have continued to grow steadily. By film that has an adhesive effect. The solution the late 1990s, more than 100,000 tons were is physiologically harmless, and is approved being produced; by the 2000s, production had as a food additive both in Japan and overseas. even overtaken rayon fiber, as shown in Fig. Due to these characteristics, CMC has a wide 4.5. range of uses, including as a dispersion stabilizer for food, a binder for (2) Acetate film pharmaceutical tablets, a wettable powder for Another use for acetate other than fiber is pesticides and a surface sizing agent and photographic film. To ensure the fireproof internal strengthening agent for papermaking. properties of photographic film, there was a Methylcellulose is produced by reacting worldwide trend away from nitrocellulose methyl chloride with cellulose treated with film to acetate film. In 1948, Eastman Kodak sodium hydroxide so some of the hydroxyl successfully industrialized a fireproof groups in the cellulose form methyl ether.

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Unlike CMC, it is a nonionic cellulose ether. almost completely absorbed into Since it is water-soluble and forms a viscous petrochemical industry in the 1950s and the solution, its uses include an emulsion 1960s. Incidentally, the fermentation ethanol stabilizer and thickener in food and cosmetics, industry revived again in Brazil in the 1970s a protective colloid agent for thermal paper as a result of the oil crises, and once again and a binder for pharmaceutical tablets. experienced a sudden revival and subsequent development in the United States in the 2000s 4.2 Industrial organic chemicals and as an environmental countermeasure. polymers from fermentation-based industrial organic chemical 4.2.1 Fermentation ethanol products There have been industries for obtaining spirits with high ethanol concentrations by Industrial organic chemicals produced by distilling fermented alcohol since before the fermentation process of carbohydrates modern era. However, many of these include fermentation ethanol and industries could not really be called chemical fermentation acetone/butanol, as shown in industries, as they used batch methods. The Fig. 4.6. Production of ethanol and butanol as development of continuous distillation gasoline-substitute fuels and octane process turned fermentation ethanol into an enhancers increased in many countries by industrial organic chemical industry. national policy from the 1920s to the 1940s. As this resulted in an abundant supply, a (1) The start of ethanol fermentation in number of chemical industries emerged using Japan these as raw materials. The military munitions factory imported However, in the 1950s, as crude oil from Ilges-method distillation apparatus from the Middle East started being supplied in Germany to produce solvents for making abundance to the rest of the world, the gunpowder, and was able to start production demand for fermentation ethanol as a fuel around 1902. This was the first introduction source decreased, and the fermentation-based of continuous ethanol distillation apparatus to industrial organic chemical industry lost its Japan. industrial base. Fermentation-based industrial organic chemicals and their derivatives were

Fig. 4.6 Product categories of industrial organic chemicals as raw material produced by fermentation process.

Ilges-method distillation apparatus was made up of two distillation columns. The

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mash distillation column was made up of a as extraction or precipitation solvents for baffle tray overlaid with a plate shaped like a digitalis extraction or diastase precipitation. gabled roof over the top of a parallel Ethanol has long been used as a raw arrangement of slit holes. This was designed material for industrial organic chemicals, to prevent blockages, since the fermented such as for vinegar and diethyl ether. Vinegar mash had a lot of solid content. However, this accounted for around 20% of all ethanol equipment had poor distillation efficiency, as usage, while ether accounted for around 10%, a lot of liquid would flow down through the although consumption levels plateaued. slits. The crude ethanol obtained from the Incidentally, from around 1933, there was an mash distillation column was refined in the increasing growth in demand for ethanol as a rectifying column, comprising a regular raw material for ethers and other chemical bubble cap tray. The ethanol concentration compounds such as ethyl acetate, and the after refining was around 92%. usage of ethanol for non-vinegar industrial Prompted by this introduction by the organic chemicals rose to account for a military munitions factory, Nihon Shusei quarter of all ethanol usage. Behind this, there Seizo also imported Ilges-method distillation are thought to be factors such as the domestic apparatus and set up a factory in Asahikawa production of photographic film, and changes in 1902. The company had aimed to produce in varnish, lacquer and other coating fermentation ethanol from potatoes, but it was products. disestablished the following year. However, similar attempts were made by Nippon Sugar Table 4.1 Major use of ethanol specified in Refining Company and other companies. By the industrial alcohol tax rebate law (1906 to 1919, Guillaume-method apparatus, with an 1935) inclined mash distillation column, was also being imported; by 1920, there were 44 plants with Ilges-method distillation apparatus and 24 with Guillaume-method apparatus. Alcohol tax was a major obstacle to using ethanol for non-liquor purposes. Accordingly, the government enacted the Industrial Alcohol Tax Rebate Law in 1906, not long after the introduction of Ilges-method distillation apparatus. This meant that the alcohol tax could be exempted for designated applications for the alcohol. For the first time, (2) Petroleum-alternative fuel ethanol was recognized as a chemical With the First World War underlining the substance that was distinct from liquor. The importance of petroleum, there began to be a first 12 tax-exempt applications were growing interest in Europe in anhydrous designated in 1906: gunpowder (government alcohol as a fuel alternative to petroleum. In and private sector), tobacco fermentation the 1930s, Germany, France, Italy and (government), varnish (private sector, also the various other European countries enacted following), ether, soap, tannic acid, borneol, compulsory alcohol blending policies. Since vinegar, celluloid and its processing, perfume ethanol forms an azeotrope with water at a for export and steam engine fuel. These were concentration of 96%, the azeotrope (hydrous successively added to until 1935. These alcohol) obtained by ordinary distillation designated applications provide a lot of detail could be easily isolated even if the ethanol on the uses of ethanol at that time; these are was mixed with gasoline. If it was made into broadly categorized in Table 4.1. The most anhydrous alcohol, it could be mixed at ratios common applications were for solvents as of up to 20%. The anhydrous alcohol was product components, such as in perfume or produced by reacting the azeotrope with collodion, for processing solvents, such as quicklime. Azeotropic distillation was celluloid processing, or other solvents, such developed around 1930, and anhydrous alcohol became more easily obtainable.

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Azeotropic distillation was developed in with a concentration of 90% or higher were Germany using the Drawinol process, which all deemed to be state business, and state-run uses trichlorethylene, and in France using the alcohol factories were established one after Guinot process, which uses benzene or another from Hokkaido to Kyushu, using benzine. Distillation technology for potatoes and sweet potatoes as raw materials. fermentation ethanol had a significant impact Thirteen factories were set up and running on the development of cryogenic distillation between 1938 and 1942. Most factories had technology by Linde, as mentioned in Section an annual production capacity of 3,600 kL, 2.3.2; this became a fundamental while some had twice that at 7,200 kL. While petrochemical technology. Similarly, these factories were a little larger in scale azeotropic distillation technology to produce than many of the ethanol factories previously anhydrous alcohol also became an operated by private sake brewing companies, indispensable petrochemical technology. this was a far smaller scale than Showa Shuzo. In Japan, Ryūkichi Takahashi also Rather than the conventional fermentation developed an anhydrous alcohol azeotropic technology of using malt to convert starch distillation process using trichlorethylene. into sugar, which is then fermented using Takahashi operated Takahashi Ironworks in yeast, the state-run alcohol factories used Osaka, manufacturing boilers and chemical amylo fungus for sugar conversion, then yeast machinery. The Takahashi Ironworks mash for fermentation. The distillation apparatus distillation column comprised a bubble cap was mainly Takahashi Ironworks equipment, tray designed to prevent mash blockages. In the same as had been used by Showa Shuzo 1934, Teikoku Seishu in Nagareyama, Chiba, and other private companies. As a result of started producing anhydrous alcohol (300 kL the enactment of the Alcohol Monopoly Law, per year) using Takahashi Ironworks the ethanol factories owned by private sake equipment. The following year, Showa Shuzo brewing companies were put under in Kawasaki started large-scale production state-consigned production with the products (around 1,200 kL in 1935; around 4,500 kL in supplied to the state; accordingly, freedom of 1936; around 13,500 kL in 1937), also using operation became increasingly impossible. Takahashi Ironworks equipment. Both The enacting of the Alcohol Monopoly companies were manufacturing synthetic sake Law and the Volatile Oil and Alcohol from anhydrous alcohol. Showa Shuzo was a Blending Law significantly altered the synthetic sake company founded by Chūji demand volume for ethanol and the spectrum Suzuki for processing waste liquid from of its uses from 1937, as shown in Fig. 4.7. monosodium glutamate production. Synthetic Rapid growth was seen in the use of ethanol sake was invented by Umetarō Suzuki of for gasoline mixtures and for munitions. In RIKEN in 1922, and was widely popularized 1935, the demand for fuel was less than 1,000 by Showa Shuzo under the “Sanraku” brand. kL; this had risen to 19,000 kL by 1938 and In 1939, Showa Shuzo established a new to 66,000 kL by 1940. The breakdown of plant in Yatsushiro, Kumamoto, that was demand from 1941 to 1945 is unknown due capable of an annual production of 18,000 to the controls in place at that time. kL. As the construction of state-run factories The Japanese government enacted the could not keep up with the growth in demand, Alcohol Monopoly Law and the Volatile Oil a lot was being imported from Taiwan. and Alcohol Blending Law in 1937, a little Fermentation ethanol production in Taiwan later than similar movements in Europe. also rapidly developed as a result of Japanese These aimed to rapidly increase ethanol government directives and technical guidance. production for use as a fuel alternative to Since sugarcane was being used as a raw petroleum. Another aim was to rescue the material for fermentation in Taiwan, flagging rural economy by increasing the production was more efficient, as it did not production of tubers as raw materials for the require the sugar conversion step in the ethanol. Under the Alcohol Monopoly Law, process, required when tubers were used as a the production, import and sale of ethanol raw material. However, as wartime conditions

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intensified, marine transport became dibromide (a scavenging agent for octane problematic; the volume of imports dropped enhancers) were produced from ethylene. rapidly from 1944 onwards. This was Tetraethyl lead (an octane enhancer) was also compensated for by increasing production at being produced on a large scale from ethanol state-run factories and increasing the volume via ethyl chloride. Ethylene chlorohydrin was of production consignments to private sake also reacted with hydrogen cyanide to companies. produce acrylonitrile, a raw material for oil-resistant synthetic rubber NBR. Antifreeze was used on the northern war front, and octane enhancers were indispensable in aviation fuel. Octane enhancers were used by mixing with scavenging agents, but up until just before the Second World War, these were all imported from the United States Ethyl Corporation. These industrial organic chemicals were all produced with domestic technology developed in absolute secrecy. The system of products made from Fig. 4.7 Change of demand for usage of ethanol via ethylene, shown in Fig. 4.6, are ethanol in the early Showa period. far more highly specific than the system of petrochemicals discussed in the previous (3) The development of chemical chapter, or the system of acetylene and coal industries from fermentation ethanol tar products that shall be discussed later. The Figure 4.7 shows another area of growing industrial organic chemical ethanol is used to demand for ethanol other than gasoline produce the basic chemical product ethylene, mixtures and munitions, namely, the demand which in turn can be used to produce new for ethanol for chemical industries. It has product categories. Calculating by theoretical already been mentioned that this demand product output level, since the product output started growing from around 1933. As an level at the time is unknown, equivalent ample supply of fermentation ethanol became ethylene production estimated from the available from 1937 onwards, there was an production volumes of EG and other ethylene increase in ethylene-based industrial organic products would have been 600–700 tons chemicals that used it as a raw material. The between 1940 and 1944. Ethylene and demand for ethanol for chemical industries ethylene products were far smaller in scale grew from 16,000 kL in 1935 to 35,000 kL in than the equivalent ethylene production 1939. Ethylene was produced by dehydrating volume of 8,000–10,000 tons calculated from ethanol, as indicated in the product categories carbide/acetylene products (overwhelmingly, shown in Fig. 4.6. Ethylene can also be synthetic acetic acid), discussed later. produced by partial hydrogenation of However, assuming that all fermentation acetylene; however, this method also ethanol was made from ethylene, given the produces ethane, making the ethylene specificity of fermentation ethanol products, difficult to refine. Producing ethylene by the equivalent ethylene production volume dehydrating ethanol required a fixed-bed, would have peaked at 60,000–70,000 tons in vapor-phase, continuous reactor using a solid 1942, around 20,000 tons of which would acid catalyst such as acid clay. Since ethylene have been used by chemical industries other and its halogen derivatives had already been than fuel or vinegar. Thus, the fermentation designated under the Industrial Alcohol Tax ethanol industry was a more significant Rebate Law in 1928, there is proof that chemical industry in the early 1940s than the ethylene was being produced in Japan from carbide/acetylene industries. around this time. Ethylene chlorohydrin, EG (a raw (4) The decline and revival of the material for antifreeze) and ethylene fermentation ethanol industry after the

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Second World War As a result, there was a marked decrease in In Europe and Japan alike, the greatest domestic fermentation. demand for the chemical industries based on Against this backdrop, the circumstances fermentation ethanol from the 1930s to the surrounding the fermentation ethanol industry early 1940s was munitions. Consequently, worldwide completely changed after the oil once the war was over, there was no revival crises, and a stable supply of crude alcohol of the chemical industries based on became available. Brazil is the largest fermentation ethanol. As the demand for supplier of crude alcohol. In an attempt to rid gasoline substitute fuels also faded, for a long itself of petroleum imports, Brazil started time fermentation ethanol production large-scale production of fermentation remained dormant. ethanol from sugarcane as a The late 1960s saw the start of petroleum-alternative fuel right after the oil petrochemical ethanol (synthetic alcohol) crises. production from ethylene in Japan. Within a The United States started making short space of time, this had overtaken the extensive policies on alcohol additives to fermentation process, supplying the demand gasoline in the 2000s. This was a for solvents, chemical raw materials, etc. countermeasure for automobile emissions and However, the rising cost of petrochemistry a means of raising octane values. As Fig. 4.8 resulting from the two oil crises, and the rapid shows, these policies saw a rapid increase in increase in applications for food preservatives the production of fermentation ethanol from (food additives) [Footnote 1], which were maize in the United States within one short monopolized by fermentation ethanol, decade. Recent fermentation ethanol sparked a revival of fermentation ethanol in production volumes in the United States are the 1980s, turning the tables on the more than six times higher than petrochemical method once more. Survival petrochemical ethanol production in the early had been achieved by opening up areas of 1980s. Production volumes in the 2010s have demand in which there was no competition reached around three times those of Brazil. from petrochemistry. Refining technology was licensed from French company Melle in the 1950s using the Allospas distillation process. This method involved adding water to already highly-concentrated ethanol and distilling it again. Adding water increased the relative volatilities of the ethanol and any impurities, thus making it easier to remove the impurities. This is called extractive distillation using water. Such technological improvements significantly lowered the Fig. 4.8 Change of production volume of amount of impurities (methanol, fusel oil, ethanol in the U.S. aldehydes) in the ethanol, meaning the growing demand in food product industries Judging from equivalent ethylene (the could be met by fermentation ethanol. amount of ethylene required calculated on the Most significantly, renewed cost assumption that it was petrochemically competitiveness by dramatically altering the synthesized from ethylene), production of fermentation ethanol business also made a fermentation ethanol in 2010 reached 25 major contribution to the revival of million tons in the United States. An fermentation ethanol in Japan. The industry equivalent volume of ethylene was produced started importing crude alcohol fermented in the United States in 2012. From the 2000s, and distilled overseas as a raw material, fermentation ethanol has made a rapid leaving only the refining to be done in Japan. comeback for around a decade due to

[Footnote 1] All around the world, fermentation ethanol rather than environmental policies. petrochemical ethanol is used in vinegar, food preservatives, and other areas in which it may be absorbed into the human body.

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4.2.2 Industrialization of polyethylene Meanwhile, Japan first became and polystyrene from fermentation acquainted with LDPE in 1942 in the form of ethanol a radar cable captured from the American It has been noted in the history of military. Domestic production of it became a Japanese petrochemical technology that pressing issue in Japan. Research began in the LDPE and polystyrene made from fall of 1943 by three groups commissioned by fermentation ethanol started being produced the navy through the Electrotechnical domestically in Japan in 1944, towards the Laboratory. These were led by Prof. Yukichi end of the Second World War, as there was a Go of Osaka University and Mitsui need for high-frequency insulating materials Chemicals, Dr. Taizō Kume of the Noguchi for radars. This is discussed in greater detail Institute and Nippon Chisso Hiryō and Prof. below. Kodama Shinjirō of Kyoto University and It has now almost been forgotten that Sumitomo Chemical. LDPE and polystyrene made from The Noguchi Institute started fermentation-ethanol-based ethylene was experimenting in early 1944, with little produced in Japan using Japanese technology. literature to rely on, and, with astounding The military had a pressing need for these speed, had already established a two new plastics at the time. However, this manufacturing method using ethylene was a very small-scale demand, as the liquefaction and filling by summer that same intended application was for insulating year. In the summer of 1944, Nippon Chisso components for radars. Accordingly, although Hiryō (now Chisso) started construction on a these plastics were industrialized, it was on a plant at its factory in Minamata. Fit-out of the far smaller scale than the early plant was completed by the end of December industrialization in the petrochemical industry with a 1,000 atm compressor supplied by the after the war. Since the industrialization took navy fuel factory. Operation started place towards the end of the war, there were successfully in early 1945, and by March the concerns about a shortage of resources and Noguchi Institute researchers were no longer raw materials. Ultimately, air raid damage needed. However, everything was completely meant the fledgling industry had to cede destroyed in an air raid in May 1945. defeat after a short period of operation. Following the Second World War, this Almost none of this technology was passed domestic technology was completely buried. on, as the postwar industrialization was based In November 1944, Mitsui Chemicals on introduced technology. Nevertheless, this started construction on a facility with a 20 kg early industrialization using domestic monthly production capacity, but this ended technology indicates the heights reached by without reaching production stage. In January Japanese organic synthesis technology and 1944, Kyoto University started research with polymer synthesis technology during the a 40 cc reactor, but this came to an end in Second World War. March with only a small amount of specimens obtained. However, research (1) Polyethylene began again after the Second World War, LDPE was invented in 1933 by British with Kyoto University taking on a company ICI and industrialized in 1939, commission from the Nippon Telegraph and using fermentation ethanol as a raw material. Telephone Public. The university conducted a Around 100 tons were produced in 1940, and continuous industrialization experiment from its superior properties as a high-frequency 1951 to 1953 with a daily output of 10 kg, insulating material were recognized. The using fermentation ethanol as a raw material. Second World War had already begun; ICI Based on this research, Sumitomo Chemical supplied the technology to American used an industrialization testing subsidy from company DuPont at the request of the United the Ministry of International Trade and States Navy. In 1943, a plant with a 900 tons Industry to build and operate an intermediate annual production capacity was built in the testing plant with a 3-ton monthly output United States. capacity at its factory in Niihama in 1953.

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This record of achievement made Sumitomo ethylbenzene dehydrogenation reaction had a Chemical the company of choice when ICI low yield and produced tar as a byproduct. was looking for a technology licensing Accordingly, various alternative methods partner in Japan. were developed. During the Second World War, Japan (2) Polystyrene industrialized styrene with three production A major challenge with polystyrene was methods using different raw materials, as coming up with a manufacturing method to shown in Fig. 4.9. These were the Hodogaya produce the monomer styrene. German Chemical method, from ethanol via ethylene, company IG Farben had started industrial ethylbenzene and 2-chloroethylbenzene; the production of styrene in the early 1930s using Nihon Yuki method, from acetylene via a method of dehydrogenating ethylbenzene acetophenone and α-phenyl ethyl alcohol with an alumina-chromia catalyst. (methyl phenyl carbinol); and the Shiono Ethylbenzene was synthesized from ethylene Kōryō method, by dehydrating rose perfume and benzene using an aluminum chloride β-phenyl ethyl alcohol. catalyst. This was a reaction often used in the oil refinery industry. However, the

Fig. 4.9 Production method of styrene industrialized in Japan during the Second World War.

Hodogaya Chemical started research in was difficult to remove these trace amounts 1938, with a request from the military to of impurities by distillation. Instead, the industrialize polystyrene. It came up with the researchers at Hodogaya Chemical removed alternative method of reacting chlorine with the acetylene-based impurities by exposing ethylbenzene to produce the styrene to an aqueous solution of copper, 2-chloroethylbenzene, which was and then successfully synthesized dehydrochlorinated to form a styrene high-molecular-weight, low-dielectric-loss monomer. This method was deemed to have a polystyrene. Care had to be taken with the higher yield than the IG Farben method. generation of copper (I) acetylide, as there is However, the polymerized polystyrene was a risk of explosion when handling brittle with a low molecular weight, and acetylene-based compounds. This was a could not be made into a product. This was superb piece of refining technology, using found to be caused by a secondary this to the opposite effect. This indicates the dehydrogenation reaction in the level of analysis technology and organic dehydrochlorination reaction process, synthesis technology Japanese chemical producing traces of phenyl acetylene. This companies had at the time. A year of impurity was preventing the radical industrialization experimentation took place polymerization of the styrene. However, it from the fall of 1941; by the fall of 1942,

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production technology had been completed to Chaim Weizmann of the University of produce polystyrene from ethanol via Manchester (later the first president of Israel) ethylene. However, there was a shortage of isolated a potent strain of bacteria in 1912, resources and the construction of plants took and patented an acetone/butanol production longer than anticipated; a plant with a 5-ton method using this strain in 1915. This monthly production capacity was finally fermentation process was industrialized in the completed in August 1944 in Komatsugawa, United Kingdom and Canada during the First Tokyo. The factory started out operating well, World War, as acetone was needed for but was damaged by a fire in January 1945 making gunpowder. In 1920, DuPont and an air raid in March, and was never able invented nitrocellulose coating, which used to reopen. butyl acetate as a solvent; this resulted in Nihon Yuki, a joint venture between Kao large-scale acetone/butanol fermentation in Sekken Nagase Shokai and Tekkosha, was the United States as well. In 1931, Koei (now established in 1940 with polystyrene Koei Chemical Company) started industrial production as one of its aims. The Tekkosha production in Japan as well. Sucrose was factory at Sakata produced acetic acid, and used as the raw material. subsequently acetyl chloride, from acetylene In 1936, three companies (Godo Shusei, via acetaldehyde. The acetyl chloride was Takara Shuzo and Dai Nippon Shurui Seizo) reacted with benzene to produce jointly established a research institute, and acetophenone, which was transported to the started researching isooctane aviation fuel Nihon Yuki factory at Hirai, Tokyo. The from butanol [Footnote 2]. This led to the acetophenone was then high-pressure establishment of Kyowa Hakko Kogyo after hydrogenated to produce α-phenyl ethyl the war. The research gained the attention and alcohol. The high-pressure hydrogenation support of the Imperial Japanese Army Air technology had been mastered by Kao Service. At the end of 1940, an isooctane Sekken for producing higher alcohols from sample was presented to the army, and the fats and oils. The α-phneyl ethyl alcohol was Air Service headquarters urged industrial then dehydrated to produce styrene, which production. As a result, a pilot plant was built was then made into polystyrene. Operations at the Godo Shusei factory in Asahikawa, started in 1944, producing 12 tons by 1945. which had already been working on However, the plant was hit by an air raid in acetone/butanol fermentation. Unlike March 1945, and was unable to reopen. fermentation ethanol, fermentation Shiono Kōryō is a perfume and fragrance acetone/butanol research and production was company in Mikuni, Osaka, with a history of spearheaded by private companies. extracting and producing natural perfumes At the start of the Pacific War, the and fragrances. The company developed itsgovernment was inclined towards isooctane own technology to obtain styrene by production from fermentation butanol, as it had dehydrating the β-phenyl ethyl alcoholannexed regions to the south with a ready supply fragrance found in roses and other flowers, of sucrose. As a result, the Toyobo factory in and then independently developed the Hofu was converted over to the production of technology to produce polystyrene from this.acetone/butanol and isooctane in 1943. A Designated as a polystyrene supplier by thelarge -scale, 400 kL fermenter was constructed at Ministry of Munitions in 1944, the company the Hofu factory, and butanol production started produced around 1 ton a month, although it at the end of 1943. had a 2 tons monthly production capacity. This invention was a commendable idea that turned the tables on the wartime slump in the perfume and fragrance business.

4.2.3 Fermentation acetone/butanol [Footnote 2] n-butanol is dehydrated to produce n-butylene, which is Louis Pasteur discovered that butanol then isomerized to produce isobutylene. The isobutylene is dimerized and reduced further to produce isooctane. A method of could be made from anaerobic bacteria. reacting isobutylene with isobutane to produce isooctane was also known at the time.

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However, with plans afoot for transitioning to petrochemical methods, the price of acetone and butanol began to drop from the late 1950s onwards, with the expectation that the cost of petrochemical production would decrease. Accordingly, fermentation companies and acetylene synthesis companies alike abandoned their existing facilities and quickly started shifting Fig. 4.10 Production volume of butanol in to petrochemistry. As a result, fermentation Japan during the Second World War. process production came to a halt within two years of the start of the petrochemical method. However, with the wartime situation Unlike fermentation ethanol, fermentation intensifying in 1944, it was no longer acetone/butanol has not continued anywhere possible to ensure possession of the regions in in the world to the present day. the south, which made it difficult to obtain sucrose. The government issued instructions 4.3 Industrial organic chemicals and for the factory in Hofu to suspend production polymers from fats and oils of isooctane and switch from acetone/butanol to producing anhydrous alcohol from tubers. The main chemical products made from Accordingly, the factory in Hofu continued fats and oils that have existed since before the anhydrous alcohol production from 1944 until modern chemical industry are soap and the end of the war. coating. Soap has been produced since Butanol can also be produced from ancient times by boiling fats and oils in carbide/acetylene. However, synthetic alkalis. butanol production stopped at the trial Coatings have also been made since production stage, as shown in Fig. 4.10, and ancient times by mixing pigments with drying the butanol supply was almost entirely oil (oils containing large numbers of provided for by fermentation process. unsaturated bonds, such as linseed oil or tung Right after the end of the war, the oil) or semi-drying oil (such as soybean oil). managers and operators of the Hofu factory The unsaturated bonds in the oil are oxidized devised a plan to resume production of by the oxygen in the air and polymerize, thus acetone/butanol from cheap, imported resulting in a weather-resistant polymer molasses instead of sucrose. Although the product. While not an oil, Urushi lacquer has permit to import the molasses took more than similarly been made since ancient times in two years from the time of application, it was Japan and East Asia using an air oxidation finally granted in 1948. After several years, polymerization process. One drawback with the fermentation process overtook the these coatings is that they were very slow to carbide/acetylene synthesis method resumed dry (polymerize) once applied. In order to shortly after the war. quicken the drying (polymerization) process The demand for butanol rapidly increased slightly, the oil was mixed with lead, as a raw material for polyvinyl chloride manganese, or cobalt oxide and then boiled. plasticizers DBP and DOP. This resulted in a With the development of oleochemistry rapid postwar revival of fermentation in the 20th century came the production of a acetone/butanol, unlike fermentation ethanol. number of industrial organic chemicals and This situation continued until the advent of polymers from fats and oils, as shown in Fig. the petrochemical method in 1962. In the 4.11. early 1960s, the fermentation process accounted for 27,000 tons of butanol per year, 4.3.1 Soap/hydrogenated oil while the carbide/acetylene synthesis method Soap took hold in Japan as an imported accounted for no more than 6,000 tons per product in the early Meiji Period. A number year. of newcomers appeared in the market,

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expecting the demand to grow, and of handicrafts using open-fire saponification technology was introduced from the West. kettles and mold-kneading technology. However, this never grew beyond the domain

Fig. 4.11 Product categories of fats and oils as raw materials.

The Japanese soap industry became established as a modern chemical industry 4.3.2 Expansion into diversified around 1900. Nagase Shokai (now Kao) oleochemistry advocated the production of high-quality soap In the 1930s, companies started moving and set up factory production facilities, away from the soap/ fats and oils industries introducing steam saponification kettles and and into diversified oleochemistry. For machine mixing technology. In 1910, the reference, Fig. 4.12 shows the chemical company started production of high-purity structures of the fats and oils and fat and oil fatty acids and glycerin by high pressure products discussed below, as it is difficult to hydrolysis of fats and oils using autoclave explain the developments in oleochemistry equipment imported from Germany. This using words alone. In the early 1930s, made it possible to produce good quality synthetic surfactant higher alcohol sulfuric soap. acid ester salt (AS) (see Section 3.4.7 (2)) Up until the First World War, all glycerin was imported for the first time from Boehme had been imported. In 1911, Nagase Shokai in Germany. While this surfactant is still used started recovering crude glycerin from the as a neutral detergent for washing high-end liquid waste from its soap, and many other garments, etc., at the time it was used more as companies followed suit. Refined glycerin a dyeing auxiliary for helping dyes permeate was needed by the military for gunpowder, and adhere uniformly to fabric than for and so glycerin became subject to the Law laundry. This product spurred Japan into Promoting the Production of Dyes and initiatives to produce its own higher alcohol Pharmaceuticals (1915). Based on this law, sulfuric acid ester salt. the national policy concern Nippon Glycerin was established in 1916 with a capital stock of ¥6 million to produce refined glycerin. Around the same time, hydrogenated oil began being produced by hydrogenating fats and oils. At the time, there was an abundant supply of fish oil (sardine oil, etc.). Since fish oil contains a lot of unsaturated fatty acids, it would form solid hydrogenated oil at normal temperatures when hydrogenated with a nickel catalyst. The hydrogenated oil was used as a substitute for the imported beef Fig. 4.12 Major molecular structures of tallow used for making soap. oleochemistry products.

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oils contributed to the postwar revival of the Dai-ichi Kogyo Seiyaku used sperm oleochemical industry. This was n-octyl whale oil (spermaceti) as a raw material. The alcohol for the plasticizer DOP, used in PVC. main component in spermaceti is a wax However, straight-chain octyl alcohol from (higher alcohol ester of a higher fatty acid) fats and oils was not as good a plasticizer as rather than an oil (higher fatty acid branched-chain octyl alcohol synthesized triglyceride). Specifically, it is the ester of from acetylene/acetaldehyde, and the later palmitic acid and cetyl alcohol. Consequently, growth in plasticizers was through the it produces a higher alcohol (mainly cetyl acetaldehyde method. alcohol) when hydrolyzed, and esterizes with The emergence and subsequent sulfuric acid. Dai-ichi Kogyo Seiyaku significant development of synthetic developed this production technology in 1934, detergents from petrochemical products in the and started production in 1938. It was first 1950s–1960s placed significant pressure on marketed as the household neutral detergent soap and synthetic detergents made from fats “Monogen,” safe on wool and other delicate and oils. However, the early rapid growth in fabrics. This was the first synthetic detergent synthetic petrochemical detergents was produced with Japanese technology. However, accompanied by some environmental issues high pressure hydrolysis technology was (foam pollution in rivers) in the 1960s, both introduced in the 1910s that could extract the in Japan and in the West. The cause of this cetyl alcohol from spermaceti. Since it is a was investigated, followed by initiatives to wax rather than an oil, the higher alcohol “soften” synthetic detergents [Footnote 3]. could be obtained by high pressure Environmentally biodegradable surfactants hydrolysis. began to be produced from straight-chain Kao used high-pressure reduction of higher alcohols and straight-chain α-olefins coconut oil to produce a higher alcohol, using fat and oil high-pressure reduction which was then subjected to sulfuric acid technology. The synthetic detergent esterification and marketed as the synthetic “softening” process only took six years in detergent “Exceline” in 1938. Kao’s Japan, and was fully completed in the early technology reduced the higher fatty acid 1970s. This process was accompanied by a using hydrogen at high pressure. revival in large-scale production of higher High-pressure reduction technology had a fatty acids and higher alcohols from fats and broad range of applications, and marked the oils. Diversified oleochemistry joined with beginnings of diversified oleochemistry. In petrochemistry to expand in new directions. 1939, Kao successfully produced an aircraft lubricant by reducing a higher fatty acid at 4.3.3 Oil-modified alkyd resin high temperature and pressure using a zinc An alternative to the drying-oil coatings catalyst to obtain α-olefins, which were then that have been used since ancient times is oligomerized with aluminum chloride. In nitrocellulose coating, made up of 1940, the United States started imposing nitrocellulose and an organic solvent. Due to high-octane gasoline and aircraft lubricant its quick drying time, this coating suddenly embargoes on Japan. At the request of the grew in popularity in the 1920s, alongside the military, at the end of 1941, Kao started flourishing American automotive industry. construction of an aircraft lubricant factory Oil continued to be used in coating, with an annual production capacity of 100 kL. thanks to the development of oil-modified High-pressure reduction technology was also alkyd resin in the late 1920s, made from used in the production of sorbitol from drying oil, semi-drying oil and phthalic glucose (industrialized in 1943), and α-phenyl anhydride. When oil (higher fatty acid ethyl alcohol from acetophenone (raw triglyceride) reacts with glycerin, material for styrene, mentioned in Section transesterification occurs, producing a mix of 4.2.2 (2), industrialized in 1943). higher fatty acid monoglycerides and The production of one particular higher [Footnote 3] Detergents with poor environmental biodegradability alcohol by high-pressure reduction of fats and are termed “hard,” while those with good biodegradability are termed “soft.”

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diglycerides [Footnote 4], as shown in Fig. resources in order to reduce greenhouse gases. 4.13. When this reacts with phthalic One such example is the rapid increase in anhydride, the monoglyceride molecules, production of fermentation ethanol in the which have two hydroxy groups, form several United States, discussed previously. These bonds (oligomerization). The diglycerides, initiatives have even extended as far as fats which only have one hydroxy group, stop the and oils. Europe has seen a rapid increase in bonds from extending, thereby regulating the the use of biodiesel oil from palm oil, length of the oligomer molecules. Since the rapeseed oil, sunflower oil and other such unsaturated bonds contained in the higher sources. Biodiesel oil is a higher fatty acid fatty acid remain as they are, as indicated by methyl ester produced by the R1 and R2 in Fig. 4.13, once the coating has transesterification of oil (higher fatty acid been applied, oxidative polymerization occurs triglyceride) and methanol. Technically, it through contact with the oxygen in the air, only refers to product that has already been similar to drying-oil coatings. This is shown used in the course of higher alcohol in Fig. 4.13 as alkyd resin. production. However, biodiesel oil Since the alkyd resin has more production has increased dramatically due to unsaturated bonds per oligomer molecule its use as an automotive fuel, with the than the original unsaturated oil, it dries faster production of palm oil rapidly increasing and is also more weather-resistant and more from 300,000 tons in 1995 to 41 million tons flexible. Like boiled oil, alkyd resin dries in 2009. even faster when combined with cobalt naphthenate, lead naphthenate, or other additives. Alkyd resin has been produced domestically in Japan since the start of the 1930s, and is also known as phthalic acid resin. After the war, a mixture of alkyd resin and amino resin (butylated melamine formaldehyde resin, butylated urea formaldehyde resin, etc.) emerged in 1948 in the form of amino-alkyd resin baked coating. However, as the petrochemical industry moved into domestic production and expansion, a number of petrochemical polymers began to be used in coatings, significantly reducing the role played by oil-based coatings. Amidst such trends, however, some products, such as epoxy alkyd resin coating, are still being produced that utilize the strengths of both petrochemical and oil-based coatings.

4.3.4 Biodiesel oil There have been significant changes in the directions taken in oleochemistry in recent years. Policies such as the Biofuels Directive issued by the EU in 2003 have aimed to accelerate the use of renewable

[Footnote 4] The molecular structure of glycerin is CH2OH – CHOH – CH2OH. Oil (higher fatty acid triglyceride) has a molecular 1 2 3 structure of CH2OCOR – CHOR – CH2OR , where R represents the alkyl group. When the glycerin and oil are transesterified, one or two alkyl groups in the oil break away to form hydroxy groups OH. These are called diglycerides and monoglycerides.

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Fig. 4.13 Molecular structures of glycerides and oil-modified alkyd resin.

4.4 Industrial organic chemicals and in terms of industrial organic chemicals, and polymers from coal no further details have been included here.

Coal chemistry, or the forest of products 4.5 Industrial organic chemicals and made from coal, flourished for a long time polymers from carbide/acetylene before and after the advent of petrochemistry. Coal chemistry falls into three broad Carbides are made from coke, produced categories, each of which has developed so by distilling coal, and as such are one of the significantly that it has been assigned a forests of petrochemistry. Carbides are separate section here. These separate forests produced by reacting coke with quicklime in are carbide/acetylene chemistry, coal an electric furnace at a temperature of tar/aromatic chemistry and coke/syngas 2,000°C or higher. This requires a lot of chemistry. electricity and can also be counted as an Another such forest was the use of gas electrochemical industry. (called coke oven gas or coal gas) produced Lime nitrogen is produced by exposing in the dry distillation of coal chemicals. The carbides to a nitrogen flow at 1,000–1,100°C. main components in coke oven gas are Lime nitrogen on its own is used as a hydrogen and carbon monoxide; these were nitrogenous fertilizer. Since it produces widely used in city gas supplies, as well as ammonia when reacted with steam, it can also providing the raw material by which the be absorbed into sulfuric acid and then used ammonia industry was established. Coke as a nitrogenous fertilizer in ammonium oven gas also contains various other sulfate form (converted ammonium sulfate) substances in addition to hydrogen and [Footnote 5]. When carbides react with water carbon monoxide, including ammonia, sulfur at normal temperatures, acetylene is produced. compounds and hydrocarbons – including This reaction was discovered in 1862 by ethylene. It is difficult to extract and refine German chemist Friedrich Wöhler, one of the the ethylene from coke oven gas to use it as a founders of organic chemistry. raw material for industrial organic chemicals, While lime nitrogen was industrialized and this was largely not done in Japan.

However, it was done in Germany, and in [Footnote 5] Ammonium sulfate (ammonium sulfate fertilizer) made wartime it ranked among the most significant from ammonia produced directly from nitrogen and hydrogen is called synthetic ammonium sulfate. By contrast, ammonium sulfate sources of ethylene next to dehydration of made from ammonia produced by reacting lime nitrogen with steam fermentation ethanol and partial is called converted ammonium sulfate. Ammonium sulfate produced in the treatment of waste sulfuric acid from the production of hydrogenation of acetylene; it was also a caprolactam or other chemical compounds other than ammonium source of EG and other such substances. The sulfate is called recovered ammonium sulfate, while ammonium sulfate made from ammonia found in coke-oven gas generated in coke oven gas forest is not a significant one coal carbonization is called byproduct ammonium sulfate.

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several years after the industrialization of industrialized in 1911 by German company carbides, the acetylene chemical industry was BASF. This technology provided some not established until the 20th century, around competition for the method of manufacturing 50 years after Wöhler’s discovery. nitrogenous fertilizer from carbides. Direct ammonia synthesis spread around the world in the 1920s, with a succession of Japanese 4.5.1 Carbides companies also entering the direct ammonia Carbides were industrialized by synthesis market and producing synthetic American company Union Carbide in 1894, ammonium sulfate in the 1920s and the 1930s, and around the same time in Europe. following its industrialization in 1923 in Acetylene was initially used as acetylene gas Nobeoka (now Asahi Kasei) by Nippon for lighting. One useful application that was Chisso Hiryō using the Casale method from developed was safety lamps for mineshafts. Italy. However, even the emergence of Later, a number of improvements were made synthetic ammonium sulfate did not result in to carbide production, including shifting the a dramatic decrease in demand for carbides electric furnaces from single-phase to for fertilizer. After the Second World War, three-phase current, and changing the carbon there was a call to increase fertilizer source from charcoal to anthracite and then production, and the carbide industry quickly coke. By 1915, 10,000 kW large-scale revived in response. electric furnaces were being built. Lime nitrogen formation was discovered A detailed examination of carbide in Germany in 1897. Later furnace consumption reveals that from the 1950s improvements resulted in the industrialization onwards, there was a decrease in carbide use for fertilizer as the main area of demand, of the Frank-Caro furnace in 1908. This made replaced by a rapid increase in its usage in the it possible to produce large volumes of acetylene chemical industry. However, nitrous fertilizer from the nitrogen in the air, acetylene chemistry came under pressure as well as ammonia, and lime nitrogen / from petrochemistry in the 1960s, and had converted ammonium sulfate plants began to almost disappeared by the end of the decade. be established all around the world, such as Carbide production peaked in 1965 and the American Cyanamid Company at Niagara rapidly declined after that. Falls in the United States in 1909.

In Japan, Tsuneichi Fujiyama and 4.5.2 Acetylene chemical industry Shitagau Noguchi successfully produced The acetylene chemical industry based on carbides with a 50 kW electric furnace in acetylene made from carbides was founded in Sankyozawa, Sendai, in 1902. Later, Noguchi 1916 by German company Wacker, with the established Nippon Chisso Hiryō (now JNC), production of acetyl aldehyde by reacting and in 1908 built a plant in Minamata with acetylene and water. Many companies soon four German-made 3,000 kW carbide entered the market in Germany, Canada and furnaces, and started producing lime nitrogen. the United States, resulting in the demise of Meanwhile, Fujiyama established Hokkai the wood carbonization industry, as Carbide Plant (now Denka) in Tomakomai in mentioned in Section 4.1.1. 1912. He established a plant in Ōmuta, In Japan, the Nippon Synthetic Chemical Fukuoka, in 1916, and another in Ōmi, Industry started producing acetaldehyde in Niigata, in 1921, significantly expanding the 1928 as an intermediate for synthetic acetic carbide, lime nitrogen and converted acid production. The acetylene chemical ammonium sulfate industries. industry continued to expand in Japan for Up until around 1950, 50–80% of another 40 years. Up until the 1950s, the carbides were used for fertilizer, and 20–30% Japanese acetylene chemical industry mainly were used for lighting, welding and cutting, revolved around the production of as shown in Fig. 4.14. acetaldehyde and synthetic acetic acid. The process of directly synthesizing During these two decades, organic synthesis ammonia from nitrogen and hydrogen was (the acetylene chemical industry) accounted for around 10% of all carbide consumption,

76 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) other than during the Second World War, as shown in Fig. 4.14.

Fig. 4.14 Change of production volume and demand detail of calcium carbide.

The 1950s and the 1960s, however, saw a oxychlorination process. sudden increase in organic synthesis. This Below, we shall discuss the main meant an accompanying rapid increase in products and technologies of the acetylene carbide production, far exceeding peak chemical industry, as well as the industry prewar volumes. The main reason for this policies aimed at boosting industrial organic increase was vinyl chloride, which was solely chemical industries just before the Second used for making PVC. Acetylene chemistry World War in Japan. also rapidly expanded in scale, with growing demand for monomers and polymers. Vinyl (1) Acetaldehyde acetate, chlorine-based solvents and many Acetic acid and acetone were supplied by other industrial organic chemicals were also the wood carbonization industry from the late produced from acetylene, as shown in Fig. 19th century onwards. As mentioned 4.15. previously, acetylene-based acetaldehyde was However, carbide production volumes industrialized by German company Wacker dropped rapidly at the end of the 1960s. The during the First World War. Since acetic acid main reason for this was also organic could be produced cheaply from acetaldehyde synthesis. With the production of using manganese acetate as a catalyst, acetaldehyde, vinyl chloride and nearly every Germany started exporting synthetic acetic other industrial organic chemical made from acid around the world after the war, putting acetylene changing over to petrochemical the wood carbonization industry at risk of methods, the acetylene chemical industry fell disappearing. Japan also investigated the into rapid decline. The main reasons for this domestic production of synthetic acetic acid, were the rising cost of electricity, which and several negotiations were made with meant that carbide-based acetylene could no German company IG Farben over technology longer compete with basic petrochemicals, as licensing. However, a compromise on the well as the fact that a succession of low-cost conditions could not be met, so the four production methods were being developed for companies of the Dai Nippon Acetic Acid producing industrial organic chemicals from Manufacturers’ Association started jointly basic petrochemicals, such as the researching under the supervision of the Hoechst-Wacker process and the Osaka Municipal Technical Research

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Institute and sharing their results. Their started in 1928, with an output of 60 tons per industrialization experiments ended in 1927. month. The lifting of the gold export embargo That same year, the four companies jointly in 1930 increased imports of synthetic acetic funded the establishment of Nippon Gohsei acid, synthetic methanol and other imports, Kagaku Kenkyusho (now The Nippon prompting the four companies financing The Synthetic Chemical Industry). Since carbides Nippon Synthetic Chemical Industry to were needed as a raw material, a factory was rapidly reduce their own wood carbonization constructed in Ogaki on a site adjoining operations and instead boost the synthetic carbide manufacturer Ibigawa Electricity acetic acid production capacity of The Company (now Ibiden), and production Nippon Synthetic Chemical Industry.

Fig. 4.15 Product categories industrialized using acetylene as raw material in Japan.

Acetaldehyde, via acetic acid, was used the acetylene synthesis method, as shown in to produce acetone using lime acetate Fig. 4.16 (see Section 4.2.3). Initially, there pyrolysis. It was also possible to make were no other significant industrial organic butanol by aldol condensing acetaldehyde in chemicals made from acetylene except for the presence of an alkali catalyst, then acetaldehyde and acetic acid. dehydrating it to produce croton aldehyde CH3CH=CHCHO, and then hydrogenating this to produce butanol. The Nippon Synthetic Chemical Industry constructed a factory in Uto, Kumamoto, in 1939 as a production base for integrated acetone and butanol production from carbides. This factory directly synthesized its acetone from acetylene and large quantities of steam using iron oxide or zinc oxide as a catalyst, rather than from acetaldehyde and acetic acid. This Fig. 4.16 Change in production volume of process produced hydrogen and carbon acetone and butanol from the 1930s to the dioxide as byproducts. However, the start of 1950s. acetone/butanol fermentation from sucrose in the 1940s and molasses in the 1950s saw the (2) The Organic Synthesis Industry Law fermentation process overtake and dominate The large-scale industrial organic

78 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) chemical industry and synthetic polymer resin) and polystyrene. Besides these, industry underwent significant expansion in chlorohydrin was also being produced from Japan from the late 1930s, when the wartime ethanol via ethylene, and small volumes of economy system came into force. This can be polystyrene were also being produced from seen in laws such as the Artificial Petroleum ethanol and the fragrance β-phenylethyl Production Industry Law and Alcohol alcohol, besides from acetylene, as discussed Monopoly Law of 1937 and the Organic previously. Synthetic rubber will be discussed Synthesis Industry Law of 1940. The in the following section. Methanol was being Artificial Petroleum Production Industry Law produced from syngas since before the aimed to promote the synthesis of petroleum Organic Synthesis Industry Law was enacted. from coal as a national policy. This is Synthetic tannin was industrialized by Nitta discussed later in the section on products Chemical, Nihon Kasei (now Mitsubishi made from syngas (Section 4.7.2). The Chemical) and Mitsui Chemicals. Mitsui Alcohol Monopoly Law promoted the rapid Chemicals used spent sulfite liquor as a raw increased production of fermentation material in its manufacturing process. anhydrous ethanol for a petroleum fuel alternative as a national policy, as discussed Table 4.2 Eighteen products designated by in Section 4.2.1. the Organic Synthesis Industry Law in The Organic Synthesis Industry Law January 1941 aimed for the rapid expansion of organic synthesis businesses. Therefore, while free entry into the main organic synthesis businesses was restricted by government licensing, license holders were given special protection, such as commercial code exemptions in relation to issuing corporate bonds, land expropriation rights as needed, import restrictions on goods that could hinder the establishment of business and manufacturing incentive grants. Organic synthesis businesses essential to the defense Meanwhile, benzene and toluene were industry (synthetic rubber, synthetic toluene, expected to start being produced by etc.) were given additional protection carbide/acetylene synthesis rather than the measures, such as exemptions from income conventional method of fractional distillation tax and sales tax for certain periods, from coal tar (mainly a byproduct of coke exemptions from import tax on necessary production for iron manufacturing). Tokyo imported machinery and testing and research Industrial Research Institute developed this incentives. technology in 1938, and Nippon Carbide Under the Organic Synthesis Industry industrialized 400 tons annual production Law, production expansion or urgent before the Organic Synthesis Industry Law commercialization was deemed necessary for was enacted. However, it was not even able 18 designated industrial organic chemical or to triple this volume before the end of the polymer products (Table 4.2). Many of these war. were industrial organic chemicals or Synthesis of aviation fuel isooctane was polymers made from carbide/acetylene. Of subject to the Artificial Petroleum Production these, the products that could still be Industry Law rather than the Organic classified as being industrially produced from Synthesis Industry Law. Domestic production carbide/acetylene by 1945 were acetaldehyde, was not achieved by the end of the war, acetic acid, acetic acid ester, acetone, vinyl although Chōsen Chisso Hiryō, a Korean acetate (vinyl acetate resin), acetic anhydride subsidiary of Nippon Chisso Hiryō, achieved (acetate), trichloroethylene, vinyl chloride large-scale production in 1942 at its industrial (PVC), methyl methacrylate (methacrylate complex in Hyungnam. By the end of the war,

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production capacity had reached 45,000 tons polymerized. While 2,000 tons of synthetic of acetaldehyde, 30,000 tons of butanol and rubber were produced during the First World 20,000 kL of isooctane. This scale of War, the industry fell into decline after the production was incredibly large for industrial war, as it could not match the performance of organic chemicals at the time, and was made natural rubber. However, a wealth of research possible by large-scale hydroelectric power was conducted on butadiene manufacturing generation, which was not available in and polymerization methods after the war, mainland Japan. The isooctane was both in Germany and in the United States. synthesized through an acetylene – Some of this research found that a acetaldehyde – butanol – butadiene-styrene copolymer showed very evaporation/isomerization/dimerization/hydro good performance and could be used in many genation process. The process from acetylene of the applications for natural rubber. This to butanol was carried out using Nippon copolymer was Buna-S, now called Chisso Hiryō technology, and then the styrene-butadiene rubber or SBR. IG Farben process from butanol to isooctane was carried was granted the German and American out using technology developed by the navy patents in 1929, and constructed a test plant fuel factory. in 1934. Meanwhile, DuPont developed CR From the enactment of the Organic by emulsion polymerization of chloroprene, Synthesis Industry Law in 1940 through to and started industrial production of it in 1932. 1945, the consumption of carbides was Although CR never became a substitute for discouraged for fertilizer, and encouraged for natural rubber, it had a use of its own due to organic synthesis, mineshaft lighting, welding its superior oil resistance. The Standard Oil and cutting, as shown in Fig. 4.14. (New Jersey) developed IIR, an Accordingly, while organic synthesis isobutylene-isoprene copolymer, and started accounted for around 10% of carbide industrial production of it in 1943. IIR was consumption before and after this time period, used in tire tubes due to its low gas it rose to around 15% of carbide consumption permeability. during this period only. This usage was During the Second World War, the entirely for the military. United States had to focus on developing and The Organic Synthesis Industry Law producing synthetic rubber as a national served as an opportunity to develop policy, as Japan had quickly annexed much of large-scale industrial organic chemical and Southeast Asia. The United States produced polymer industries in Japan, and provided a 2,400 tons of SBR in 1942, 180,000 tons in platform for launching a large-scale 1943, 670,000 tons in 1944 and 720,000 tons petrochemical industry within a short space in 1945. By the end of the war, Germany had of time in the 1950s. These industrial an annual production capacity of 150,000 development laws, or business laws, were the tons and produced 110,000 tons in 1944. starting point for the Japanese government’s The industrialization of synthetic rubber idea of strong policy intervention in the in Japan was one of the main objectives for petrochemical industry from the 1950s to the enacting the Organic Synthesis Industry Law. 1980s. Table 4.3 shows the companies that produced synthetic rubber in Japan during the Second (3) Synthetic rubber World War, as well as their production Synthetic rubber was first industrialized methods and products. The Osaka Industrial during the First World War by German Research Institute of the Ministry of company Bayer, amidst a naval blockade. Commerce and Industry started researching The rubber produced was methyl rubber synthetic rubber in 1935, and established a polymerized from 2,3-dimethyl-1,3-butadiene. method of producing butadiene from ethanol Acetone was synthesized from acetylene, by dehydration, dimerizing and then dimerized by pinacol coupling using dehydrogenating using a magnesium oxide metallic magnesium, and then dehydrated to catalyst (the alcohol method). The Institute produce dimethylbutadiene, which was then also perfected a method of extracting

80 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) butadiene using cuprous chloride, and in 1938 Industrial Research Institute transferred to constructed a plant with a 10 kg daily Nihon Kasei (now Mitsubishi Chemical), production capacity. The institute also while a butadiene plant with a 1-ton daily conducted research on polymerization using production capacity was completed in 1942 metallic sodium, as well as copolymerization under the Organic Synthesis Industry Law. with acrylonitrile and styrene. In 1939, a Production then started on NBR synthetic number of engineers from the Osaka rubber.

Table 4.3 Synthetic rubber manufactured in Japan during the Second World War

At the same time, Prof. Junji Furukawa of construction of a butadiene plant with a 1-ton Kyoto University perfected the technology to daily production capacity under the Organic produce butadiene by monovinyl acetylene Synthesis Industry Law. It also built an (MVA) reduction. This technology offered a acrylonitrile plant at the same time, and simpler butadiene production process than the produced NBR synthetic rubber from 1944 alcohol method, and the equipment was also until the end of the war. cheaper. Although Nihon Kasei also built an Nippon Carbide made some advances MVA-reduction NBR plant, the war ended into chloroprene rubber research, based on without it reaching an adequate production studies by Prof. Munio Kotake of Osaka stage due to a shortage of raw materials. University, and developed a production Sumitomo Chemical shifted the Kyoto method using an amino hydrochloric acid University pilot test facilities to its plant in catalyst rather than the ammonium chloride Niihama, and also separately built an used by DuPont. The company completed a acrylonitrile plant and started producing small plant with a 1-ton daily production capacity quantities of NBR synthetic rubber. in Uozu in 1943, but its actual production was Kanegafuchi Industrial Company (now significantly lower than its nominal capacity Kaneka) also completed an MVA-method due to a shortage of raw materials and butadiene-NBR plant in early 1945, but the resources. war ended without it having reached Up until the start of the war, the Japanese sufficient production levels due to air raids government and military took the and other factors. development of a wide range of synthetic Mitsui Mining started its own research in rubbers, including SBR, very seriously. 1937 and perfected a method of producing However, with Japan annexing the southern butadiene via acetaldol by dimerizing regions very soon into the war, it was able to acetaldehyde (the aldol process), and also secure a plentiful supply of natural rubber. developed NBR synthetic rubber production After that, it only encouraged the technology. In 1941, the company started development and production of the highly oil

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resistant NBR and chloroprene synthetic oxidized and reused as acetic acid. rubbers. From 1943 onwards, once the However, in the 1950s, a large-scale wartime situation intensified and the supply demand emerged that completely differed of natural rubber started becoming from the acetaldehyde-acetic acid products problematic, there were not enough resources that had been the main focus of the acetylene in the country and it was not possible to build chemical industry since before the Second general-purpose synthetic rubber plants no World War, and within a short space of time, matter how much the government supported became the mainstay of the acetylene it. chemical industry. This was vinyl chloride and PVC. (4) Vinyl chloride and PVC Vinyl chloride is synthesized by reacting When Japan lost the war in 1945, it lost acetylene with hydrogen chloride. Emulsion its munitions demand in one fell swoop. The polymerization of vinyl chloride produces carbide industry turned its focus to fertilizer PVC. PVC was industrialized in the late once more, as shown in Fig. 4.14. The 1920s in Germany and the early 1930s in the postwar shortages of food and supplies also United States. It appeared in Japan as an meant an increase in the demand for fertilizer, imported sample in 1937, and initiatives and carbide production volumes revived. towards domestic production started right Organic synthesis went back to accounting away. In 1941, Nippon Chisso Hiryō for around 10% of carbide usage. However, industrialized production of PVC (3-ton acetic acid manufacturers began exploring monthly capacity) at its plant in Minamata, areas for large-scale demand outside of the with the idea of exploring new applications conventional areas of acetic acid use for carbides. It also developed its own (solvents, acetic acid esters, vinegar). One monomer and polymer production technology. such area of exploration was the In 1939, it also produced vinyl chloride industrialization of acetate fiber using acetic copolymers. However, the Nippon Chisso anhydride. Another was the development of Hiryō plant in Minamata was destroyed in an products from vinyl acetate. Vinyl acetate air raid in 1945. could be made into vinyl acetate resin, After Japan lost the war, Western polyvinyl alcohol, and the synthetic fiber technology and market information began to vinylon. Production of vinylon started in flow into Japan once more. In 1948, Japan 1949 by Kurashiki Rayon (now Kuraray), imported PVC scraps from the United States, with high hopes for domestically invented which were distributed out to a dozen and producible synthetic fiber. This was manufacturers to research. From 1950 followed by the production of vinylon by onwards, companies started importing a Dainippon Spinners (now Unitika), using succession of Western PVC processing technology developed by Ichirō Sakurada of equipment. The imported PVC made it Kyoto University. Industrial production of possible to create a number of molded acetate fiber was started in 1955 by Teijin products, including wire coatings, film, sheets, using introduced technology; the following leather, belts, tubes and hoses. A number of year, Ryoko Acetate also started production companies noted these market trends and under Mitsubishi Rayon. embarked on domestic PVC production. Acetic anhydride and vinyl acetate were Nippon Chisso Hiryō, which had been in linked in their production. The reaction of production during the war, started out in 1949 acetic acid and acetylene co-produces vinyl with a monthly production capacity of 5 ton, acetate and ethylidene diacetate, as shown in followed by a number of other Fig. 4.15. Over-supply of acetylene at low carbide-acetylene manufacturers in 1950 and temperatures raises the vinyl acetate yield, 1951, including Nihon Kasei (later while the opposite yields more ethylidene industrialized in 1951 as Mitsubishi diacetate. Since pyrolysis of ethylidene Monsanto Chemical, now Mitsubishi diacetate produces acetic anhydride and Chemical), Mitsui Chemicals, Kanegafuchi acetaldehyde, the acetaldehyde can be Chemical Industry (now Kaneka), Tekkoosha

82 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) and Denki Kagaku Kogyo (now Denka). The and vinyl chloride synthesis by chlorine or Yokohama Rubber Company, which had hydrogen chloride addition reactions. Various trialed PVC production during the war, other acetylene-based industrial organic established Zeon in 1950, in conjunction with chemicals were mainly synthesized using Nippon Light Metal, Furukawa Electric and acetaldehyde as an intermediate. Acetylene American company B. F. Goodrich dimerization and pyrolysis reactions rarely Chemicals. Once Mitsubishi Monsanto attained to product production. Chemical and Zeon started producing PVC Meanwhile, Walter Reppe of IG Farben using suspension polymerization method, in Germany was building up fundamental other Japanese PVC manufacturers noted its studies on pressurized acetylene and superior product quality compared to developed technology to handle it safely, as it emulsion polymerization, and all started carried a risk of explosive decomposition. switching over to suspension polymerization Reppe went on to discover four major method in 1952 and 1953 using introduced reactions, shown in Fig. 4.19, and technology. systematized acetylene chemistry. The growth in PVC production volumes Addition reactions of hydroxy groups and was astounding. As Fig. 4.17 shows, it hydrogen halide at atmospheric pressure were quickly dominated the acetylene chemical generalized as vinylation to produce vinyl industry, overtaking acetic acid, which had compounds, whereby alcohols with active been the mainstay of the industry since the hydrogen, phenol, carboxylic acid, amines, acetylene chemical industry began, as well as amides and sulfur compounds add to triple acetic anhydride/acetate and other acetic acid bonds under pressure, as shown in Fig. 4.19. products with expected postwar growth, and Dimerization reactions expanded into also vinyl acetate and vinylon. trimerized or tetramerized cyclic oligomerization. This is also called cyclic polymerization. Reactions not found among acetylene reactions at atmospheric pressure include ethynylation and carbonylation, as shown in Fig. 4.19. Ethynylation is a reaction of methine hydrogen (hydrogen immediately adjacent to a carbon-carbon triple bond) in which the carbon triple bonds in the acetylene are preserved. The method of using an

Fig. 4.17 Change of production volume of ethnylation reaction of acetylene and major acetylene products after the Second formaldehyde to produce 1,4-butynediol, then World War. hydrogenating and dehydrating it to obtain butadiene was industrialized in Germany (5) Reppe reactions during the Second World War. This was one Industrial development of acetylene of the methods of producing butadiene, the chemistry in Japan was mainly through raw material for synthetic rubber, in Germany. atmospheric pressure reactions, as shown in Carbonylation is a reaction of acetylene, Fig. 4.18. The main products were carbon monoxide and substances with active acetaldehyde and vinyl acetate synthesis by hydrogen, using a carbonyl complex of cobalt, hydroxy group addition reactions at nickel and iron as a catalyst. This produces atmospheric pressure, and trichloroethylene acrylic acid derivatives.

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Fig. 4.18 Technology system and major products of acetylene chemistry in Japan before and after the Second World War.

Fig. 4.19 Technology system and major products of Reppe reaction.

Reppe reactions were a type of organic industrialize Reppe reactions in Japan soon synthesis technology from Germany, which died out, and Reppe reactions were forgotten. had no petroleum or natural gas resources, Nevertheless, the idea behind the only coal. After the Second World War, in development of Reppe reaction technology the late 1940s, both the academic world and continued on in later-developed the industrial world in Japan started petrochemical reactions, such as the allyl enthusiastically researching this topic, armed hydrogen reaction [Footnote 6 ] and the oxo only with the domestic resources of coal and process [Footnote 7] to produce carbonyl hydroelectric power. When the United States compounds by reacting olefins with carbon published the PB Report on German wartime science and technology, there was a lot of [Footnote 6] A reaction that preserves the double bonds of the olefin interest in Reppe reactions. However, once but reacts with the hydrogens in the surrounding methyl groups, large quantities of petroleum soon began to producing acrylonitrile, acrylolein/acrylic acid, allyl chloride, maleic anhydride, etc. See Section 6.1.2 (2). be imported from the Middle East, and as [Footnote 7] A reaction that produces butyraldehyde from propylene, petrochemistry developed, the move to higher aldehydes from α-olefins, and propionaldehyde from ethylene. See Section 6.1.2 (1) 5).

84 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) monoxide and hydrogen, although the well. The synthetic pharmaceutical industry reaction mechanisms differ from Reppe started at the end of the 19th century, as reactions. It is fair to say that Reppe reactions typified by Bayer’s aspirin (acetylsalicylic had a significant impact on later acid). Perfumes and fragrances and flavorings, developments in petrochemical technology. artificial sweeteners and a number of other fine chemical industries also began at this 4.6 Industrial organic chemicals and time. After the Second World War, coal tar polymers from coal tar products also came to serve as raw materials for DDT, BHC, 2,4-D, PCP and other The coal carbonization industry began in pesticides. A very diverse range of aromatic the 18th century for producing coke for iron chemical synthesizing technologies manufacturing, as well as for city gas developed before the advent of the production (street lighting, fuel, heating). petrochemical industry. The coal tar chemical Coal tar was an unwanted byproduct of coal industries produced the most diverse range of carbonization. Distilling coal tar produced products and had the most complex structures benzene, naphthalene, anthracene and other of all the forests of coal chemistry. aromatic hydrocarbons, as well as phenols, However, many of these low-quantity, cresols, pyridines and other aromatic organic high-diversity coal tar chemical industries compounds, as shown in Fig. 4.20, with a had no relation to petrochemistry. The residue of around 60% (pitch). While mass-produced aromatic industrial organic aromatic hydrocarbons from petroleum chemicals that were related to petrochemistry distillation are mainly monocyclic (benzene, were phenol and phthalic anhydride. Phenol toluene, xylene), coal tar also produces a was produced from benzene, while phthalic number of fused-ring hydrocarbons anhydride was produced from naphthalene, as (naphthalene, anthracene). For reference, Fig. shown in Fig. 4.20. Other mass-produced 4.21 shows the chemical structures of the aromatic industrial organic chemicals main aromatic hydrocarbons produced from included TDI and MDI from coal tar coal tar, as well as the main industrial organic chemical industries. TDI and MDI were chemicals produced from them. classic coal tar chemistry products: aromatic The coal-tar-based industrial organic amines made by nitrating and reducing chemical industries were based around the aromatic hydrocarbons. However, they are main products produced by distilling coal tar: omitted in this section as their most benzene, toluene, naphthalene and anthracene. significant developments took place in the The synthetic dye industry started in 1856 by petrochemical era. William Henry Perkin, with industries later developing in Germany and Switzerland as

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Fig. 4.20 Major product categories of coal tar as raw material.

4.6.1 Phenol technology in 1916. Phenol can be directly obtained from coal With the industrialization of phenol resin tar, and was used in disinfectants and in the United States in the 1910s, the demand synthetic dyes in the 19th century. The for phenol grew even more. A chlorobenzene demand for phenol increased significantly in process was industrialized in the United the 1880s when picric acid started being used States in the 1920s. This method chlorinated as an explosive, and the production scale had benzene to produce monochlorobenzene, then to shift from that of a dye intermediate to that reacted this with solution of sodium of an industrial organic chemical. Meanwhile, hydroxide in an autoclave to produce phenol industrial production of phenol by coal-tar sodium salt, which was then neutralized with benzene sulfonation process started in hydrogen chloride to produce phenol. Germany in the 1890s. The benzene was The Raschig process was developed and sulfonated in concentrated sulfuric acid, then industrialized in the 1930s. This method neutralized and melted with sodium reacted benzene with hydrogen chloride and hydroxide to produce phenol sodium salt, air with a copper oxide - iron oxide - alumina which was then neutralized to produce phenol. catalyst to produce monochlorobenzene, This was a very complicated and which was then hydrolyzed at the gas phase labor-intensive method of production. In using a silica catalyst to produce phenol. The Japan, Yura Seiko (now Honshu Chemical byproduct hydrogen chloride was then Industry) industrialized production using its re-used. The Raschig process was a far more own developed technology in 1915, while the sophisticated method of production. Mitsui Mining Mitsui Dye Plant (now Mitsui Chemicals) did the same using licensed

86 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Fig. 4.21 Aromatic hydrocarbons and industrial organic chemicals from coal tar.

In 1939, American company DuPont benzene as well. However, since coal tar was industrialized 6,6-nylon. The adipic acid used only produced as a byproduct of coke, it as a raw material for this was made from could not support the rapidly-growing phenol. DuPont claimed it was “fabricated demand for benzene. from such common raw materials as coal, In 1953, the cumene process, a new water and air … as strong as steel, as fine as phenol production method, was developed in the spider’s web.” German company IG the United States and United Kingdom, and Farben industrialized 6-nylon in the early industrialized first in Canada. The cumene 1940s, slightly later than DuPont. The raw process produces cumene from benzene and material for 6-nylon, ε-caprolactam, was also propylene, which is then oxidized and made from phenol. With nylon production cleaved to co-produce phenol and acetone. increasing rapidly after the Second World During the Second World War, cumene was War, the demand for phenol also suddenly produced by petroleum companies as a increased. In Japan, phenol production also gasoline-base material for high-octane rapidly increased from the late 1950s, when gasoline. The cumene process was certainly a industrial production of nylon began in technology suited to petrochemistry. Right earnest, as shown in Fig. 4.22. Production when the petrochemical industry was levels after the war in the early 1950s were on booming in the West, this method took hold a completely different dimension from prewar worldwide, ahead of the chlorobenzene and levels. Raschig methods. It was industrialized in Japan in 1959 by Mitsui Petrochemical Industries using introduced technology. Despite having produced the highest demand for coal-tar benzene, phenol now became completely removed from the coal tar industry, in terms of both supplying raw materials and production technique.

4.6.2 Phthalic anhydride Phthalic anhydride was industrialized in Fig. 4.22 Change of production volume of 1896 by BASF as an indigo dye intermediate. synthetic phenol after the Second World War. It was produced by stoichiometrically

oxidizing coal-tar naphthalene using an The rapid increase in demand for phenol oxidant such as oleum. An atmospheric meant a rapid increase in the demand for oxidation process was developed and

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industrialized in 1916 using a vanadium of phthalic anhydride continued long after the pentoxide catalyst. The development of petrochemical method came into being, and oil-modified alkyd resins in the late 1920s continued to compete with it. This is thought saw an increase in demand for phthalic to be firstly because the catalyst was almost anhydride. In Japan, synthetic dye companies the same and there was no significant started producing phthalic anhydride for their difference in production process costs, unlike own use in the 1930s, while in the 1940s it phenol, and secondly because there was no started being marketed for use in alkyd resins. demand for naphthalene other than for In the United States, where o-xylene was phthalic anhydride, so it ensured the readily available from catalytic reformate, the consumption of products from byproduct coal raw material switched from naphthalene to tar. o-xylene in 1945, using the same catalyst. However, in Europe and Japan, the raw material continued to be naphthalene from coal tar. The rapid increase in PVC production after the Second World War was accompanied by a rapid increase in the demand for phthalic ester as a plasticizer for flexible PVC. In 1952, the first Henkel process, which isomerizes orthophthalic acid made from phthalic anhydride, was developed as a production method for Fig. 4.23 Change of production volume of terephthalic acid, a raw material for polyester. phthalic anhydride for each raw material after In 1958, Kawasaki Kasei Chemicals was the the Second World War. first in the world to industrialize this, followed by Teijin in 1963, resulting in 4.7 Products and technologies from greater increased demand for phthalic coke syngas anhydride. However, the first Henkel process never became a mainstream method of Syngas is a gas mixture of carbon producing terephthalic acid; even in Japan monoxide and hydrogen. Up until the Second production had stopped by the early 1970s, World War, syngas was produced by passing and the demand for terephthalic acid did not red-hot coke through air and steam. last long. Consequently, the forest of chemical products In 1960, Nippon Shokubai started from syngas came to being as the third of the producing phthalic anhydride from o-xylene. coal-based forests. When coal is carbonized, Later, a number of other companies also it produces large quantities of coke oven gas, transitioned to production using o-xylene, which contains carbon monoxide and resulting in the rapid popularization of this hydrogen. While the synthetic ammonia method in the late 1960s, as shown in Fig. industry started in the 1910s using the 4.23. Whereas production from coal-tar hydrogen from coke oven gas, coke oven gas naphthalene lost two of the naphthalene was not enough to supply all the ammonia on carbons as carbon dioxide, o-xylene process its own. Therefore, large-scale production of lost no carbons. Therefore, the naphthalene syngas from coke started in the 1910s. This method was expected to go into rapid decline. was followed by the large-scale production of However, following the 1970s oil crises, syngas in the 1920s as a raw material for there was a revival of the naphthalene methanol synthesis, as shown in Fig. 4.24. production method, as shown in Fig. 4.23. Production of artificial petroleum from The naphthalene method continues to syngas also started in Germany in the 1930s, compete with the o-xylene method despite its using the Fischer-Tropsch process, increasing prevalence. the production of syngas even further. Unlike phenol, coal-tar-based production

88 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

In Japan, Edogawa Industrial (now Mitsubishi Gas Chemical Company) started production of formaldehyde in 1926, with a number of other companies later following suit. This was right when phenol resin production was rapidly increasing, as shown in Fig. 4.25. By 1937, there was enough formaldehyde being produced domestically to Fig. 4.24 Major products made from syngas cover all phenol resin production. The before the emergence of petrochemistry. Organic Synthesis Industry Law designated methanol and formalin (formaldehyde) as raw Another use for syngas is carbon materials for phenol resin, aiming to boost monoxide. Carbon monoxide is used for production from syngas. carbonylation of acetylene with a Reppe reaction. Carbon monoxide also reacts with chlorine to produce phosgene, which is used as a carbonylation agent in the production of dye intermediates and other compounds. Phosgene production and application technology was used after the Second World War to aid the upscaling of isocyanate production as a raw material for polyurethane.

4.7.1 Methanol and formaldehyde Fig. 4.25 Change of production volume of Methanol was extracted from plastic and usage of phenols before the pyroligneous acid in the wood carbonization Second World War. industry and used as a solvent and chemical raw material. When methanol synthesis from While there were essentially no changes syngas was industrialized in Germany in in methanol production methods after the 1925, wood-carbonization-based methanol Second World War, the raw material for suddenly came to an end. Methanol synthesis syngas shifted from coke to natural gas. In technology could be said to be an extension Japan, Japan Gas Chemical (now Mitsubishi of ammonia high-pressure synthesis Gas Chemical Company) started producing technology. It was industrialized in Japan in syngas and methanol from natural gas from 1932 by Gosei Kogyo (now Mitsui Niigata as early as 1952. This was the Chemicals) based on research from the foundation of the Japanese petrochemical Temporary Nitrogen Research Institute (later industry, as shall be discussed in Section the Tokyo Industrial Research Institute; now 5.3.3. In 1958, Toyo Koatsu (now Mitsui the National Institute of Advanced Science Chemicals) started methanol production using and Technology). This was followed by a natural gas from Mobara, while Akita number of other companies entering the Petrochemical (a joint venture between industry. Sumitomo Chemical and Teikoku Oil) did the The main use for methanol was, and still same using natural gas from Akita, followed is, formaldehyde. Formaldehyde was used as in 1962 by Nissan Chemical Industries using a raw material for phenol resin, and was natural gas from Nagaoka and Kyowa Gas produced by dehydrogenation or oxidative Chemical using natural gas from Nakajo. dehydrogenation of methanol. A copper Petrochemical industries developed all over catalyst process originated in Germany in Japan using this rare domestic resource. Thus, 1889; in 1910, a silver catalyst process was although the production technology for developed as well, with a liquid phase methanol, the core product for syngas reaction carried out with excessive methanol. chemistry, had been developed in the coal

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chemistry era, it continued on into the petrochemical era and survived. 4.7.2 Artificial petroleum While many other raw materials for The Artificial Petroleum Production syngas came along later, such as naphtha, Industry Law was enacted in 1940, aimed at petrochemical waste gas and LPG, ultimately, reinforcing artificial petroleum research, there was not enough affordable natural gas industrialization, and increased production in in Japan, and it came to a sudden end in the Japan as a matter of national policy. The 1980s. following four technologies were the main An oxidation method of producing technologies targeted. formaldehyde using excessive air and an iron (1) Low-temperature coal carbonization oxide or molybdenum oxide catalyst was (2) The Bergius process (direct liquefaction developed during the Second World War and of coal) industrialized by DuPont. Many of the (3) The Fischer–Tropsch process processes in this gas-phase oxidation method (4) Oil shale retorting were developed after the war by eliminating Of these, the processes that became the the reaction heat, and increasing the mainstay of production from 1941 to 1945 concentration of formaldehyde produced. were (4) followed by (1), as shown in Table Formaldehyde gained new areas of postwar 4.4. Oil shale retorting (4) is an old demand for urea resin and melamine resin, technology that had already been along with phenol resin. Urea resin in industrialized in the mid-19th century. Since particular had the highest production volume Japan had access to a thick oil shale layer of all plastics, overtaking phenol resin from above the Fushun coal mine in Manchuria, it the late 1940s to the early 1950s, as shown in had been exploring uses for it between 1912 Fig. 4.26. It was used in adhesives and and 1926. However, it was not very electrical components, like phenol resin, and economical to use European technology, as also in tableware, buttons and other everyday the Fushun oil shale had a lower oil content molded products, as it did not go brown like than the oil-rich European oil shale, at 6–8%. phenol resin. Manchuria Railway developed an internally-heated retorting furnace, and built a factory in 1929. As the shale oil obtained was heavy, a Dubbs process pyrolysis furnace was promptly brought in from the United States, and production started in 1935.

Table 4.4 Production volume of artificial petroleum in Japan and Manchuria during the Second World War

Fig. 4.26 Change of production volume of major plastic after the Second World War.

Thus, formaldehyde maintained an important position as a raw material for plastic for around a decade following the Second World War. However, in the late 1950s, urea resin was dispossessed by PVC as the chief among plastics, and furthermore

it was outstripped by polyethylene, the The technology for (1) low-temperature mainstay product of petrochemistry, in the coal carbonization was also very old early 1960s. Thus, formaldehyde lost its place technology, originating in 18th-century as a key raw material to acetylene, and then Germany. In Japan, Osaka Kanryu Kogyo to ethylene. started production using this technology in

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1922. During the Second World War, eight world started working on how to improve it. large-scale plants were established: Chōsen In Japan, this was done at the Genitsu Kita Chisso Hiryō in Hamgyong (1932), Japan Laboratory at Kyoto University, and later Iron & Steel in Muroran, Ube Nitrogen developed independently using an iron Industry in Ube, Mitsubishi Mining in catalyst. Naihoro, Tokyo Gas in Tsurumi, Nissan In Germany, the process was Chemical in Wakamatsu, Ube Yuka in Ube industrialized in 1936 by Ruhrchemie, with a and Sakhalin Artificial Petroleum in Naibuchi. number of other companies following suit. As While six of the plants used non-caking coal a result, Germany had a production capacity as a raw material and were able to use of 740,000 tons during the Second World introduced technology from Germany, the War, with production levels reaching as high Japan Iron & Steel plant in Muroran and the as 570,000 tons. In Japan, Mitsui Mining Tokyo Gas plant in Tsurumi used caking coal signed a technology licensing agreement as as a raw material and so had to use their own early as 1936, constructing a plant in Omuta technology. and starting operation in 1940. While the By contrast, technology for (2) the company underwent a variety of changes Bergius process (direct liquefaction of coal) during the war, the majority of product made and (3) the Fischer–Tropsch process was using the Fischer–Tropsch process was developed early in the 20th century in produced at this factory in Omuta, as shown Germany. The Bergius process (2) was in Table 4.4. developed in the 1910s by Friedrich Bergius. In 1937, the government enacted the In this process, coal powder was added to Imperial Fuel Industry Company Act, and heavy oil and then liquefied by high-pressure established a special company for the purpose hydrogenation. IG Farben acquired the patent of producing artificial petroleum. Plants using from Bergius in 1927 and carried out further a 10 atm increased pressure method were research and improvements. A low level constructed in Takigawa (Hokkaido Artificial sulfur poisoned catalyst was developed, and Petroleum) and Amagasaki (Amagasaki industrial production started in 1932 using Artificial Petroleum), and the Takigawa plant lignite as a raw material. The resulting started production in 1943. In 1944, the product was high in aromatic hydrocarbons Omuta, Takigawa and Amagasaki artificial and served as the artificial petroleum most petroleum companies merged to form the suitable for aviation fuel. Since IG Farben Nippon Artificial Petroleum Company, with kept the technology a secret, in Japan, the the aim of boosting artificial petroleum navy fuel factory carried out its own production through technology exchange, independent research. In 1935, the navy utilizing materials and facilities, dedicating commissioned the construction of plants in Omuta to catalyst production and other Fushun by Manchuria Railway and Aoji by initiatives. However, although the Fischer– Chōsen Chisso Hiryō. However, these never Tropsch process was where the government reached sufficient production levels by the spent most of its efforts, artificial petroleum end of the war as the technology was production using this method also remained incomplete, as shown in Table 4.4. low at the end of the war, as shown in Table Meanwhile, the Fischer–Tropsch process (3) 4.4. used a cobalt catalyst to synthesize liquid The artificial petroleum division at hydrocarbons from syngas at pressure levels Omuta branched out on its own as Miike from 1–10 atm. Since the resulting product Gosei Chemical Industry in 1946, using the was a straight-chain hydrocarbon, it had the artificial petroleum plant coke ovens and disadvantage of a low octane number. It also syngas facilities to supply syngas to had a wide carbon number distribution and neighboring Toyo Koatsu as a raw material would not always produce adequate quantities for ammonium sulfate. The company later put in the necessary gasoline fraction. the rest of the unused artificial petroleum Nevertheless, when the German patent was facilities to use and started producing disclosed in 1925, researchers all around the petroleum-based synthetic detergent.

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Of all the Mitsui chemical companies, [2] T. Watanabe, ed. “History of postwar Miike Gosei Chemical Industry is notable as Japanese chemical industries,” The the first postwar petrochemical industry and Chemical Daily, 1973. for having played a pioneering role in [3] T. Iijima, “Japanese chemical domestic petrochemical production. The technology,” Kogyo Chosakai, 1981. company’s experience with artificial [4] T. Takahashi, “History of the chemical petroleum technology arguably gave it the industry,” Sangyo Tosho, 1973. insight to see the potential in the [5] “History of the Japanese chemical fiber petrochemical technology developed in the industry,” Japan Chemical Fibers United States. However, in the late 1950s, as Association, ed., Japan Chemical Fibers the raw material for ammonia gas started Association, 1974. changing in earnest from coke and coal [6] H. Uchida, “New revised edition: The gasification to petroleum gasification, natural synthetic fiber industry,” Toyo Keizai, gas and petrochemical waste gas, Miike 1970. Gosei could no longer support its coke oven [7] K. Fukushima, “Viscose rayon (1), (2), operations. Thus, all operations using (3),” Kagaku Kōgyō., pp. 623-631, inherited artificial petroleum facilities came 711-719, 800-807, 1988. to an end. [8] I. Iwai, Polyfile., vol. 52, 2013, pp. There are various opinions on the role 12-15. played by artificial petroleum technology in [9] H. Ōsuga, Journal of Packaging the formation of petrochemical technology. Science & Technology, Japan, vol. 22, IG Farben, which had worked on the direct pp. 254-261, 366-373, 2013. liquefaction of coal, (2) above, collaborated [10] “A 30-year history of the alcohol with the Standard Oil (NJ) and other monopoly,” Ministry of International companies in the early 1930s by providing Trade and Industry, Chemical Industry hydrogenation patent rights. Since this Bureau, Alcohol Division, ed., contributed to the development of heavy oil Fermentation Association of Japan, hydrocracking technology and other 1969. American technologies, there is an idea that [11] “A 50-year history of the alcohol this formed the basis for the creation of monopoly Business,” Ministry of petrochemical technology. However, heavy International Trade and Industry, Basic oil pyrolysis technology developed in the Industries Bureau, ed., Japan Alcohol United States in the 1910s, and ethane steam Association, 1987. cracking technology in the early 1920s, [12] K. Kurono, “Alcohol and anhydrous before artificial petroleum technology was alcohol,” Senbai Kyokai, 1937. developed. Accordingly, it is difficult to give [13] B. Katō, ed., “The history of alcohol in credence to the idea that artificial petroleum Japan: Its industries and technologies,” technology gave rise to petrochemical Kyowa Hakko Kogyo, 1974. technology. In terms of mastering large-scale, [14] “A 50-year history of Sanraku,” continuous operation technology, methanol Sanraku History Compilation Office, and artificial petroleum can be viewed as Sanraku, 1986. having laid the foundation for the ready [15] “History of Japanese naval fuel, I & II,” adoption in the 1950s of American Fuel Society, ed., Hara Shobo, 1972. petrochemical technology in areas like [16] T. Kume, “Early polyethylene Europe and Japan, where no large-scale production in Japan,” Journal of the petroleum refining technology had developed. Society of High Pressure Gas Industry, vol. 21, pp. 274-281, 1957. Bibliography [17] “20th-century Japanese chemistry [1] T. Watanabe, ed., “History of the technology,” The Japanese Society for development of the modern Japanese the History of Chemistry, ed., The industries 13: chemical industries (I),” Japanese Society for the History of Kojunsha, 1968. Chemistry, 2004.

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[18] “Magazine for the 50th anniversary of [30] E. Munekata, “Coal liquefaction by the institute,” Hodogaya Chemical internally-heated reaction tube,” Institute, ed., Hodogaya Chemical Kagaku Kōgyō, pp. 189-199, 1989. Central Research Institute, 1989. [31] M. Esaki, “Synthetic methanol (1), (2),” [19] “The 200-year journey of Shiono Koryo Kagaku Kōgyō, pp. 958-967, 1036-1043, Kaisha Limited,” Shiono Koryo Kaisha, 1990. ed., Shino Koryo Kaisha, 2010. [32] “History of Mitsui Toatsu Chemicals, [20] “From there to there: Kyowa Hakko’s Inc.,” Mitsui Toatsu Chemicals, Mitsui 50-year journey and the foundation for Toatsu Chemicals, 1994. the new century,” Kyowa Hakko 50th [33] “An outline of the development of poly Anniversary History Compilation vinyl chloride technology in Japan, Committee, ed., Kyowa Hakko Kogyo, including a description of historical 2000. materials,” Survey Report on the [21] “A 70-year history of Kao Sekken,” Systematization of Technologies, no. 1, Kao Sekken, 1960. National Museum of Nature and [22] “100-year history of Kao,” Kao History Science, March 2001. Compilation Office and Japan Business [34] “Systematic survey of technological History Institute, Kao, 1993. development in laundry soaps and [23] H. Nagata, “The organic synthesis detergents,” Survey Report on the industry law,” Journal of the Society of Systematization of Technologies, no. 9, Rubber Science and Technology, Japan, National Museum of Nature and vol. 13, pp. 537-544, 1940. Science, March 2007. [24] “Chemical industries: The postwar [35] “Systematic survey of the development half-century and 21st century prospects,” of paint technologies,” Survey Report Chemical Economy Research Institute, on the Systematization of Technologies, 1996. no. 15, National Museum of Nature and [25] “History of the carbide industry,” Science, March 2010. Calcium Carbide Association, ed., [36] “Systematic survey of dye technologies,” Calcium Carbide Association, 1968. Survey Report on the Systematization of [26] K. Ishibashi, “Petrochemicals,” Technologies, no. 16, National Museum Kyoritsu Shuppan, 1953. of Nature and Science, March 2011. [27] “German organic synthesis technology: [37] “Historical development of pesticides in PB report compilation I,” The Society Japan,” Survey Report on the of Synthetic Organic Chemistry, Japan, Systematization of Technologies, no. 18, ed., Maruzen, 1954. National Museum of Nature and [28] S. Murahashi, “Studies of Science, March 2013. Reppe-reaction in Japan”, Journal of [38] H.A. Wittcoff, B.G. Reuben, J.S. Synthetic Organic Chemistry, Japan, Plotkin “Industrial Organic Chemicals,” vol. 13, no. 5, pp. 195-202, 1955. Wiley, New York (Third Ed.), 2013. [29] H. Akune, “Development and future [39] S. Kodama, “The road to research and challenges of synthetic petroleum (1), development,” Tokyo Kagaku Dojin, (2)”, Kagaku Kōgyō, pp. 1058-1087, 1978. 1988; pp. 99-111, 1989.

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History of the petrochemical industry 5

As mentioned at the beginning of the and fraught with many issues. Since letting previous chapter, petrochemistry began as a the chemical industry deteriorate was not an small forest in the United States in the 1920s, option, regions that were not blessed with existing alongside and competing with forests these resources went through a process of from other more prevalent materials for 30 trial and error to keep petrochemistry alive. years. The field as we know it today did not From this came initiatives in functional exist in Europe and Japan; however, it began chemistry that stretched beyond the making inroads into Europe in the 1950s and conventional scope of the field of changed dramatically with the incorporation petrochemistry as well as the development of of European chemical technology. Crude oil new technologies with the potential to was discovered in the Middle East in the transform petrochemistry from its roots. 1930s, but major exports did not begin until the 1950s, after which time it became a 5.1 The 1920s: An industry is born in cheaper source of energy than coal and the United States products derived from fermentation. This is another major reason for the change in the The oil industry in the United States petrochemical industry. began with the successful drilling of an oil The 1960s proved to be a period of Sturm well in Pennsylvania by Edwin Drake in 1859. und Drang for petrochemistry. Researchers in By the end of the 19th century, a raft of new the field were developing a rapid succession oil fields had sprung up across the United of technologies that could enable the cheaper States, in states such as Illinois, Kansas, production of products typically yielded Oklahoma, Texas, Louisiana and California. through other chemical processes. Thus, Initially, kerosene was the primary driver of petrochemistry soon overtook other fields the demand for oil; however, when the Model engaged in the mass production of chemical T Ford went on sale in 1908 and ushered in products to assume sole possession of the an era in which the automobile became chemical industry. From the 1970s onward, accessible to everyone, the demand for oil in several crises, from environmental and the United States shifted to gasoline, which energy issues to chemical pollution and remains the case to the current day. global warming, have threatened to unseat It was in this context that oil refining petrochemistry. This has led to a partial technologies were developed, as shown in revival of the fields of oleochemistry and Table 5.1, and from this grew the fermentation chemistry, with some countries, petrochemical industry. such as China, trying to put policy measures in place to restore coal chemistry for the sake 5.1.1 Thermal cracking of heavy oil of economic security. For over 50 years, The oil refining system for continuous however, the field of petrochemistry has distillation was introduced in 1910. Gasoline successfully maintained its position at the accounted for a large portion of the oil foundation of the chemical industry by demand in the United States, but the offering solutions to various problems that distillation of crude oil resulted in an excess have arisen. of heavy oil. Therefore, to increase the From its origins in the developed nations, gasoline yield from crude oil, refineries began petrochemistry began to spread to every to thermally crack oil, and in particular, corner of the world in the 1970s. heavy oil. The Burton process was developed Consequently, regions rich in raw materials in 1912, followed by the Dubbs process in of oil and natural gas came to develop a 1914, and multiple other thermal cracking strong competitive edge in the field of processes were developed thereafter. petrochemistry. In many cases, this shift was Thermally cracked heavy oil yields gasoline politically motivated, such as Saudi oil prices, and other light distillates, as well as

94 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) petroleum waste gas containing hydrogen, propylene and butylene) and large amounts of alkanes and lower olefins (i.e. ethylene, carbon.

Table 5.1 Oil refinery and petrochemical industry in the U.S. in the 1920s to the early 1930s (excluding organic chemicals or polymers made from raw materials other than natural gas or oil)

5.1.2. The birth of the petrochemical reduced partial pressure and shortened industry retention time with the addition of steam. In 1920, chemists at Standard Oil (NJ) Thus was born the method for steam cracking Bayway Refinery caused a reaction between oil and natural gas, which remains to this day the propylene from petroleum waste gas and an important technique for the production of sulfuric acid to create propyl sulfate, which basic petrochemicals. The technique used to they then combined with water to produce separate ethane from natural gas and ethylene Isopropyl alcohol (IPA). This is considered to from product gas was low-temperature be the beginning of the petrochemical distillation. Linde Air Products, one of the industry. Isopropyl alcohol was oxidized to four companies involved in the establishment give acetone, and also used as a solvent. of Union Carbide and Carbon, contributed Using a similar technology, Shell altered the significantly to the development of this concentration of the sulfuric acid in butylene, technology in 1917. Linde AG, the German yet another substance in waste gas, to parent company of Linde Air Products successfully separate out n-butylene and initially achieved the successful industrial isobutylene. In 1931, the company went on to application of air liquefaction equipment and produce sec-butyl alcohol and MEK from equipment that used the distillation of liquid n-butylene. MEK, like acetone, was also used air for separation from around the end of the as a solvent. 19th century to the turn of the 20th century (see Section 2.3.2). 5.1.3 Steam cracking of ethane Meanwhile in 1920, Union Carbide and 5.1.4 Development of ethylene products Carbon founded a subsidiary called Carbide In 1925, Union Carbide and Carbon and Carbon Chemicals which began reacted ethylene and chlorine with water to producing ethylene in its Clendenin, West create ethylene chlorohydrin, which it then Virginia facility by the steam cracking of hydrolyzed to produce EG. At that time, EG ethane separated out from natural gas. Unlike was solely used as automotive antifreeze, and the old process that entailed the thermal the company held a monopoly over the cracking of heavy oil at a high temperature substance up until the Second World War under high pressure, this innovative method broke out. By developing a use for ethylene

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dichloride (EDC), a byproduct from the acetaldehyde by oxidizing ethanol. production of ethylene chlorohydrin, the Coinciding with this, the company ceased company also pioneered the market for dry producing acetylene-based acetaldehyde at its cleaning solvents. In 1929, the company Niagara Falls plant. began producing polyvinyl chloride In 1922, Standard Oil (NJ) began (monomer), which was created from the commercially manufacturing tetraethyl lead, a thermal cracking of EDC. Around this time in gasoline octane enhancer discovered by GM Germany, a polyvinyl chloride was developed, the year before at its Bayway refinery. The although polyvinyl chloride had been ethyl chloride used in this process was recognized as a compound since the 19th derived from ethylene contained in the waste century. Union Carbide and Carbon had gas produced during the thermal cracking of also attempted to polymerize this compound, heavy oil. There was more ethylene in the but failed for the lack of the waste gases produced during thermal photostabilization and molding technologies cracking than in the catalytic cracking of required to produce polyvinyl chloride. Not heavy oil, a process that was developed later long after this, however, the company and adopted widely. In 1923, DuPont also succeeded in developing a special polyvinyl opened a factory to produce tetraethyl lead. chloride by copolymerizing polyvinyl DuPont used fermentation ethanol to produce chloride and vinyl acetate; this polyvinyl ethyl chloride. GM and Standard Oil joined chloride started being used by the vinyl forces to establish a tetraethyl lead record industry in the United States. manufacturer called Ethyl, thus putting the In 1926, Union Carbide and Carbon production of the compound into high gear. synthesized ethylene oxide by To supply Ethyl with the ethylene it needed, dehydrochlorinizing ethylene chlorohydrin in Standard Oil built a propane steam cracking an alkaline solution. As mentioned in Section facility to replace the old practice of 3.4.2 (2), ethylene oxide is a highly reactive collecting ethylene from heavy oil pyrolysis organic intermediate that now has myriad waste gas. This technology was based on the applications. At that time, however, it was ethane steam cracking process used by Union reacted with cellulose to produce Cellosolve, Carbide and Carbon, but using propane an ingredient in lacquer solvent. In 1931, the yielded more products, so new separation and French chemist T.E. LeFort invented a collection technologies were needed. The method for creating ethylene oxide by the company also pursued research into the steam direct oxidation of ethylene using a silver cracking of naphtha and gas oil, as will be catalyst. Union Carbide and Carbon adopted discussed in the next section. this method, and launched the first industrial Thus, the petrochemical industry application of this method in 1937. After this, gradually grew in step with the expansion of it was found that EG could be produced by the oil refining industry during the 1920s and reacting ethylene oxide with water, thereby the 1930s. Notwithstanding, the demand for eliminating the need to first produce ethylene compounds other than tetraethyl lead was chlorohydrin. In the early days of the limited to solvents and antifreeze agents such petrochemical industry, the invention of as oxygen-containing alcohols and ketones. methods like LeFort’s, which permitted the At this point, no connection had been made direct oxidation of olefins with a solid with polymers, and the industry remained catalyst, was astonishing. small. The biggest oxygen-containing In 1930, Union Carbide and Carbon compound of this era was still fermentation began producing ethanol from ethylene by ethanol. Therefore, even though it is true that applying the sulfuric acid process to ethylene. the petrochemical industry originated in the This was the same technique that Standard United States, its scale remained limited. Oil (NJ) used to produce IPA and Shell used to produce sec-butyl alcohol, as mentioned 5.1.5 Wood chemistry and coal chemistry previously. Around this time, Union Carbide usher in the polymer era and Carbon also began producing The United States of the 1920s was the

96 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) world’s first mass consumer society. In 1930, World War, with the mass production of the first supermarket was opened. Concurrent synthetic rubber as the catalyst. An outline of with this, the use of plastic began to spread the advancements in oil refining and throughout the United States from the 1920s petrochemical technologies in the latter half onwards, ushering in the dawn of an era of of the 1930s can be found in Table 5.2. polymer materials. These polymers, however, were not derived from oil, but from wood and Table 5.2 Oil refinery and petrochemical coal. The polymers that were frequently used industry in the U.S. in the late 1930s to the in the United States in the 1920s included 1940s celluloid, phenolic resin, viscose rayon and (excluding organic chemicals or polymers acetate. By the 1930s, these were joined by made from raw materials other than natural moisture-proof cellophane, urea resin, gas or oil) polyvinyl acetate, polyvinyl chloride, methacrylate resin and chloroprene rubber. Nylon was developed at the end of the 1930s, leaving a lasting impression on people the world over, and marking the dawn of the polymer era, not only for the United States, but for the rest of the world as well. Other than the United States, many of the countries that developed these polymers were in Europe. Consumerism had yet to take root there at that time. Plastic was seen as a cheap 5.2.1 Catalytic cracking of heavy oil substitute for other materials, and its benefits, In 1938, French engineer Eugene Houdry such as the freedom it allowed in product developed the fixed-bed catalytic cracking design, were not as highly regarded as they process as a replacement for the thermal were in the United States. Accordingly, the cracking of heavy oil, with the aim of polymer age had not yet begun in Europe. increasing gasoline yield. Once this In Japan, meanwhile, the industrial technology was adopted in the United States, production of celluloid and viscose rayon had it spread like wildfire. Fluidized catalytic begun in the early 20th century and started cracking (FCC), the process currently used booming in the 1920s. By 1937, Japan had around the world today, was developed by become the world’s biggest producer of both Standard Oil (NJ) and was adopted at their of these polymers (see Section 4.1). This, Baton Rouge refinery in 1942. However, however, was merely in response to export FCC was not widely adopted in the United demand from the United States; Japan had not States or anywhere else in the world until yet experienced the full effects of consumer after the war. Since catalytic cracking society. The production of synthetic employed a different reaction mechanism compound phenol resin began in the 1910s, from thermal cracking, it generated much and the use of electric lamps, radio parts and more petroleum waste gas. This, however, other electrical components, rayon had a different composition from the manufacturing pots and spinning machinery petroleum waste gas generated by thermal components started spreading in the 1930s, , cracking; it contained very little ethylene and although Japan was still a far cry from the large amounts of propylene and butylene. dawning of the polymer era. With the widespread adoption of catalytic cracking, the supply of lower olefins began to 5.2 The 1940s: Advances in the skyrocket in the United States in the early American petrochemical industry 1940s. Thus began the fully-fledged development of olefin chemistry. After roughly 20 years, the petrochemical industry in the United States transitioned out 5.2.2 Mass production of gasoline-based of infancy with a major boom in the Second materials from petroleum waste gas

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As mentioned previously, alcohol is As mentioned previously, Standard Oil produced by causing a reaction between an (NJ) successfully developed a method for the olefin and sulfuric acid. By changing the steam cracking of naphtha, which it put into reaction conditions and using hot sulfuric commercial use in its Baton Rouge refinery in acid, butylene undergoes acid-catalyzed 1941. Unlike the processes based on ethane dimerization to generate polymer gasoline and propane, the use of naphtha enabled the [Footnote 1]. This polymer gasoline can then production of butadiene, an important be hydrogenated to obtain isooctane. compound for the United States during the Isooctane was a key ingredient in aviation Second World War, as outlined below. In fuel, which has to have a high octane number. order to obtain butadiene from a C4 fraction Shell opened an isooctane plant in 1934, and from the steam cracking of naphtha, Standard Standard Oil (NJ) soon followed suit. Oil (NJ) first developed an extraction method In 1939, both companies succeeded in using a copper ammonia solution. commercially producing alkylate gasoline through the alkylation of isobutane with 5.2.4 Synthetic rubber production butylene and propylene. As opposed to increases polymer gasoline, alkylate gasoline does not During the Second World War, the need to undergo hydrogenation after United States government put the Synthetic dimerization. In 1942, Shell successfully used Rubber Program into action, which was a an acid catalyst to synthesize cumene from plan to build factories to boost the production benzene in coal tar and propylene in of synthetic rubber. This served as the largest petroleum waste gas. Cumene, polymer trigger for the advancement of the American gasoline, isooctane and alkylate gasoline all petrochemical industry. As the Japanese army have high octane numbers and were used as had captured the Malay Peninsula and key ingredients in good quality Indonesia early in the war, it became clear to gasoline-based materials. In particular, they the United States that it would soon suffer a were in high demand as essential aviation shortage of natural rubber. Accordingly, the fuels during the Second World War. While government devised a plan to dramatically these gasolines were mass produced using increase the production of synthetic rubber. olefin chemistry, it was the petroleum The United States needed a particularly large refining industry that created and used them, amount of SBR, which was used to make tires rather than the chemical industry. (see Section 4.5.2 (3)). It also needed the Also in 1939, German company IG highly oil-resistant NBR. These synthesizing Farben developed a process for the catalytic technologies were part of IG Farben’s reforming of naphtha (using a molybdenum synthetic rubber research conducted under an oxide-alumina catalyst). During the war, this expanded technology alliance agreement technology was applied by Standard Oil (NJ), concluded between IG Farben and Standard Standard Oil (Indiana), and the Kellogg Oil (NJ) in 1930; thus, it was through Company, which helped boost the supply of Standard Oil (NJ) that the government high-octane gasoline. However, since a became aware of these technologies. sufficient supply of aromatic hydrocarbons to Accordingly, the government was able to the chemical industry in the United States execute its Synthetic Rubber Program within could be obtained from the distillation of coal an extremely short time frame. By contrast, as tar, it was exclusively obtained this way mentioned in the previous chapter, Japan was during the Second World War, other than much further behind in its efforts to some obtained from toluene [Footnote2]1.. commercialize synthetic rubber.

5.2.3 Steam cracking of naphtha 5.2.5 Butadiene There were several avenues for the

[Footnote 1] Polymer gasoline is an imprecise term used in the supply of butadiene, the primary raw material petroleum refining industry. It is an established term, although as a in synthetic rubber. In 1943, Humble Oil, a hydrocarbon with around C8, it is not a true polymer. [Footnote 2] The demand for toluene during the war focused heavily subsidiary of Standard Oil (NJ), built a on its use as a raw material for explosives.

98 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) butylene dehydrogenation plant. When the United Kingdom, fermentation ethanol was supply of butylene from petroleum waste gas the raw material used to make ethylene. grew short, it then developed a method to During the Second World War, ICI provided dehydrogenate butane (i.e. the Houdry its technology to the United States, and in process). This technology was abandoned 1943, both Union Carbide and DuPont after the Second World War due to its high opened ethylene factories. cost. In addition, the company also used the Meanwhile, Standard Oil (NJ) developed aforementioned process developed by and commercialized butyl rubber, which has Standard Oil (NJ) to extract butadiene from a an excellent gas barrier, making it ideal for C4 fraction from the steam cracking of use in tire tubes. This was a special rubber naphtha. Surprisingly, however, the greatest produced by the polymerization of source of butadiene was fermentation ethanol. isobutylene and a small amount of butadiene In the United States, fermentation ethanol at low temperatures. After the war, isoprene was made from corn. Due to the influence of obtained from the steam cracking of naphtha the agricultural lobby, the mainstream was used in place of butadiene. process was a long one: acetaldehyde and In this way, the United States aldol were condensed from fermentation petrochemical industry, which had been ethanol, then hydrogenated and dehydrated. unable to create any lasting linkages with During the war, Union Carbide significantly polymers up through the 1930s, finally started shortened the process with the development doing so during the Second World War with of a new method for producing butadiene by polymers such as synthetic rubber, condensing ethanol and acetaldehyde using a polyethylene and polystyrene. Meanwhile, silica catalyst. Union Carbide mass produced private-sector demand shrank during the synthetic ethanol from the ethylene obtained Second World War for celluloid, phenol resin, by the steam cracking of ethane and used this urea resin, polyvinyl chloride, methacrylate as the raw ingredient for butadiene. resin and nylon, which had already ushered in the polymer age in the United States in the 5.2.6 Linking olefin chemistry and 1920s and 1930s, while demand coming polymers almost exclusively from the military led to Styrene, the other main ingredient in SBR stepped up production. For example, the synthetic rubber, was first put into production nylon fibers that first went on sale in the form by German company IG Farben in 1930 in of stockings were used during the war for the form of polystyrene. In the United States, parachutes, tents and ropes as well as a Dow Chemical began producing polystyrene variety of other wartime goods, such as in 1937, but the scale of the operation was so mosquito nets used to protect soldiers in the small that almost no one in the market knew tropics. Polyvinyl chloride, used to make soft about it. However, during the Second World vinyl chloride products, was also important as War, styrene became an indispensable raw a flame-retardant wire coating material. material for SBR tires, so efforts to step up However, these plastics and synthetic fibers production were undertaken by four that were mass produced in the United States companies: Dow Chemical, Monsanto, during the war were still mostly derived from Koppers, and Union Carbide. The benzene wood and coal. for synthetic rubber was obtained entirely from coal tar. During the war, styrene 5.2.7 Interest in polymers increases demand was essentially driven by SBR alone. The United States army brought with it Meanwhile, polystyrene production volume American-made plastic and synthetic fiber remained small, as it was primarily only used products to the European front, resulting in by the military as an insulating material for the superiority of these products coming to be radars. Another essential material used in recognized in Europe as well. Meanwhile, in radar insulation was low-density polyethylene Germany, which had also ramped up its (LDPE), invented by British company ICI in synthetic rubber production during the war 1933 and put into production in 1939. In The like the United States had, demand for

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butadiene increased rapidly. The demand for concentration of these compounds it contains. the antifreeze EG and ethylene, the source of Meanwhile, in the United States, a method the styrene used in synthetic rubber, also was developed to extract and recover skyrocketed. In Germany, the primary raw aromatic hydrocarbons from catalytically material for these chemical products was coal reformed naphtha, mass produced in an effort (from acetylene, coke oven gas and coal tar), to obtain high-octane gasoline, and it was but fermentation ethanol was also an soon adopted widely. This technology was important raw material. also used to recover aromatic hydrocarbons Products that were manufactured in the from cracked gasoline. Throughout the 1950s, United States as important military goods the source of aromatic hydrocarbons in both were also known in Japan, such as polyvinyl the United States and in Europe shifted chloride, polyethylene, polystyrene, synthetic significantly from coal tar to petroleum. The rubber and nylon fiber. Japan scrambled to same shift began in Japan in the late 1950s, ramp up its domestic production of these about five years behind Europe. goods, and, as mentioned in the previous In the field of industrial organic chemical chapter, research was undertaken, backed by production technologies, a direct catalytic the government and the military. The raw hydration process was also developed in materials for these products were place of the sulfuric acid process traditionally domestically-available coal and fermentation used in the production of ethanol and IPA; ethanol. Research and development this was commercially applied in 1948. Thus, progressed despite the lack of information technologies were developed that used from the West, and, during the war, Japan catalysts, in particular solid catalysts to managed to put several polymers into achieve direct production, or production of production, although production volumes organic intermediates from olefins and were minimal. 1940s Japan had yet to see the aromatic hydrocarbons, and these dawning of the age of synthetic polymers that subsequently became the mainstream in the would replace the cellulose-based polymers petrochemical industry. of the 1930s. In the 1950s, polymer production technology took a great leap forward with the 5.3 The 1950s: The fusion of American discovery of Ziegler-Natta catalysts. The petrochemical technologies and discovery of these organometallic complex European chemical technologies catalysts not only became, and continues to be, the key driving force behind By the 1950s, the petrochemical industry advancements in polymer production was no longer confined to the United States; technology, it also triggered dramatic leaps in it had spread to Europe and Japan. The the petrochemical industry in terms of integration of petrochemical technologies production volume. What is notable is that with manufacturing technologies for the mass this discovery was made in Germany and production of chemical products, which had Italy, not in the United States, which had made advances in Europe even before been the birthplace of the petrochemical petrochemistry began, kick-started a massive industry. By this point, the United States no expansion of those products and technologies. longer had sole reign over petrochemical Since Europe and Japan did not produce technologies; this was the beginning of new their own ethane-containing natural gas, the advances through the marriage between primary method for obtaining basic American and European technologies. petrochemicals was the steam cracking of naphtha and other light petroleum products. 5.3.1 The American petrochemical The steam cracking of naphtha and other industry expands substances yielded a variety of olefins and (1) Olefins cracked gasoline. Cracked gasoline became From the 1920s to the 1940s, the growth the main source of aromatic hydrocarbons of the petrochemical industry in the United due to the large amount and high States was based on olefins, such as those

100 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) sequestered from petroleum refining waste distillation. Meanwhile, having peaked gas and those obtained from steam cracking around 1950 steel production in the United ethane and propane in natural gas. By the States began to decline. As a result, coal tar 1950s, the steam cracking of ethane and production also began to decline, and propane in natural gas became the manufacturers were becoming unable to cope mainstream method for producing ethylene in with the rapidly growing demand for the United States. At the same time, the rapid aromatic hydrocarbons needed for spread of fluidized catalytic cracking (FCC) polystyrene, nylon and other products. led to an increased supply of propylene and Between 1950 and 1959 in the United States, butylene, thereby achieving a production the source of aromatic hydrocarbons shifted system for other olefins in which the key completely from coal tar to reformates and ingredient was waste gas from oil refining. cracked gasoline, obtained from the steam Naphtha steam cracking was still being cracking of naphtha. In particular, as the used, although it only accounted for a small United States relied primarily on the steam percentage of olefin production in the United cracking of ethane, cracked gasoline supplies States. In contrast to steam-cracked naphtha were scarce, and aromatic hydrocarbons had gas, steam-cracked ethane gas and oil refining to be sourced mainly from reformates. waste gas contained almost no butadiene; accordingly, the supply of butadiene in the (3) Industrial organic chemicals United States was obtained via butylene The alcohol production processes that dehydrogenation. Furthermore, the practice of gave birth to the petrochemical industry in the obtaining butadiene from fermentation 1920s also experienced major technological ethanol was abandoned in peacetime for cost innovation in the 1950s. A direct hydration reasons. process using a solid catalyst was developed and put into commercial use, replacing the (2) Aromatic hydrocarbons old indirect hydration process using sulfuric Major changes also occurred in the acid. With the sulfuric acid process, olefins production of another basic petrochemical, were reacted with sulfuric acid to create aromatic hydrocarbons, which were supplied organosulfate, which was then hydrolyzed to exclusively from coal tar during the Second obtain alcohol. The diluted sulfuric acid World War. During the war, a process for the byproduct was concentrated by heating and catalytic reforming of naphtha was developed then reused. In essence, this process was a and commercialized. Not long afterwards, in combination of stoichiometric reactions. By 1949, UOP developed the Platforming contrast, Shell developed and commercialized Process, which used platinum as a catalyst a method to synthesize ethanol by using a instead of the conventional molybdenum phosphate-silica catalyst to react ethylene in oxide. In no time at all, this became the its gas phase directly with steam in 1948. The primary process used for catalytic reforming. same process was also developed by British In 1952, UOP developed the Udex process to Petroleum (BP), who achieved the industrial recover aromatic hydrocarbons from application of it in 1951. Also in 1951, reformates (i.e. mixtures of hydrocarbons). It British company ICI commercialized an IPA has been known for some time that production method involving a direct reaction reformates contain large quantities of of propylene with steam using a tungsten aromatic hydrocarbons, but, in contrast to oxide-silica catalyst. coal tar distillation, reformates contained As previously mentioned, manufacturers many azeotropes, meaning that these in the United States were mass producing aromatic hydrocarbons could not be cumene from propylene and benzene for use efficiently recovered by distillation. The in high-octane gasolines. Again in 1951, Udex process enabled the recovery of Hercules Inc. developed a method for the aromatic hydrocarbons from reformates by co-production of phenol and acetone from skillfully combining extraction with a solvent cumene. This process was first applied mixture of glycol and water and extractive industrially in Canada in 1953. The following

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year, it was adopted in the United States and into the petrochemical industry. throughout Europe. This was a major Great strides were also achieved in innovation that changed how phenol was polymer forming technologies during the produced the world over. Compared to past Second World War. In addition to the processes, this enabled production under conventional techniques of compression much milder conditions and yielded fewer molding and calendar molding, the 1950s saw byproducts; it remains the mainstream the growth of extrusion molding, which had process utilized throughout the world to the already been used extensively during the war present day. to produce synthetic fibers, pipes, films, sheets and wire coating, as well as growth in (4) Polymers the size of the machinery used. Injection At the end of the Second World War, the molding, which was already in use before the United States government sold off its war for the fabrication of small plastic state-owned synthetic rubber and other components, also made leaps after the war, as factories inexpensively to chemical the size of machinery grew and processes companies. With the sudden loss of this were accelerated and automated. massive demand from the military, synthetic Consequently, the United States rubber and a host of other chemical products petrochemical industry was able to develop experienced a temporary decline in rapidly in the postwar years with two production; however, the nation’s thermoplastics, polyethylene and polystyrene, well-equipped factories did not remain idle as the main driving force. for long as the mass consumer demand in the United States was quick to blossom, having 5.3.2 The birth and development of the been suppressed during the war. European petrochemical industry Unsaturated polyester, An industry evolved from the mass polytetrafluoroethylene and silicone joined production of chemicals from coal and the lineup of polymers in addition to those fermentation ethanol in the first half of the developed in the 1940s; furthermore, LDPE 20th century in Europe, the birthplace of the and polystyrene triggered significant modern chemical industry. During the Second advances in the United States petrochemical World War, coal liquefaction using industry, having gone into full-scale high-pressure hydrogenation and the production for military use during the war production of artificial petroleum via the and then emerging as all-purpose Fischer-Tropsch process were both carried commercial-use polymers. Following on the out on a large scale in Germany. heels of nylon, the demand for synthetic Technologies for large-scale production and fibers acrylic and polyester started growing in continuous operation comparable to those the United States in the 1950s. Meanwhile, used to make petrochemicals made great manufacturers leveraged the advances made strides in Europe; however, since it lacked the in production and molding technologies abundant supply of natural gas that the United achieved during the Second World War to States had, the petrochemical industry did not bring about even more widespread emerge there until the 1940s. commercial use of a raft of polymers that had been made primarily from coal since the (1) European energy revolution 1930s, namely, vinyl chloride, phenolic resin, In the 1930s, large reserves of oil were urea resin, methacrylate resin and nylon. discovered in the Middle East. After the Manufacturers began using the EDC process Second World War, this crude oil started to make vinyl chloride, the raw material for being exported around the world in large polyvinyl chloride, from ethylene, and the quantities. Given these circumstances, large cumene process used to make phenol, the raw oil refineries were erected, primarily in the material for phenol resin and nylon, and coastal areas of Europe, as part of the United acetone, the raw material for methacrylate States’ Marshall Plan for European resin. Thus, these polymers were incorporated reconstruction. Refining oil in oil-consuming

102 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) areas rather than in oil-producing areas was a extremely large number of products, since major shift, resulting in Europe transitioning they had to make effective use of the many from coal to crude oil-based energy. This was types of olefins and aromatic hydrocarbons the European energy revolution. However, that were co-produced. It was also typified by passenger cars had a low penetration rate in a large number of joint venture companies Europe, unlike the United States, so the backed by American or British oil or demand for petroleum products focused chemical companies paired with chemical heavily on heavy fuel oil rather than on companies in the various countries of Europe. gasoline. For this reason, European refineries For instance, in West Germany, BASF joined did not undertake catalytic cracking and with Shell to form Rheinische Olefinwerke catalytic reforming on as large a scale as their (ROW), while Bayer joined with BP to American counterparts, nor did they supply establish Erdölchemie to undertake the steam large amounts of petroleum waste gas. cracking of naphtha; both were fifty-fifty Nevertheless, refineries in France began joint ventures. Yet another feature of the producing small volumes of propylene-based industry in Europe was the formation of solvents from petroleum waste gas in 1949, complexes that included industrial organic which can be deemed as the start of chemical and polymer production plants petrochemistry in Europe. centered around the naphtha steam cracking plants, which themselves were adjacent to oil (2) Origins of the European petrochemical refineries in the coastal areas. A similar industry situation emerged in Japan, but not in the The full-fledged development of the United States (see Section 2.5.2) petrochemical industry in Europe originated with the steam cracking of naphtha, gas oil (3) Successive development of European and other liquid hydrocarbons produced from petrochemical technologies European refineries to generate olefins and Europe was home to a large number of aromatic hydrocarbons. In 1950, British companies with top-tier chemical company ICI adopted a superheated steam technologies. Therefore, although the cracking process from American company industry began with the steam cracking of Kellogg and built Europe’s first naphtha naphtha, by the time olefins and aromatic steam cracking plant in Wilton in northeast hydrocarbons could be supplied in abundance, England, thus forming the beginnings of a European petrochemical technologies were petrochemical complex in the area. The being developed in rapid succession. United Kingdom was also home to the BP In the 1950s, European governments refinery in Grangemouth, northern Scotland, were heavily involved in the setting of prices and the Esso Fawely refinery in the suburbs for crude oil and petroleum products, and for of Southampton, in the south of England. a time the pricing system was distorted, as Thus, an increasing number of large shown in Table 5.3. Accordingly, ethylene petrochemical complexes grew up around production technologies that were developed large oil refineries. In the early 1950s, France, in the United States were adopted, but that Italy and the Netherlands also began their was not all. Soon, a raft of domestic ethylene own petrochemical industries. Meanwhile, production technologies, including the (West) Germany, which had just suffered Catarole process, sand cracking process, the defeat in the Second World War, remained BASF process and the Hoechst process, were far behind its European neighbors, and was developed and put into commercial use by not able to establish a petrochemical industry European companies. Some of these until the latter half of the 1950s. In West companies co-produced ethylene with not just Germany, reconstruction began with the field olefins but also acetylene in an effort to make of coal chemistry. use of their existing acetylene-based Given its origins in the steam cracking of technologies and facilities. However, as naphtha, the European petrochemical industry pricing for petroleum products normalized was typified by each complex producing an and technologies were developed that enabled

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the production of almost all of the industrial French company Rhone Poulenc in 1956. organic chemicals from olefins without This polyethylene, which possessed very having to depend on acetylene, the primary different functions and applications than method for producing ethylene transitioned to polyethylene produced using a high-pressure external heat-pipe steam cracking by the end process, was called high-density polyethylene of the 1960s. (HDPE). In the United States, meanwhile, Many important manufacturing Phillips Chemical used a chromium oxide technologies for industrial organic chemicals catalyst, while Standard Oil (Indiana) used were developed in Europe. Factories began catalysts such as molybdenum oxide in their using the Hoechst-Wacker process in 1959 respective technologies developed in 1957 for (see Section 6.1.2 (2) 1)). This enabled the the polymerization of HDPE at pressures of production of acetaldehyde through the air 30 to 40 atmospheres. For this reason, oxidation of ethylene. As mentioned in the manufacturing methods using the Ziegler previous chapter, acetaldehyde was an catalyst are referred to as low-pressure important intermediate product of carbide and processes, while those used by Phillips and acetylene chemistry, and after the war, it other similar methods are called remained one of the two pillars of acetylene medium-pressure processes. chemistry, along with vinyl chloride. The However, even with the high-pressure Hoechst-Wacker process spread around the process for producing LDPE (i.e. radical world almost immediately, and in 1962, polymerization) and the catalytic Union Carbide and other American polymerization of HDPE, it was not possible companies converted their factories to to obtain high performance polymers by employ this process. Thus, one of the major polymerizing propylene. Italian chemist pillars of acetylene chemistry was undone by Giulio Natta successfully obtained high the Hoechst-Wacker process. performance PP by developing a method for In 1960, a method was developed in the the stereospecific polymerization of Soviet Union to synthesize vinyl acetate from propylene in the presence of a Natta catalyst. ethylene and acetic acid in the liquid phase Montecatini was the first company to put using the same catalyst from the polypropylene into commercial production. In Hoechst-Wacker process; this was put into 1957, it produced resins for plastics at its practical use by British company ICI and Ferrara (Italy) plant, and in 1960 it began American company Celanese in 1965. Not producing synthetic fibers in its Terni (Italy) long after, Bayer and others developed a gas plant. Ziegler and Natta catalysts are now phase process. collectively referred to as Ziegler-Natta The biggest contribution from Europe in catalysts.[Footnote3]2 the history of the petrochemical industry was the discovery of Ziegler-Natta catalysts. It is fair to say that the class of polymers produced using Ziegler-Natta catalysts (namely, HDPE, L-LDPE, PP, EPR, BR, IR, etc.) now account for more than half of all olefin consumption. As has been already mentioned, LDPE was invented by British company ICI in 1933. It was manufactured using radical polymerization under a high pressure (2,000 atmospheres) with oxygen or other initiator. Meanwhile, German chemist Karl Ziegler developed a technique for producing polyethylene at atmospheric pressure using a

Ziegler catalyst. This method was put into use [Footnote3] Refer to Section 3.4.2 (1) for the performance and by Italian company Montecatini in 1954, purposes of various polyethylenes, Section 3.4.3 (1) for PP, Section 3.4.4 (1) and (5) for various rubbers and Section 6.1.3 (1) for West German company Hoechst in 1955, and polyethylene and PP manufacturing processes and Ziegler-Natta catalysts.

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Table 5.3 A variety of ethylene production technologies developed in the 1940s to the 1960s

Ziegler-Natta catalysts have a wide range rubber (Germany), Hoechst’s low-pressure of applications. Using them in tandem with HDPE (Germany) and Montecatini’s PP the stereospecific polymerization of (Italy). Therefore, once factories were built butadiene yielded high performance BR, and for the steam cracking of naphtha, and then in 1960, Phillips Petroleum put this process olefins and aromatic hydrocarbons could be into practical use in the United States. IR was supplied in abundance in Europe, polymer also developed as a result of the production rapidly expanded. stereospecific polymerization of isoprene, and The same was true for synthetic fibers. this went into commercial use in the United During the Second World War, Germany States in 1959. In 1958, Montecatini produced Nylon 6 from phenol. In 1946, the developed an ethylene-propylene copolymer, Calico Printers’ Association (the United but was unable to vulcanize it. Then, in 1961, Kingdom) won approval for its polyester British company Dunlop commercialized fiber patent. With the transfer of this patent to EPDM rubber by adding a third component the rest of the world excluding the United for vulcanization. States, ICI began conducting research with an eye on commercialization, and in 1955, ICI’s Wilton (the United Kingdom) plant (4) The European polymer revolution commenced full-fledged production. In the In terms of demand, Europe’s transition meantime, DuPont, which had received the to mass consumerism in the 1950s led to right to use the patent, started full-scale large quantities of polymers being used; this production in the United States in 1953. is sometimes called the polymer revolution. DuPont had already begun production of This is when a large number of acrylic fibers in 1949, while West Germany’s petrochemical-based general-purpose Bayer AG launched production in 1951 in polymers and all-purpose synthetic rubbers Dormagen (in the outskirts of Leverkusen). In were developed and put into practical use in this way, not only did European companies Europe. Examples include ICI’s LDPE (the begin producing synthetic fibers soon after United Kingdom), IG Farben’s polyvinyl their counterparts in the United States, it was chloride, polystyrene, and SBR synthetic often the case that they developed their own

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technologies instead of relying on technology transfers.

5.3.3 The birth of the Japanese petrochemical industry In many ways, Japan was in a situation similar to that in Europe. Lacking access to large amounts of oil and natural gas, Japan developed a large-scale chemical industry based on coal and fermentation ethanol before and during the Second World War. Fig. 5.1 Change in production volumes of Like Germany, Japan had to start from major synthetic polymers in Japan in the scratch upon its defeat in the war. 1950s. Reconstruction of the industry started with (2) Natural gas kick starts petrochemistry coal chemistry centering on coal, in Japan hydroelectric power, limestone and other As shown in Table 5.4, domestically domestically available resources. produced natural gas (primarily methane without ethane or other gases) became the (1) The advent of Japan’s polymer age raw material for syngas. From this, Japan Gas By the late 1940s, Japan had access to an Chemical began producing methanol in its abundance of information about the Niigata plant in 1952, followed by ammonia advancement of the petrochemical industry and urea in 1957. The following year, Toyo and utilization of polymer products in the Koatsu began producing methanol from United States. Japan resumed production of natural gas at its Mobara factory. In terms of the important organic intermediate how petrochemistry is defined in this study, acetaldehyde from acetylene soon after the 1952 can be considered to be the year in end of the war. Not long after that, in the which the field came into being in Japan. early 1950s, the production of a range of acetylene-based compounds, including vinyl Table 5.4 First production of petrochemical chloride, polyvinyl chloride, vinyl acetate, products in Japan in the 1950s. polyvinyl alcohol, vinylon and methacrylate resin was in full swing. Japan also Year Product Company, factory Household mineral commenced production of phthalic anhydride, 1951 oil-based synthetic Lion Fat and Oil phenol, caprolactam and nylon from coal. detergent Methanol from natural Japan Gas Chemical, The production of urea resins from urea, 1952 methanol and formaldehyde generated from gas Niigata coke oven gas and coke-based syngas Monsanto Kasei Kogyo, 1957 Polystyrene Yokkaichi; Asahi increased rapidly. Together with celluloid, Dow,Kawasaki phenol resins and rayon, which Japan had Maruzen Petroleum, 1957 sec-Butyl alcohol, MEK been producing before the war, vinylon, Shimotsu Japan Gas Chemical, nylon, polyvinyl chlorides, urea resins and 1957 Ammonia, urea Niigata other polymers spread rapidly throughout Nippon Petrochemicals, 1957 IPA, acetone post-war Japan. LDPE and polystyrene Kawasaki Mitsui Petrochemical imported from the United States were added Ethylene (naphtha steam 1958 Industries, Iwakuni; to the lineup, and Japan found itself thrust cracking) Sumitomo Chemical, Oe fully into the polymer era even before its Low-density polyethylene 1958 Sumitomo Chemical, Oe petrochemical industry had fully gotten off (ICIprocess) Ethylene oxide glycol (SD the ground. As shown in Fig. 5.1, the Mitsui Petrochemical 1958 process) polymers that were used particularly Industries, Iwakuni; 1959 Ethylene oxide glycol Nippon Shokubai, Kawasaki frequently from the late 1940s to the 1950s (Nisshoku process) were polyvinyl chlorides and urea resins. High-density polyethylene Mitsui Petrochemical 1958 (Ziegler process) Industries, Iwakuni

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Aromatic hydrocarbons Mitsui Petrochemical of the refineries along the Pacific coast, and 1958 from cracked gasoline Industries, Iwakuni these remained closed for more than four (UOP process) 1958 Polyester fiber Toyo Rayon, Mishima years. In July 1949, the refineries were finally Aromatic hydrocarbons allowed to be reopened after United States 1958 Mitsubishi Oil, Kawasaki from reformates occupation policy shifted due to the Nissan Chemical Industries, 1958 Hard type alkylbenzene intensifying Cold War. Nevertheless, many of Ltd., Nagoya Phenol, acetone (cumene Mitsui Petrochemical the refineries did not commence actual 1958 process) Industries, Iwakuni operation until 1950. During this time, many Terephthalic acid (SD Mitsui Petrochemical of the Japanese oil companies had entered 1958 process) Industries, Iwakuni capital and business tie-ups with major Mitsubishi Rayon, Otake; Western oil companies. 1959 Acrylic fiber Japan Exlan, Saidaiji; Asahi Kasei, Fuji The restarting of the oil refineries High-density polyethylene combined with Japan’s shift towards 1959 Mitsui Chemicals, Nagoya film consuming Middle Eastern crude oil imports Yokkaichi Chemical 1959 Non-ionic surfactant served to lay the foundation for the Company 1959 Propylene oxide, glycol Asahi Denka, Oku petrochemical industry in Japan. Stimulated Mitsubishi Petrochemical, by stories of petrochemical breakthroughs 1959 Styrene monomer Yokkaichi; Asahi Dow, from Europe and the United States, Japan’s Kawasaki interest in petrochemical commercialization Nippon Petrochemicals, 1959 Butadiene Kawasaki continued to grow. As a result, many plans High-density polyethylene were devised from the late 1940s onwards to Showa Yuka, Kawasaki; (Phillips process), foster the growth of petrochemistry in Japan. 1959 Furukawa Kagaku Kogyo, High-density polyethylene Kawasaki However, compared to the mass-production (standard process) chemical industry that Japan had employed Zeon Corporation, 1959 Nitrile rubber, SBR latex Kawasaki thus far, the petrochemical industry had Source: Reference [12] and others product categories with a larger number of co-products, and required much vaster Not only did Japan Gas Chemical use expanses of land, which in turn necessitated domestic resources to produce its methanol, it massive funding. In addition, many new also used domestic technology in the form of products were not known in the Japanese repurposed scrap equipment from an old market (e.g. polyethylene, polystyrene, Imperial Navy fuel factory. At that time, the polyester fibers, acrylic fibers, synthetic only other competitors making methanol were rubbers etc.), and companies were often using coke oven gas, as they had done since reluctant to enter into production of these before the war. However, in order to survive, alone due to the risks involved. For this they soon had to switch from the raw reason, Japan needed more time even more so materials they were using to natural gas, and than Europe, for its petrochemical industry to then to naphtha and LPG. In this sense, the be established. The involvement of the bold choice of raw materials by Japan Gas government was also significantly more Chemical, which was established in 1951, substantial than in Europe or the United was the precursor of subsequent innovations States, and this was a major factor in the in petrochemical technologies. Methanol and length of time it took for plans to reach urea were the key ingredients in urea resins, fruition. In fact, there were many areas of whose production was skyrocketing. government involvement on several fronts, namely, permits for the sale of former army (3) The run-up to petroleum-based and navy fuel factories, permits for coastal petrochemistry reclamation, restrictions on foreign capital In Japan, the situation regarding inflows, low-interest financing from large-scale refineries, which would later government-affiliated financial institutions become the basis for the establishment of the and other kinds of aid, and permits for nation’s petrochemical industry, was entirely technical transfers. By using these kinds of different from that in Europe. After the war, carrot-and-stick measures, the Japanese the occupation forces ordered the shutdown

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government was not only trying to cultivate petrochemical industry in Japan began with the petrochemical industry, it was also the steam cracking of naphtha (Table 5.4), as embarking on a sustained period of it had in Europe. The first steam cracking intervention, which lasted until the 1980s, plant to go online in Japan was Mitsui with regard to the construction and expansion Petrochemical Industries’ Iwakuni Plant. In of facilities, supply and demand and raw addition to its polyethylene plant, the material pricing and procurement. This company launched plants to produce aromatic marked the return of the Organic Synthesis hydrocarbons, ethylene oxide and glycol at Industry Law, as mentioned in the previous almost the same time, and its facility for the chapter. From the 1970s onwards, these kinds production of phenol and acetone using the of policies were repeated in various cumene process went into operation several developing countries as they nationalized months later. Meanwhile, Sumitomo their petrochemical industries, although the Chemical’s Oe Plant, which started operation periods of government intervention differed in the same year, began producing greatly from country to country. polyethylene alone. It turned surplus In 1957, seven years after the refineries hydrocarbons into syngas using a steam resumed operation, Maruzen Petroleum began reformer to create the raw material for using catalytically cracked petroleum waste producing ammonia. Mitsubishi gas to produce sec-butyl alcohol and MEK Petrochemical began domestic production of from n-butylene at its Shimotsu Plant. Also styrene monomer and butadiene at its around this time, Nippon Petrochemicals Yokkaichi Plant, which went into operation began using catalytically cracked petroleum the following year. By 1963, five years after waste gas to produce IPA and acetone the first ethylene plants opened in Japan, the propylene at its Kawasaki Plant. Some percentage of ethylene consumption historians identify this as the birth of the dedicated to polyethylene had grown to 60% petrochemical industry in Japan (Table 5.4). (see Fig. 5.2), significantly higher than in the These refineries had catalytic crackers and United States or Germany. This is likely due used the petroleum waste gas they generated to the fact that the products were highly themselves. However, as in Europe, the profitable amid the rapid expansion of the demand for petroleum products in Japan at polyethylene market. The Japanese that time was dominated by heavy fuel oil; petrochemical industry in the 1950s relied accordingly, catalytic cracking and catalytic almost entirely on ethylene products reforming were not carried out on a very especially polyethylene, whose market had large scale. Therefore, unlike in the United begun to grow at fever pitch. The States, the subsequent growth of the management style employed at Sumitomo petrochemical industry was not based on Chemical’s Oe Plant is considered to be petroleum waste gas. typical of the Japanese petrochemical That same year, Monsanto Kasei Kogyo industry in the 1950s. produced polystyrene at its Yokkaichi Plant using styrene monomer imported from the United States, while Asahi-Dow did the same at its Kawasaki Plant. The objective behind this was to quickly gain control of the fast growing polymer market, assuming that petrochemical complexes with naphtha steam crackers would soon become able to produce these products. In the 1960s, both companies grew to become leaders in Japan’s petrochemical industry. Fig. 5.2 Percentage of polyethylene in ethylene consumption in 1963. (4) Steam cracking of naphtha The full-fledged birth of the

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postwar period of rapid economic growth. 5.4 The 1960s: Sturm und Drang for Furthermore, plastics were essential as petrochemistry agricultural materials, such as plastic greenhouse films, and construction materials, Due to the rapid development of its such as sewer pipes, rain gutters and petrochemical industry, Japan started keeping corrugated roofing. Furthermore, glue, pace with the United States and Europe by coating and other chemical products that were the 1960s, and these three regions became the previously made from natural polymers or three dominant forces in the global polymers derived from the oxidation of petrochemical industry. Despite having only unsaturated fats and oils came to be just begun at the end of the 1950s, the comprised mainly of synthetic polymers. A Japanese petrochemical industry grew so lifestyle in which plastics came to be rapidly in the 1960s that it overtook many commonplace and were consumed en masse European countries in ethylene production took root in Japan in the 1960s. capacity (including the United Kingdom, The production of plastics in Japan which was the first out of the gate in this topped 100,000 tons in the mid-1950s, before area). By the end of the 1960s, Japan’s increasing more than fivefold to nearly petrochemical industry was second only to 600,000 tons just five years later in 1960. A the United States worldwide. further ten years later, production leapt In the 1960s, not only did remarkable almost ninefold to 5 million tons, as shown in technological innovations occur in the field of Fig. 5.3. Due to its light weight, low cost, petrochemistry, but the industry came to form water resistance and excellent moldability, the basis for the chemical industry as a whole. there was a surge in demand for plastic as it This was truly a period of Sturm und Drang came to replace a wide range of existing for petrochemistry. Having kept up with the materials, including paper (e.g. wrapping times, Japan was fortunate enough to make its paper and boxes), natural rubber (e.g. wire way into the global arena. The following coatings and hoses), celluloid/cellophane (e.g. sections will primarily discuss the Japanese packaging and daily necessities), metal (e.g. petrochemical industry, for which statistics daily necessities and pipes), glass (e.g. are readily available. containers and daily necessities) and pottery (e.g. containers and daily necessities). From 5.4.1 The Japanese polymer revolution the 1970s to the present day, the four main Polymers gradually permeated the United general-purpose resins (polyethylene, PP, States market between the 1930s and the styrene-based resin and PVC) account for 1950s, and spread at an explosive rate in more than 70% of all plastics, as shown in Japan from the mid-1950s into the 1960s. Fig. 5.3. Thus, Japanese society truly felt the impact of what could be called a polymer revolution. Supermarkets first appeared in Japan in the mid-1950s. As in the United States, supermarkets were an essential driver of polymer demand due to the massive amount of films and trays used for wrapping foods and the plastic daily goods sold. In other words, the growth of supermarkets went hand in hand with increased polymer consumption. Plastics were used for beer containers, Fig. 5.3 Changes in plastic production fertilizer and rice bags, and flexible volumes in Japan. containers used for transporting bulk items. Plastics were also used in televisions, radio Due to the difficulty in using statistics to receivers, refrigerators, washing machines present the overall picture of how plastic and other trademark appliances of the permeated the entire realm of existing

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materials, let us outline its permeation into the biggest products were rayon and acetate, two fields: rubber, in the form of synthetic which used natural polymers. However, the rubber, and textiles, in the form of synthetic latter half of the 1960s saw a boom in the fibers. synthetic fibers industry. By 1970, the textile In postwar Japan, the domestic industry was 40% synthetic fibers, 20% rayon production of synthetic rubber was and acetate, and 40% natural fibers: synthetic significantly delayed, having been banned for fibers had finally usurped the top position in several years by the United States occupying the market. After that, the ratio of synthetic forces. In 1959, synthetic rubber production fibers continued to increase, and now they finally began with Zeon, which was a joint account for over 80% of fiber production in venture between the American company B. F. Japan. Goodrich Chemicals and the Furukawa Electric Group. The use of synthetic rubber in Japan dates back to the early 1950s. In 1960, 52,000 tons of the product were imported, while 23,000 tons were produced. Accordingly, as Fig. 5.4 shows, the ratio of synthetic rubber to new rubber consumption in 1960 was 27%. In 1965, synthetic rubber production reached 161,000 tons versus 30,000 tons of exports and 27,000 tons of Fig. 5.5 Changes in production volumes of imports, bringing the ratio of synthetic rubber thread in Japan by material. to new rubber consumption to 47%. In 1970, this ratio increased to 64% on the back of 5.4.2 The shift from coal-based to 698,000 tons of synthetic rubber production. petroleumbased products From then until the present day, the ratio has Rayon and coal chemistry saw postwar steadily remained around 60%. production top their prewar peak in the

chemical industry, which existed before the petrochemical industry. As has been already mentioned in the previous section, a major shift from rayon to synthetic fibers occurred in the late 1960s. This section discusses the shift from coal-based to petroleum-based products.

(1) Aromatic hydrocarbons The shift from coal-based to petroleum

Fig. 5.4 Change of consumption volume of products began with aromatic hydrocarbons. new rubber in Japanese rubber molding Japan began producing aromatic industry. hydrocarbons from cracked gasoline and reformates in 1958, about five years behind Let us turn our attention to textiles. Japan the United States. In 1958, phenol was was a massive producer of rayon before the produced by applying the cumene process to Second World War, and the rayon industry benzene obtained from cracked gasoline. was one of the first to recover after the war. In the same year, production began on As Fig. 5.5 shows, by 1965, rayon, acetate terephthalic acid (SD process), the raw and other chemical fibers containing synthetic material for polyester fiber. This was a fibers accounted for 48% of all textiles; these superior process that enabled the one-stage fibers came to rival almost all of the natural manufacturing of terephthalic acid by the fibers, such as cotton, wool, hemp and silk. direct oxidation of paraxylene. Developed by Synthetic fibers accounted for just under half Scientific Design (SD) in 1955, this process of all chemical fibers. At that point in time, was first used in commercial production in

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1958, after testing by Amoco. Accordingly, process) Nihon Sekiyu Senzai, production in Japan began at the same time as 1962 Alkylbenzene Kawasaki production in the United States. Paraxylene, Acrylamide (sulfuric Mitsubishi Chemical 1963 the raw material used in this process, was acid hydration process) Industries, Kurosaki Hamano Seni Kogyo, difficult to obtain from coal tar, but readily 1963 ABS resin accessible from cracked gasoline and Urawa Methyl isobutyl ketone Mitsui Petrochemical 1963 reformates. Mixed xylenes, paraxylene, (MIBK) Industries, Iwakuni otake terephthalic acid and polyester fibers were the Source: Reference [12] and others aromatics that came to represent petrochemistry. As Table 5.5 shows, the The production of phthalic anhydride production of paraxylene in Japan began in from orthoxylene also began in 1960 (Table 1960, just two years after terephthalic acid. 5.5). The demand for phthalic anhydride was Domestic production of paraxylene did not growing rapidly at the time as a raw material begin until the production of terephthalic acid for phthalic ester (polyvinyl chloride from imported paraxylene had properly plasticizers). This was a typical coal-based commenced. chemical product. Naphthalene, an intermediate that was originally obtained Table 5.5 First production of petrochemical from coal tar at the end of the 19th century products in Japan in the 1960s and used as a synthetic dye, was used to stoichiometrically produce oxidants, such as Year Product Company, factory fuming sulfuric acid. In the 1910s, a process Phthalic anhydride 1960 Nippon Shokubai, Suita was developed to enable the oxidation of (o-xylene method) 2‐Ethylhexanol, naphthalene with a solid catalyst (vanadium Mitsubishi Chemical 1960 iso-butanol (oxo pentoxide). In 1945, an o-xylene oxidation Industries, Yokkaichi process) process was put into commercial use in the Styrene-butadiene Japan Synthetic Rubber, 1960 United States using the same vanadium rubber (SBR) Yokkaichi Maruzen Petroleum, pentoxide catalyst. It took Japan 15 more Matsuyama; Mitsui years to make the switch from coal-based to 1960 p-Xylene Petrochemical Industries, petroleum products, despite the fact that the Iwakuni technologies were developed proprietarily. Maruzen Petroleum, 1960 Alkylphenol Shimotsu This is because the production of mixed 1961 Polypropylene glycol Sanyo Yushi xylenes and o-xylene did not begin until 1961 Polycarbonate resin Teijin Kasei, Matsuyama much later. Consequenly, the first phthalic Mitsui Petrochemical 1961 Petroleum resin anhydride produced in Japan used imported Industries, Iwakuni orthoxylene, although production was Dainippon Celluloid, Sakai, Mitsubishi domesticated in 1962 following a spike in 1961 AS resin Monsanto Kasei, o-xylene imports. Yokkaichi Ever since the commercial introduction Maruzen Petroleum, 1962 o-Xylene of a process to manufacture nylon from Matsuyama Mitsubishi caprolactam, phenol was used as the raw 1962 Epoxy resin Petrochemical, Yokkaichi material used to make caprolactam. Phenol 1962 Polypropylene fiber Toyo Rayon, Shiga had been previously produced from benzene Caprolactam obtained from coal tar, but when production 1962 (photonitrosation) Toyo Rayon, Nagoya process via the cumene process began in 1958 it, too, 1962 Polypropylene resin Mitsui Chemicals, Otake became a petrochemical product. Meanwhile, Acetaldehyde Toyo Rayon developed a proprietary process Mitsui Petrochemical 1962 (Hoechst-Wacker Industries, Iwakuni otake for manufacturing caprolactam from process) cyclohexane, which was cheaper than phenol. Acetate, butyl acetate 1962 (naphtha direct Dainihonkasei, Otake This process was called photonitrozation, and oxidation process) it was industrialized in 1962 (Table 5.5). This Nippon Shokubai, 1962 Ethanolamine cyclohexane was made by hydrogenating Kawasaki benzene. The production of benzene from 1962 Acrylonitrile (Sohio Asahi Kasei, Kawasaki

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cracked gasoline and reformates began in the acetate late 1950s, meaning that the switchover to In 1962, the Hoechst-Wacker process for petrochemicals as raw materials was already synthesizing acetaldehyde from ethylene was in progress. Cyclohexane, a non-aromatic introduced into Japan and put into cyclic hydrocarbon, was also a prototypical commercial use. The Hoechst-Wacker petrochemical. Around this same time, process was first commercialized in Germany several other processes not involving in 1959, and was later adopted throughout photonitrosation for manufacturing Europe. In 1962, it was commercialized in the caprolactam from cyclohexane were United States and Canada via technical developed in Europe and the United States, transfer. Mitsui Petrochemical Industries and the transition from phenol to cyclohexane adopted the technology the same year, continued. These Western technologies were followed by Daikyowa Sekiyu Kagaku in adopted in Japan from the latter half of the 1963, Kasei Mizushima and Chisso 1960s onward. Soon, caprolactam Petrochemical in 1964 and Tokuyama Sekiyu manufacturers other than Toyo Rayon began Kagaku in 1965. All of these companies using cyclohexane, and this quickly stepped launched ethylene-process plants, which were up the pace at which the transition to capable of achieving much higher capacity petrochemical methods progressed. Between than the conventional acetylene-based plants. 1963 and 1969, a number of companies With this shift, companies that had previously successively started reducing benzene to manufactured acetic acid from acetylene and create cyclohexane. acetaldehyde began either investing in producers who used the ethylene process to (2) Transition from carbide-acetylene manufacture acetaldehyde or procuring their chemistry acetaldehyde from these producers. In 1962, In the 1960s, new petrochemical 93% of acetaldehyde was manufactured from technologies based on olefins were developed acetylene; this had nosedived to 29% by 1965 in rapid succession. These technologies were and 20% by 1967. By 1969, synthetic acetic almost immediately adopted by Japanese acid was no longer being produced from companies, and at the same time, domestic acetylene at all. In 1962, a process for technologies were also developed. This meant producing acetic acid by the direct oxidation that carbide-acetylene chemistry had all but of naphtha was commercialized. disappeared in Japan by the end of the 1960s. Companies that had previously produced vinyl acetate using acetylene also began 1) Oxo alcohols switching technologies en masse in 1967. In As shown in Table 5.5, the conversion of 1968, Tokuyama Sekiyu Kagaku and acetylene from a chemical to a petrochemical Kurashiki Rayon switched to using ethylene product began with the production of to produce vinyl acetate, followed by The 2-ethylhexanol by the oxo process in 1960. Nippon Synthetic Chemical Industry and 2-ethylhexanol is the raw material used to others in 1969. Between 1970 and 1986, the create the polyvinyl chloride plasticizer called production of vinyl acetate from acetylene dioctyl phthalate (DOP). Previously, this had gradually dwindled to zero. been synthesized from acetaldehyde, an important intermediate in acetylene chemistry. 3) Acrylonitrile The production of 2-ethylhexanol by the oxo Acrylonitrile had been used for many process involves synthesis from years in the synthetic rubber called NBR. The butyraldehyde, itself obtained from propylene early 1960s saw a spike in demand for the (see Section 3.4.3 (6)). Furthermore, this polymer for use in acrylic fibers and ABS process was proprietarily developed by resins. The method for producing Mitsubishi.Chemical Industries (now acrylonitrile had undergone several Mitsubishi Chemical). transformations; at that time (the end of the 1950s) it was being produced from acetylene 2) Acetaldehyde, acetic acid and vinyl and hydrogen cyanide. Hydrogen cyanide

112 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) could be made in various ways: from Kawasaki Perchlorethylene, ammonia, methane and air using the Kanto Denka Kogyo, 1965 trichlorethylene (EDC Mizushima Andrussow process, or from methanol, process) carbon monoxide and ammonia using the Japan Synthetic alcohol, 1965 Synthetic ethanol formamide method, to name just two. By Kawasaki Butadiene Zeon Corporation, contrast, the Sohio process developed in 1958 1965 (GPBprocess) Tokuyama was a superior process that enabled the Higher alcohol (Ugine Nissan Petrochemicals, production of acrylonitrile directly from 1965 Kuhlmann process, Chiba propylene, ammonia and air. In 1962, the France) Ethylene-vinyl acetate Mitsui Polychemicals, Sohio process for acrylonitrile productions 1965 was put into commercial use in Japan as well. copolymer resin (EVA) Otake Linear alkylbenzene Nissan Petrochemicals 1966 In the early 1960s, Japan’s acrylonitrile (LAB) (Nissan Conoco), Chiba producers began switching to this process in Acrylic acid ester (AN Mitsubishi Petrochemical, 1966 rapid succession. Japan experienced the hydrolysis process) Yokkaichi Vinyl chloride quickest penetration of the Sohio process out Toyo Soda Manufacturing, 1966 (oxychlorination Nanyo of any country in the world, and it became a process) voracious consumer of propylene generated 1966 Epichlorohydrin Asahi Glass, Yodogawa Acrolein (propylene Daicel Chemical as a byproduct of naphtha steam cracking. 1967 process) Industries, Otake Vinyl chloride (GPA Zeon Corporation, 1967 4) Vinyl chloride process) Takaoka After the Second World War, massive Vinyl acetate (ethylene Tokuyama Sekiyu Kagaku, 1967 amounts of acetylene came to be used for process) Nanyo vinyl chloride, forming the driving force that 1968 n-Paraffin Nikko Yuka saw acetylene chemistry grow by leaps and 1968 Polyacetal resin Polyplastics, Fuji 1968 Butyl rubber Japan Butyl, Kawasaki bounds, both in Japan and the West. Mixed xylene Japan Gas Chemical, Compared to the manufacturing of vinyl 1968 isomerization, Mizushima chloride from acetylene, manufacturing from m-xylene Solution ethylene was somewhat more complex, so in 1969 AA Chemical, Oita polymerization SBR Japan, like many other countries, vinyl Toluene 1969 Toyo Rayon, Ukishima chloride was the last compound to make the disproportionation switch from acetylene chemistry to Source: Reference [12] and others petrochemistry. This transition can be seen in Table 5.6. Conventionally, vinyl chloride was produced by causing a reaction between Table 5.6 First production of petrochemical acetylene and hydrogen chloride. When using products in Japan in the late 1960s ethylene, on the other hand, ethylene has to be reacted with chlorine to create ethylene Year Product Company, factory dichloride (EDC), which is then subjected to Vinyl chloride (mixed Kureha Petro Chemical 1964 gas-phase cracking to yield vinyl chloride (i.e. gas process) Industry, Nishiki the EDC process). Several companies had put Caprolactam (new Mitsubishi Chemical 1964 Inventa process) Industries, Kurosaki the EDC process into commercial use.Since Central Chemical, the thermal cracking in the EDC process Kawasaki/Zeon yielded large amounts of byproduct Vinyl chloride (EDC Corporation, Takaoka; 1964 hydrochloride with the same number of moles process) Shunan Petrochemical, Tokuyama; Mitsui as vinyl chloride, the companies needed to Chemicals, Nagoya secure consumers for this hydrochloride. Acetic acid (Distiller's However, the issue of what to do with the method naphtha 1964 Dainihonkasei, Otake surplus hydrogen chloride was resolved by direct oxidation process running this process in parallel with the Acetone (Wacker Daikyowa Sekiyu Kagaku, conventional process involving a reaction 1964 process) Yokkaichi between acetylene and hydrogen chloride. Japan Synthetic Rubber, 1964 Butadiene rubber One mole of acetylene would eventually react Yokkaichi; Asahi Kasei, with ethylene and chlorine to create two

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moles of vinyl chloride (i.e. the Koatsu Industries (now Mitsui Chemicals), acetylene-ethylene combination process). and Toagosei Chemical Industry (now However, because this method required both Toagosei) all developed oxy-chlorination ethylene and acetylene, it was not able to take processes using domestic technology. Until advantage of the merits of the ongoing shift then, the petrochemical industry had relied to petrochemistry. Around 1960, all three heavily on technical transfers; this was the processes – the acetylene process, the EDC first major example of companies adopting process and the acetylene-ethylene technologies developed in Japan. Starting combination process – were being used in the with the adoption of oxy-chlorination at Toyo United States. In Japan, Central Chemical, Soda’s Shin-nanyo Plant in 1966, a raft of Shunan Petrochemical and Mitsubishi Japanese companies began putting the Monsanto Kasei all opened factories using process into use. With this, the share of the acetylene-ethylene combination process acetylene-based vinyl chloride production fell in 1964. sharply from 76% in 1967 to just 18% in Also in 1964, Kureha Chemical Industry 1970. put a process into commercial use that it had Oxy-chlorination, which uses hydrogen developed to produce vinyl chloride from a chloride and oxygen to chlorinate mixture of acetylene and ethylene gases hydrocarbons, was originally the first step in obtained through the flame cracking of the Raschig process for phenol production,a naphtha. (This plant remained in operation technology developed in the 1930s to create until 1982.) In 1967, Zeon opened a plant chlorobenzene from benzene. Thirty years using the GPA process, which was based on later, the very same process was applied to the same mixture of acetylene and ethylene ethylene. Immediately, numerous companies gases. (This plant remained in operation until in Japan and the West could use their own 1979.) Later, in 1970, Kureha Chemical technologies to develop many related Industry opened a plant to produce vinyl processes. chloride from a mixture of acetylene and ethylene gases obtained through the 5) Chlorinated solvents superheated steam cracking of crude oil. Another example of the shift from (This plant remained in operation until 1978.) acetylene chemistry to petrochemistry was As this shows, several ways to manufacture the adoption of processes to manufacture vinyl chloride were put into use in Japan, perchloroethylene and trichloroethylene from many of which were developed domestically. EDC in 1965. In an effort to fundamentally solve the problem of what to do with the hydrogen By the end of the 1960s, the production chloride byproduct of vinyl chloride of chemical products from acetylene had production, oxy-chlorination was developed declined significantly in Japan, and other than and put into commercial use in the United a small handful of exceptions, no major States in 1965. Oxy-chlorination employs a acetylene products remained in the 1970s. By copper chloride catalyst to generate EDC and the 1980s, the industry based on acetylene water from a mixture of ethylene, hydrogen chemistry had all but vanished. In the United chloride and oxygen (or air). When combined States, the birthplace of petrochemistry, with the existing EDC process, this process acetylene chemistry surprisingly held on until eventually produces vinyl chloride and water around the year 2000, when the last from ethylene, chlorine and air. Since acetylene-based vinyl chloride plant was shut oxy-chlorination uses absolutely no acetylene, down. this process triggered a complete shift to production using petrochemical methods. 5.4.3 Vigorous technological innovation Oxy-chlorination quickly made its way and upsizing around the globe. In Japan, companies such As previously mentioned, the production as Toyo Soda Manufacturing (now Tosoh), of alcohols on the petrochemical methods Tokuyama Soda (now Tokuyama), Toyo shifted to the direct hydration from sulfuric

114 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) acid in the 1950s. During the 1960s, similar petrochemical processes were developed in rapid succession, thus spurring an intensive burst of innovation in which the mainstream industrial processes changed dramatically over a short period of time. Table 5.7 shows examples of these kinds of manufacturing processes, including technologies for the extraction of aromatic hydrocarbons and the production of acetone, terephthalic acid and Fig. 5.6 Ethylene capacity per plant around caprolactam. In addition to these, several the 1960s. other competing technologies were developed in the 1960s, such as those for butadiene Another noticeable facet of the 1960s was extraction and hydrogenating dealkylation to the progressive upsizing of petrochemical obtain benzene from toluene and xylene. facilities, which is exemplified by the change over time in per-plant ethylene production Table 5.7 Cases of intensified competition of capacity, as shown in Fig. 5.6. Four plants manufacturing methods in the petrochemical completed at the end of the 1950s, had an industry in the 1960s initial average annual capacity of 20,000 tons. The average for the 10 plants completed between 1961 and 1964 jumped to 48,000 tons, while the average for the 10 plants that came online between 1965 and 1968 was 118,000 tons. Furthermore, the average for the five plants opened between 1969 and 1970 was 270,000 tons. In around 10 years, plant capacity had expanded more than fivefold.

Fig. 5.7 Change in maximum capacity for each petrochemical plant product in Japan (basic petrochemicals).

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Fig. 5.8 Change in maximum capacity for (high-pressure) steam, which was used to each Japanese petrochemical plant product drive the centrifugal compressors. The (industrial organic chemicals). widespread adoption of these devices contributed to the upsizing of steam-cracking plants while also decreasing their energy consumption and operating costs.

5.4.4. Integrated usage of non-ethylene olefins and aromatic hydrocarbons Although the petrochemical industry originated in the United States, there it was primarily a chemical industry driven by ethylene. In Europe and Japan, however, the industry developed based on the steam

Fig. 5.9 Change in maximum capacity for cracking of naphtha. Accordingly, this each petrochemical plant product in Japan required the integrated usage of non-ethylene (polymers). olefins and aromatic hydrocarbons found in cracked gasoline. For ethane-based steam In pace with the increase in ethylene cracking, the mainstream process in the plant capacity, the per-plant capacity also United States, all that was needed was increased at plants for basic petrochemicals, ethylene production. If a producer needed organic industrial products and polymers. propylene and butylene, they only had to Figure 5.7 shows the change in maximum refine the required quantities from FCC waste capacity for ethylene and butadiene, Fig. 5.8 gas. Likewise, aromatic hydrocarbons could shows the same for ethylene oxide, styrene, be extracted in the necessary quantities from vinyl chloride and acrylonitrile and Fig. 5.9 reformates. The steam cracking of naphtha, shows the same for LDPE, HDPE and PP. In however, produced various other the 1950s alone, petrochemical plant capacity non-ethylene olefins as well. Even at the had already outstripped the existing capacity modern naphtha steam cracking plants with of coal-based chemical plants to that point in higher ethylene yields, the amount of time. Over the next 10 years, the scale of this ethylene generated only amounts to one-third upsizing grew even more massive. The the amount of the naphtha used. The naphtha primary reason for this upsizing was the steam cracking plants in the 1960s yielded pursuit of economies of scale. Since even lower amounts of ethylene than this. construction expenses increase by an Accordingly, these plants also produced large exponent factor of 0.6 compared to plant quantities of basic non-ethylene capacity, the bigger the plant, the cheaper the petrochemical products. The more these cost of construction per unit of capacity naphtha steam cracking facilities were would become; accordingly, upsizing helped enlarged, the more important it became to to achieve significant cost reduction. effectively utilize these non-ethylene In the latter half of the 1960s, the major byproducts. technical factor underlying the successful In 1960, the only major consumers of upsizing of steam cracking plants was the propylene were plants that produced adoption of centrifugal compressors. The isopropyl alcohol and alkylbenzene (which same held true for large gas compression used propylene tetramer). Later in the 1960s, facilities, such as ammonia and methanol however, more uses for the compound were plants. Furthermore, the 1960s saw the developed. By 1970, PP, propylene oxide incorporation of transfer line heat exchangers (polyurethane), acrylonitrile, oxo alcohols (TLEs) into steam cracking plants. These (butyl alcohol, 2-ethyl hexanol, etc.), cumene exchanged the heat of high-temperature and other compounds had grown to account steam-cracked gas to enable heat recovery for almost as much propylene consumption as and production of high-temperature isopropyl alcohol. Meanwhile, propylene

116 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) tetramer, the negative aspects of which are Before the Second World War, higher described in the next section, experienced a alcohols were produced through the reduction in production as the demand for it high-pressure hydrogenation of fats and oils; decreased. these were sulfated to create mild detergents, Butadiene, the C4 olefin obtained in the such as sulfuric acid ester salts.Having highest quantity from the steam cracking of suffered a soap shortage during First World naphtha, had been used to make synthetic War due to a lack of fats and oils, Germany rubber since the 1940s. In the 1960s, various was one of the first countries to begin more effective extractive distillation researching coal chemistry-based synthetic processes were developed to take the place of surfactants. By the 1930s, it had begun conventional extraction. One of those producing alkylnaphthalenesulfonic acid soda. processes, the GPB process developed by Production of alkylnaphthalenesulfonic acid Japanese company Zeon, is an example of a soda began in the United States as well, domestic technology that was exported where it was sold as a synthetic detergent. In around the globe. Nevertheless, there still 1946, after the war, Standard Oil (California) remained a lack of demand for C4 butylenes subsidiary company Oronite developed other than butadiene in the 1960s. alkylbenzenesulfonic acid soda, which was The demand for benzene, paraxylene and sold and popularized by P&G. In Japan, the o-xylene from cracked gasoline skyrocketed. production of alkylbenzene began in 1958, Meanwhile, there was little demand for and the production of this and other synthetic m-xylene and toluene, but with the detergents soared as electric washing commercial application of isomerization and machines became more commonplace. disproportionation, these aromatic Alkylbenzene is produced by causing a hydrocarbons also came to be effectively reaction between tetramerized propylene, also utilized within the petrochemical industry. known as dodecene, and benzene. Meanwhile, Thus, the 1960s was a time of significant the production of non-ionic surfactants from growth for propylene, butadiene and aromatic domestically sourced ethylene oxide began in hydrocarbons as effective ways were 1959. In the 1960s, the primary product of the developed and adopted to utilize these detergent industry shifted from soap to ethylene co-products of naphtha steam synthetic detergent, which contributed greatly cracking. to the transition from fats and oils to petrochemical-based methods. 5.4.5 Advancements in petrochemistry in The same trend occurred in the coating the chemical industry industry. The coating industry originally used The petrochemical industry grew into a drying and semi-drying oils as raw materials, major supplier of hydrocarbon solvents, including unsaturated fatty acids. Before the various industrial organic chemicals and war, the industry had started using alkyd polymers for the chemical industry. resins made from drying and semi-drying oils Accordingly, the chemical industry as a and phthalic anhydride as resins for coating. whole came to be closely linked to the Phthalic anhydride was created by oxidizing petrochemical industry. Examples of the shift the naphthalene obtained from coal tar. After from chemical to petrochemical methods the Second World War, coating have already been mentioned for the rubber manufacturers began using amino-alkyd molding and chemical fiber sectors. The resins, polyvinyl chlorides and unsaturated 1960s was a time when a wide-range of polyester resins as resins for coating, all of sectors in other areas also shifted to which were products of coal chemistry. In the petrochemistry. 1960s, the petrochemical industry began producing excellent coating resins such as (1) The shift to petrochemistry in chemical epoxy, acrylic and polyurethane resins. industries using petrochemical Phthalic anhydride also made the jump from products using a coal-based raw material (naphthalene) At its onset, the detergent industry to a petroleum-based raw material originally used fats and oils as raw materials.

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(orthoxylene). This meant that alkyd resins to the ammonia industry switching over from and unsaturated polyester resins were also coal to oil and petroleum-based gas. As the now petrochemical products. Thus, the size of the ammonia plants grew, they started coating industry also shifted from a fats and being built inside petrochemical complexes, oils based industry to a petrochemistry-based where oil and petroleum-based gas were industry. readily available. This was also convenient The adhesives industry began with for acrylonitrile and other petrochemical natural polymers such as glue and paste. plants that consumed large quantities of Before the war, the industry used phenolic ammonia. resin, but shifted to using large quantities of Meanwhile, the world’s caustic soda coal products after the war until the 1950s, plants that produced chlorine and sodium including urea resin and vinyl acetate resin. hydroxide through the electrolysis of brine In the 1960s, the petrochemical industry were often located in areas where there was a began producing epoxy resins, polyurethane rock-salt layer underground, or where resins, acrylic resins, EVA resins and inexpensive power could be obtained by synthetic rubber. Phenol and vinyl acetate hydroelectricity. Since before the war, most also made the switchover to being of these plants in Japan had been located in petroleum-based products; thus, the adhesives areas that had hydroelectric power plants, industry also transitioned from a coal-based using the energy of falling water. to a petrochemistry-based industry. The production of carbide and acetylene Several other fine chemical industries, was also prevalent in areas where inexpensive including the pharmaceutical, pesticide and power could be obtained, since it consumed cosmetic industries, also saw most of their large amounts of power. However, an primary raw materials, namely, organic increase in the demand for electricity in Japan solvents and organic intermediates, switch to during the 1960s saw power generation petrochemical products. switch from hydroelectric to thermal power Thus, in the 1960s, the petrochemical generation using oil. The caustic soda industry became a key industry, supplying a industry had traditionally been driven by a wide range of chemical industries in Japan strong demand for caustic soda, while there with their raw materials. was little demand for the co-produced chlorine. However, chlorine demand grew (2) The shift to petrochemistry in chemical rapidly, starting with polyvinyl chlorides in industries supplying auxiliary the 1950s. In the 1960s, production materials to the petrochemical skyrocketed of chemical products that used industry large amounts of chlorine to produce, Ammonia, the basic raw material for although the chlorine did not remain in the chemical fertilizers and industrial organic product, (e.g., propylene oxide, isocyanates chemicals, was made from hydrogen obtained and polycarbonate), as did the production of either from the electrolysis of water, from chlorine-based solvents. For this reason, coke oven gas or from reactions with coke high-capacity caustic soda plants also started synthesis or water gas. Compared to coal, it being built inside petrochemical complexes. was easier to obtain hydrogen from oil, In contrast to their previous inconvenient petroleum-based gas and natural gas, since locations near hydroelectric power, chlorine these were hydrocarbons. Moreover, while and other raw materials could now be readily the large-scale transport of crude oil became transported to them by pipes, and large possible, rising wages led to an increase in amounts of thermal power were being domestic coal prices, meaning that imported generated nearby. Thus, even the mass oil and petroleum-based gases became production inorganic chemical industries that cheaper than coal. Furthermore, as the conventionally had no direct connection to demand for electricity increased, the petrochemistry started being located inside erstwhile surplus of hydroelectric power soon petrochemical complexes in greater numbers. disappeared. Thus, the 1960s played witness

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5.5 The 1970s: The end of Sturm und products. Drang for petrochemistry and new However, this sea change in the business challenges environment came too quickly for the petrochemical industries in Japan, the United The economic growth experienced in States and Europe to immediately respond. Japan, the United States and Europe during Accordingly, capital investment continued for the 1950s and the 1960s ended in the 1970s, a little while as it always had, on the back of and a similar fate befell the petrochemical forecasts for robust demand. Eventually, this industry. As polymer-based materials led to excess capacity in all three regions. continued to become more commonplace, the Since facilities had been being upsized from period of explosive demand drew to a close. the end of the 1960s onwards, the decline in Furthermore, massive crude oil price hikes by operating rates led to a dramatic increase in OPEC in 1973 and again in 1979 caused the costs, and the profitability of the oil crises. The age of cheap crude oil was petrochemical industry suffered as a result. over. Consequently, the petrochemical industry, which had been using low prices to 5.5.2 Manifestation of negative aspects its advantage, saw its growth restricted from A lifestyle of mass production, mass the supply side as well. At the same time, consumption and mass disposal spread several negative aspects brought about by quickly in the 1950s and the 1960s in step rapid economic growth manifested in the with advancements in petrochemistry. In form of environmental and safety issues, and addition, the pursuit of substantial cost the petrochemical industry was standing in reductions in logistics and other areas the firing line. Although new petrochemical propelled the centralization of production, technologies were being actively developed primarily in coastal complexes. However, the until the early 1970s, the pace of effects of these changes were not all positive. development slowed down to such a point in Previously unnoticed negative aspects started the latter half of the 1970s that many started surfacing in the 1970s; these can be divided saying the industry had matured. In addition into three main issues. The first issue was to this maturation of the technology, severe air and water pollution. This was not petrochemistry also made the jump over to limited to the petrochemical industry, but developing countries, thus the trifecta of rather was an issue shared by all heavy Japan, the United States and Europe began to chemical industries. The second issue was collapse. plastic waste, which lay squarely with the petrochemical industry. Finally, the third 5.5.1 The end of polymer revolutions in issue was the environmental and safety Japan, the United States and concerns stemming from chemical substances. Europe Again, this was not limited to the The increase in demand generated by petrochemical industry, but involved a wide replacing existing chemical industries, such range of chemical industries. In the latter half as those based on coal chemistry, with of the 1970s, petrochemical companies in petrochemistry had more or less run its course Japan, the United States and Europe were by the end of the 1960s. In the 1970s, the fully immersed in finding solutions to these spread of polymer-based materials in Japan, issues. the United States and Europe had already advanced considerably, thus ending the (1) Air and water pollution rapid-growth era for polymer-based materials. Air and water pollution were particularly Furthermore, the two oil crises caused the severe issues faced by large complexes in price of oil to soar, meaning an increase in which petrochemical facilities, oil refineries both the cost and the price of petrochemical and thermal power generations were products. This increase in cost relative to concentrated. Complexes regulated other materials was one factor that led to the concentrations of the air pollutants emitted, end of the meteoric growth of petrochemical such as sulfur dioxide, nitrogen oxide, soot

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and dust, and water-polluting substances, nurturing of a recycling industry. such as BOD and COD. Regions where Steady efforts such as these gradually emissions were particularly high also made came to produce results in Japan over the use of total pollution load control schemes. next 40 years or so. As Fig. 5.10 shows, the To reduce pollutants, companies converted to volume of plastic waste continued to increase low-sulfur fuels, installed flue gas until it peaked in 2000, and has followed a desulfurization equipment, installed dust gradual downward trend since then. collectors, modified boiler operating By contrast, the treatment of plastic waste conditions, installed denitration equipment is a different story. In the 1970s, most waste and introduced primary wastewater treatment was either buried in landfills or simply processes, such as coagulating sedimentation incinerated. However, as Fig. 5.11 shows, and oil separators, and secondary wastewater thermal recycling at municipal waste treatment processes, such as activated sludge incinerators had come to be the primary systems. These technologies were applied in treatment method by the 2000s. Strides were every industry, not just the petrochemical also being made in cooperation with other industry. Investment in such pollution industries, including the cement and steel prevention rapidly increased in the 1970s; in industries. In 2000, the utilization rate was 1975, it accounted for 22% of all investment 48%; by 2013, this had jumped to 88%. Thus, in the Japanese petrochemical industry. efforts to tackle the plastic waste problem in In Japan, measures to mitigate air and Japan are showing signs of success after years water pollution in the petrochemical industry of hard work. Notwithstanding, the problem were intensively carried out in the early continues to grow across the globe and still 1970s, after which the proportion of funds remains a major challenge. invested in pollution prevention fell away dramatically. Nevertheless, the development of low-pollution production methods that aimed to decrease the amount of byproducts came to form the core of technological development in the petrochemical industry from that time onwards.

(2) Plastic waste Coinciding with the development of disposable containers, plastic waste became a severe issue for the entire petrochemical Fig. 5.10 Change in plastic gross discharge in industry; the same was true for for old tires as Japan. well. However, this problem did not manifest

until petrochemical products that were sold and processed were disposed of after being consumed, meaning it could not be solved by the petrochemical industry alone. Since this involved local governments as well as several other related industries and also consumers, measures could not be enacted immediately. In Japan, the Plastic Management Research Association (which was reorganized into the Plastic Waste Management Institute (PWMI) the following year) was established in 1971, and long-term initiatives were commenced Fig. 5.11 Progress of plastic recycling in with regard to the processing of plastic waste, Japan. recycling research, technological development, public relations and the (3) Environmental and safety issues

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stemming from chemical substances This issue was a major blow to the Japanese As shown in Table 5.8, four major and European petrochemical industries, environmental and safety issues stemming which traced their origins to the steam from chemical substances have occurred in cracking of naphtha, because it meant the loss the field of petrochemistry, namely, issues of a key consumer for propylene, for which with synthetic detergents, issues with organic demand was still low. However, chlorine compounds, issues with gasoline manufacturers in both the synthetic detergent additives (tetraethyl lead, MTBE) and issues and petrochemical industries were quick to with chemical substances in relation to global respond to this issue. environmental problems. 2) Organic chlorine compounds 1) Synthetic detergents In 1968, the Kanemi Yusho Incident By the mid-1960s, rivers were already occurred in Japan. This was a case of mass starting to become polluted by foam from polychlorinated biphenyl (PCB) poisoning, alkylbenzenesulfonic acid soda, widely used but the problem was much bigger, involving in synthetic detergents. Alkylbenzenesulfonic dioxins as well as many other chlorinated acid soda used dodecene made from organic products and their waste products and tetramerized propylene as a raw material and byproducts. It was then linked to the issue of possessed strong cleaning power. In Japan, its chlorine-based pesticides, which had been use as the primary ingredient in synthetic pointed out as problematic in the early 1960s. detergent rapidly spread from the late 1950s PCBs were inexpensive, stable in the onwards. However, most of the presence of heat and chemicals, highly alkylbenzenesulfonic acid soda derived from insulating, and highly incombustible, so they dodecene contained branched-chain alkyl were widely used as heat transfer mediums, groups. Due to its poor biodegradability, the insulating oils for transformers and capacitors compound remained in the environment and and plasticizers, as well as in carbonless caused foam pollution in rivers. In contrast, paper. The production of PCBs began in the the alkylbenzenesulfonic acid soda containing United States in the late 1920s and in Japan in straight-chain alkyl groups were found to be the mid-1950s. The Kanemi Yusho Incident biodegradable. Straight-chain alkyl groups happened when PCBs, which were being used can be obtained from higher alcohols, which as a heat transfer medium for the heat themselves are obtained through the high treatment of food oil, contaminated food oil pressure hydrogenation of fats and oils. due to the inadequate maintenance of a heat Consequently, producers switched to using exchanger. The production and use of PCBs fats and oils to make these. Within was prohibited, and PCB-containing products, petrochemistry as well, various techniques for such as carbonless paper, were widely producing straight-chain α-olefins were recalled; however, the problem did not stop developed, thus establishing the infrastructure there. needed to supply straight-chain alkyl groups.

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Table 5.8 Safety and Environmental issues on chemical substances related to petrochemistry

Organic chlorine compounds, like PCBs, the late 1960s, questions began to arise do not break down very readily in the surrounding tetraethyl lead, which had been environment, and, since they accumulate in added to gasoline to enhance its octane body fat, they are perpetuated in high number. Tetraethyl lead was used in concentrations along the food chain. In the combination with ethylene dibromide to 1960s, it had already been pointed out that prevent the accumulation of lead oxide in the chlorine-based pesticides were causing engine when gasoline was burned. Tetraethyl environmental pollution. Furthermore, it was lead went into commercial production in the discovered that dioxins, a byproduct United States in the 1920s and was one of the generated in the process of producing various first products of the country’s nascent organic chlorine products, could potentially petrochemical industry. During the Second contaminate the primary products. Moreover, World War, it was used in large quantities as it was also found that dioxins could be an octane enhancer for aviation fuel. In Japan generated when organic chlorine products as well, it went into commercial production were incinerated. Like PCBs, dioxins are before the war, and was imported en masse organic chlorine compounds that are even after the war since domestic production non-degradable, accumulative and toxic. was not achieved until much later. Efforts were undertaken in Japan, the Since tetraethyl lead is itself highly toxic, United States and Europe to tackle this sufficient attention must be given when problem, and as a result, management handling gasoline containing the substance; techniques were adopted for all existing and this had been fully known since the 1920s. In new chemical substances, not just organic the late 1960s, air pollution caused by lead chlorine compounds, from the standpoints of compounds emitted as automotive exhaust degradability, accumulativeness and toxicity. and chronic lead poisoning among roadside Laws that were enacted in Japan around this residents became significant issues. Therefore, time include the Act on the Evaluation of efforts were undertaken to make the switch to Chemical Substances and Regulation of Their unleaded gasoline. Japan had already Manufacture and the Law concerning achieved this transition by the mid-1970s, but Pollutant Release and Transfer Register. in the United States it took until the 3) Gasoline additives mid-1990s for leaded gasoline to finally be The third problem was tetraethyl lead. In outlawed. For the petrochemical industry, this

122 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) meant that demand dissipated for ethylene in in the United States skyrocketed between the the form of tetraethyl lead and ethylene mid-2000s and the 2010s, reaching 25 million dibromide. To propel the transition to tons of ethylene equivalent. Since corn unleaded gasoline, manufacturers either had farmers are subsidized, the use of synthetic to produce gasoline containing high quantities ethanol additives made from petrochemicals of high-octane alkylates or aromatic is prohibited. With this, the petrochemical hydrocarbons or add different additives to industry has lost a major consumer of its gasoline. In the United States, gasoline products, and it has yet to recover. As this producers began using MTBE as an additive shows, the issue of using additives to enhance in the 1980s. MTBE is made by reacting the octane number of gasoline that started in methanol with t-butyl alcohol derived from the 1970s has affected and continues to affect isobutylene. The production of MTBE the petrochemical industry in many ways. increased rapidly in the United States between the 1980s and the 1990s; production 4) Chemical substances related to global in Japan began in 1992. By the end of the environmental problems 1990s, worldwide MTBE production had The fourth category of environmental and reached 18 million tons. With such a large safety problems caused by chemicals consists production volume, isobutylene from the of global environmental problems. This issue steam-cracking of naphtha and FCC waste began with the ozone layer depletion by gas went into short supply. Consequently, fluorocarbons, which contain chlorine and half of the required amount of isobutylene bromine. In the past, fluorocarbons were had to be produced by dehydrogenating widely used as refrigerants, safe solvents and isobutane. Incidentally, MTBE-contaminated propellants. Production in the United States groundwater became an issue in the United started in the 1930s, while manufacture in States in the 2000s. The underlying cause of Japan began in 1942. Fluorocarbons are this was leakage from tiny cracks in produced through a reaction between underground storage tanks at gasoline stations. hydrogen fluoride and chloroform, methyl MTBE is slightly more soluble than gasoline chloroform and trichloroethylene. in water, so it ended up contaminating In the mid-1970s, chlorofluorocarbons groundwater. Furthermore, even small (CFCs, also known as Freon) and amounts of MTBE can dissolve in water, bromofluorocarbons (Halon) were identified resulting in the water being no longer able to as primary causes of ozone layer depletion, be used for drinking due to the odor and taste. and global production and imports of these In 2002, the State of California banned the compounds were banned by the Montreal use of MTBE as a gasoline additive, and the Protocol in 1985. This resulted in an easing of remaining states followed suit. By the the ozone depletion trend from the mid-1990s, mid-2000s, petroleum companies stopped but no recovery was observed. adding MTBE to their gasoline. The logical Hydrofluorocarbons (including hydrogen) solution would have been to inspect the and perfluorocarbons (excluding chlorine and underground tanks at gasoline stations to bromine) were supplied as new CFC prevent leaks, but a government policy was substitutes. However, emissions of these put in place instead, reflecting the growing compounds later became subject to tendency to regulate chemical substances restrictions designed to further curb global without much thought. After that, gasoline warming. As a result, it became necessary to manufacturers in the United States replaced develop safer products. MTBE with fermentation ethanol. The Kyoto Protocol that was adopted in Fermentation ethanol is much more water 1997 for the purpose of reducing global soluble than MTBE, so the fundamental warming set reduction targets for six types of problem of cracks in underground tanks at greenhouse gases, including carbon dioxide. gasoline stations has still not been dealt with. In addition to the above-mentioned As mentioned in Section 4.2.1 (4), the hydrofluorocarbons and perfluorocarbons, production of fermentation ethanol from corn another chemical compound linked to

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petrochemistry is nitrous oxide (N2O). Europe and the United States, tert-butyl Nitrous oxide is a byproduct of the nitric acid alcohol and propylene oxide co-production oxidation process in the production of adipic methods were also employed in commercial acid, a raw material for nylon. The volume of production on a large scale. nitrous oxide released in the production of adipic acid was roughly equivalent to 10% of Table 5.9 First production of petrochemical the nitrous oxide produced through human products in Japan in the 1970s activity; many adipic acid producers have already introduced facilities at their plants to Year Product Company, factory Sumitomo Chiba decompose nitrous oxide byproduct. Chemical, Chiba; Nippon EP Rubber, 1970 EPDM 5.5.3 Maturing petrochemical technology Yokkaichi; Mitsui and expansion into developing Petrochemical Industries, Chiba countries Acrylic acid ester (direct Nippon Shokubai, 1970 As illustrated in Table 5.9, the intense oxidation of propylene) Himeji Kasei Mizushima, technological revolution observed in the Maleic unhydrate (B‐ 1970 Mizushima; Nippon 1960s continued in the early 1970s. Bfraction) Shokubai, Himeji Japan commercially manufactured EPDM Styrene-type thermoplastic Asahi Kasei, 1970 and IR as new polymers through elastomer Kawasaki Isoprene (GPI process), Zeon Isoprene, Ziegler-Natta catalytic reactions, and also 1971 introduced the first production of styrene-type isoprene rubber Mizushima Butanediol, THF Toyo Soda thermoplastic elastomers (a major type of 1971 co-production (butadiene Manufacturing, thermoplastic elastomers) by leveraging process) Nanyo living polymerization. Moreover, the Mitsubishi Chemical 1971 Polyacrylamide utilization of olefins other than ethylene Industries, Kurosaki Mitsubishi Rayon, derived from the steam cracking of naphtha 1972 PBT resin Toyohashi paved the way for the commercial production Matsuyama Sekiyu 1972 High purity telephthalic acid of acrylic acid ester derived from the direct Kagaku, Matsuyama Isopropyl alcohol (direct Tokuyama Soda, oxidation of propylene, maleic anhydride 1972 made from n-butylene or n-butane feedstock, hydration process) Tokuyama-higashi Ethylene-vinyl alcohol 1972 Kuraray, Okayama 1,4-butanediol (PBT resin material) made copolymer (EVOH) from butadiene feedstock and THF. The Direct polymerization Kanebo Polyester, 1972 process for polyester commercial production of high-purity Hokuriku terephthalic acid enabled direct reactions filament PAN process for carbon Toray Industries, 1973 between dimethyl terephthalate fiber Shiga (DMT)-independent terephthalic acid and EG, Adsorptive separation of Toray Industries, 1973 leading to the commercial adoption of p-xylene (Aromax) Kawasaki manufacturing technologies for polyester Styrene monomer, filaments (long fibers). This laid the platform 1975 propylene oxide Nihon Oxirane, Chiba co-production to allow polyester fiber to rise far above Toray Industries, 1976 PET resin for bottles nylon fiber and acrylic fiber from the 1980s. Mishima No decalcification process At the same time, the technology to separate Mitsui Petrochemical 1977 for polypropylene by the paraxylene, a raw material for terephthalic Industries, Chiba high activity catalyst acid, from mixed xylene was also further 1978 Superabsorbent polymer Sanyo Chemical developed in the form of Toray’s Aromax Mitsui 1978 Ionomer resin process and UOP’s Parex process, both of Polychemicals, Otake Modified polyphenylene which meant substantial cost reductions. The 1979 Asahi Dow, Chiba ether long-desired production alternative to the Source: Prepared with Reference [10] propylene oxide chlorohydrin method emerged in the form of the styrene From the late 1970s, however, the co-production method, which was number of new products and technologies incorporated into commercial production. In used in commercial production fell rapidly,

124 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) leading to the view that petrochemical and put an end to the dominance of the three technology had matured. The 1970s saw the major regions that had presided from the establishment of state-operated ethylene 1950s to the 1970s. production companies first in South Korea At the same time, the petrochemical and Taiwan, and later in the so-called newly industry in developed countries witnessed industrialized countries (NICs) (or newly several trends to cope with maturing demand, industrialized economies [NIEs]), marking environmental problems and soaring raw the launch of the petrochemical industry in material prices in the 1970s. The first of these those countries. Unlike Japan and Europe, trends was the shift toward polymer-based these nations had no prior track record in structural materials. Another trend was the coal-based chemical industry. They used development of energy-saving and polymers such as polyethylene and low-pollution technologies. polystyrene and synthetic fiber feedstock imported from the three major supply regions, 5.6.1 Emergence of the petrochemical to start production of synthetic fiber as well industry in Middle East as molded polymer products. Thanks to the As a result of the steep rise in oil prices emergence of the textile industry and the during the 1970s, the oil-producing nations of household items and home appliance the Middle East had amassed large amounts manufacturing sectors, which relied on of capital. Leveraging these funds, the synthetic fiber and molded polymer products, respective governments formulated plans to domestic demand for petrochemical products promote non-oil industries. One such area increased in these countries. Consequently, that was focused on was associated petroleum the relevant governments instituted policies to gas, which had previously been largely promote the petrochemical industry with the neglected. After collection and separation, aim of superceding foreign imports. Since the associated petroleum gas yielded methane 1980s, this pattern has governed the rise of (C1), which was used domestically as a fuel the petrochemical industry throughout the and as a raw material for syngas. It also ASEAN region, China and India, and it has contained ethane (C2), which served as a continued to be repeated to the present day. petrochemical raw material. The remaining As petrochemical technology continued propane and butane (C3 and C4, respectively) to mature, the driving force behind were exported as LPG, while the condensate technology transfer shifted from was exported as a light petroleum product petrochemical companies developing new equivalent to naphtha. While it was possible technologies to plant engineering companies. to also use propane and butane (C3 and C4, As a result, it became easier for respectively) and condensate as state-operated companies and large private petrochemical raw materials, initially only companies in developing countries to enter ethane was used as a steam cracking raw the petrochemical sector. From the 1980s, material due to problems with long-distance global demand for petrochemicals fluctuated transport. Accordingly, petrochemical notably in tandem with an increase in the production in Middle Eastern oil-producing number of market players. nations started with a small number of industrial organic chemicals and polymers 5.6 Birth of the Middle Eastern that were directly derived from ethylene, such petrochemical industry in the as polyethylene, EG, EDC, styrene and 1980s synthetic ethanol. The Middle Eastern petrochemical industry was very large in The event that had the most profound scale, but simple in structure. impact on the petrochemical ndustry in the The bulk of the petrochemical product 1980s was the emergence of a large-scale manufacturers were joint ventures between petrochemical industry in the Middle East. state-operated companies in oil-producing This development was symbolic of the nations and European and American oil maturing state of petrochemical technology capital. The technology was entirely supplied

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by developed nations, with construction producers to secure ample funds and reinvest subcontracted to plant engineering companies these into large-scale expansion of from the West. Middle Eastern oil-producing petrochemical facilities. This pattern has been nations had very little domestic demand for repeated several times to the present day. petrochemical products; therefore, virtually all production was geared toward exports. 5.6.2 Transition to polymer structural Manufactured products were sold separately materials by the state-run companies and their In the 1970s, petrochemical companies in European and American capital partners. Japan, the United States and Europe faced a As associated petroleum gas had thus far maturing demand for petrochemical products, been burned and discarded, these products resulting in overcapacity issues. In response, were supplied to petrochemical producers at sector players moved away from exceedingly low (near-zero) costs that were polymer-based packaging materials and other cheaper than energy prices as natural gas. disposable applications in the 1980s, and This was one of the reasons why the Middle instead looked at expanding into applications Eastern petrochemical industry became that could be used over the long term, such as highly competitive on the global market. That mechanical parts and construction materials. being said, the developed nations tacitly Relative to other materials, plastics offered approved such dumping policies as a means the benefits of being light and easy to process, to develop new industries in developing and the objective shifted towards maximizing nations. The reason for this was that the these advantages. The much-anticipated large volume of associated petroleum gas was new market that emerged was the automotive proportional to the volume of oil production sector. The surge in oil prices at the time had and, in the absence of a sharp increase in the increased demand for fuel-efficient vehicles. latter, it was believed there would be certain One way to improve fuel efficiency was to limits on associated petroleum gas volume. reduce vehicle weight, and plastics played a Estimates in the 1980s put Saudi Arabia’s role in this respect. Meanwhile, the market production volume of ethylene from ethane for electrical appliances experienced a included in associated petroleum gas as high maturing demand for household appliances as as roughly 6 million tons. This was the driving force of growth shifted to equivalent to roughly 1.5 times the ethylene electronic products. To meet the needs of output of Japan at the time. Based on the both of these markets, plastics required prevailing global ethylene demand, it was precision molding and heat-resistence. estimated that this additional supply could be These new requirements for plastics were sufficiently absorbed. Existing petrochemical met by the field of engineering plastics. powerhouses such as Europe and Japan were Engineering plastics had already been alarmed before Saudi Arabian petrochemical commercially manufactured from the 1950s operations began; however, given the through the 1960s in the form of concurrent emergence of, and sharp growth in, polycarbonate, polyamide (nylon), glass fiber Asian demand for petrochemical products, filled PET and other compounds, but they had the bulk of the exports were redirected to garnered little attention amidst a period of Asia. sharp growth in general-purpose resins. From In the mid-1980s, the Middle Eastern oil the late 1960s through the 1970s, the producers began Phase 1 of their so-called general-purpose engineering Petrochemical Plan, and product sales made plastics had made a cursory appearance with steady progress. Around the same time, the commercial production of polyacetal, however, the global supply-demand balance PBT and modified-polyphenyleneether. for oil slackened and oil prices declined These general-purpose engineering plastics considerably, resulting in funding issues that became a springboard for subsequent delayed the start of Phase 2 of the plan. expansion into the automotive and electronics Thereafter, oil prices resumed an upward fields. Thereafter, polymers that undercut trajectory, allowing Middle Eastern oil engineering plastics on price also came to be

126 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) used. Some examples include polyurethane, strength. This enabled resource savings in ABS resin, fiberglass reinforced unsaturated terms of product usage. The film provided an polyester and epoxy resin. alternative in fields relying on As plastics came to be more widely medium-quality packaging paper, and was adopted in automobiles, automakers started widely used in disposable shopping bags and calling for low-cost plastics. The polymer that other applications. In the field of synthetic addressed those demands was PP. Produced fiber, several energy-saving technologies that through a block copolymer with ethylene, PP shortened production processes were is a plastic that is not only light and easy to achieved through continuous polymerizing process, but also offers superior shock and spinning and high-speed spinning and resistance and other mechanical strength false twisting (partially oriented yarn - properties. Consequently, PP met the needs of partially textured yarn [POY-PTY]). the automakers and started gradually The PP highly active catalyst developed replacing the other types of plastic that had by Mitsui Petrochemical Industries (now originally been introduced in the automotive Mitsui Chemicals) also greatly contributed to sector. PP came to account for a dominant energy savings in the 1970s. The prevailing share of the plastics used in large molded Ziegler-Natta catalyst at the time produced automotive parts, such as bumpers. PP with low stereoregularity, which had to be Meanwhile, super engineering plastics corrected with a solvent. Since large such as polyimide, PPS, polyether ether quantities of catalysts were used, ketone (PEEK) and polyether sulphone (PES) decalcification was necessary to subsequently were also successively brought into remove catalyst residue from the PP. This commercial production in the 1980s, made the original PP production process followed by liquid crystal polymers and other more complex than the method producing plastics. Super engineering plastics were able HDPE. By contrast, the use of a highly active to withstand temperatures of 150°C and catalyst yielded little PP with low above, which allowed for precision molding stereoregularity and also eliminated the need and thus paved the way for the further for various catalyst removal tasks because the expansion of plastics into the electronics volume of PP generated was dramatically field. larger per catalyst volume unit. Further advances in the 1980s led to the commercial 5.6.3 Energy-saving and low-pollution production of PP via the gas-phase technologies polymerization method. Following the steep rise in oil prices and A key development in energy-saving the emergence of environmental and safety petrochemical technology in the 1980s was problems in the 1970s, a number of the commercial production of L-LDPE. As energy-saving and low-pollution technologies shown in Table 5.10, Japan already used were successively incorporated into HDPE facilities and commercially produced commercial production in the 1980s. L-LDPE in 1980, while Union Carbide (1) Energy-saving technologies (UCC) set up a new plant with gas-phase The 1970s had already seen the polymerization technology in 1983. Ever development of highly active catalysts with since ICI first engaged in commercial HDPE; the technology had progressed to the production of LDPE in 1930, the polymer had stage where there was no need to remove the been produced under a high pressure of 2,000 catalyst after polymerization. Consequently, atmospheres and at high temperatures. By slurry polymerization methods that did not contrast, L-LDPE could be produced using require decalcification and gas-phase medium-to-low-pressure HDPE production polymerization were also adopted in technology through the copolymerization of commercial production. Due to its high ethylene and lower α-olefins such as molecular weight, HDPE facilitated the 1-butylene (see Section 3.4.2 (1)). development of high strength products and production of ultra-thin film with reasonable Table 5.10 First production of petrochemical

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products in Japan in the 1980s phosgene and BPA reactions to diphenyl carbonate and BPA reactions; these found Year Product Company, factory their way into commercial production. Methanol process for Kyoudo Sakusan, 1980 acetic acid Aboshi In the 1980s, Japanese companies Linear low-density developed several variations on the MMA Showa Denko K.K., polyethylene by HDPE 1980 Oita process and integrated these into commercial facility 1983 Nippon Unicar, production, as shown in Table 5.10. For over UNIPOL process linear Kawasaki low-density polyethylene 50 years, MMA had been produced through Mitsubishi Gas the acetone cyanohydrin process, which 1981 Dimethyl ether Chemical Company, utilized a reaction between acetone and Niigata hydrogen cyanide. The major drawbacks of Nisseki Jushi Kagaku, Kawasaki this method were the reliance on hydrogen 1982 1-Butylene Mitsui Petrochemical cyanide, a highly poisonous compound, and Industries, Chiba the generation of byproduct ammonium Butane process for maleic Nichiyu Kagaku 1982 hydrogen sulfate in volumes that exceeded anhydride Kogyo, Oita 1983 Polyimide resin Ube Industries, Ube the resulting MMA by 50%. In contrast, Mitsubishi Rayon, Mitsubishi Gas Chemical developed a 1983 Isobutylene direct Otake ground-breaking process that generated no 1985 oxidation process for MMA Nihon MMA, Ehime ammonium hydrogen sulfate even when using Methacrylonitrile (MAN) 1984 Asahi Kasei, Kawasaki the acetone cyanohydrin method, and adopted process for MMA Nitto Chemical this into commercial production. Other 1984 Bio-process for acrylamide Industry, Yokohama companies such as Mitsubishi Rayon and Gas phase process for Sumitomo Chemical, 1985 Nippon Shokubai developed production polypropylene Chiba methods to manufacture MMA through 1986 PPS Tosoh (SUSTEEL) Sumitomo Chemical, oxygen oxidation reactions, with isobutylene 1987 PEEK Chiba or tert-butyl alcohol serving as raw materials. Source: Prepared with Reference [10] These were low-pollution processes that required no use of hydrogen cyanide and did (2) Low-pollution technologies not generate ammonium hydrogen sulfate as a Low-pollution technologies were byproduct. They were also effectively successively introduced into commercial leveraged for isobutylene (C4) derived production during the 1980s. As already through naphtha steam cracking. noted, new chlorine-free production methods for propylene oxide were employed in 5.7 The 1990s: A shift from commercial production in the 1970s. There petrochemistry to functional are other petrochemical products that do not chemistry contain chlorine in the final product, although chlorine is used in the production process. Global demand for petrochemical Chlorine is created through electrolysis and products continued to rise, supported by thus requires a heavy energy investment. low-cost polyethylene and other products Since it is ultimately discarded as chlorides, supplied by oil-producing nations. China in this is a waste of energy. Consequently, particular went through a polymer revolution proactive research was conducted into driven by imported petrochemical products in chlorine-free production methods in the the 1990s, and started building full-scale 1980s. At the time, commercial production of petrochemical complexes through joint isocyanate had only been partially successful ventures funded by European and American for aliphatic isocyanate. Even today, new companies in the 2000s. In the 2010s, the production methods for aromatic isocyanate center of global petrochemical demand with large output volumes have yet to be shifted to Asia. During the same period, the adopted commercially. On the polycarbonate United States underwent a shale gas front, many production methods were revolution and moved forward with an developed that shifted from traditional ethylene expansion plan targeting a 40%

128 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) increase in ethylene capacity from the 2010 markets in Japan, the United States and level. However, since there is relatively little Europe. Moving into the 2000s, China rapidly prospect of growth in domestic demand, this expanded its facilities. This forced countries plan has triggered fears of substantial such as Taiwan and South Korea, which had disruption to the global petrochemical emerged as synthetic fiber manufacturers in supply-demand balance. the 1970s, to scale back production. In the As the petrochemical industry in Japan, 2010s, China’s synthetic fiber production Europe and the Unites States grappled with a grew to account for nearly 70% of the global protracted slump, the petrochemical supply. companies in these nations adopted two In similar fashion, China’s expansion into distinct strategies: the first was to move away plastic processed goods also began through from petrochemistry altogether; the other was the importing of plastics as raw materials. In to keep petrochemistry as the foundation of the 2000s, its imports of petrochemical operations while attempting to migrate to products ballooned, prompting the functional chemistry. construction of large-scale petrochemical Petrochemical technology is generally complexes centered on naphtha steam thought to have matured in the 1970s, but the cracking in the mid-2000s. These projects 1990s witnessed unprecedented new trends were driven by joint ventures with European that were reflective of changes in the sector’s and American oil and petrochemical supply-demand environment and other companies, which supplied most of the factors. technology. China continued to add new capacity thereafter, but it was unable to 5.7.1 Emergence of the petrochemical immediately replace imports due to the high industry in China and the changing growth in domestic demand. The expansion face of the Middle Eastern has continued since the 2010s, with Asia petrochemical industry (including China, South Korea, Taiwan and The emergence of the petrochemical the ASEAN regions) and the Middle East industry in China followed the same developing into the largest markets for trajectory as it had in South Korea, Taiwan petrochemical products, both in terms of and the ASEAN region. The Chinese polymer demand and production volume. revolution started in the 1990s, when However, the shift of the petrochemical petrochemical companies in Middle Eastern industry to Asia and the Middle East was not oil-producing nations began large-scale necessarily a favorable trend. In several ways, exports of low-cost ethylene products. The this development significantly skewed the largest importer of these products was China, international character of the global which also imported other products that could petrochemical industry. The first problem is not be sourced from the Middle East from that Chinese and Middle Eastern Japan, South Korea and Taiwan. petrochemical companies have grown into The first petrochemical product to be giant organizations that rank among the five manufactured in China was synthetic fiber, top chemical companies in the world. In with production volumes increasing up countries such as South Korea, Taiwan and rapidly from the 1990s. To support this effort, Singapore, petrochemical companies started several raw materials for synthetic fiber were out under government control, but were imported, such as EG, PTA and acrylonitrile. privatized once business took off. Conversely, The Chinese textile industry came to state-operated companies in the Middle East dominate the world, firstly in the and China have shown no sign of labor-intensive sewing field, and later in privatization and have become giant woven, knit and spun materials. Building on enterprises. Another issue was the absence of its textile industry foundations, China looked international influence in raw material prices. to expand into the production of synthetic Chinese state-owned petrochemical fiber in the 1990s. Its entry into this market companies were essentially giant oil drove a contraction in the corresponding refineries, and petrochemistry only accounted

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for a fraction of their operations. Major oil Table 5.11, many of these companies companies in Europe and the United States abandoned all future prospects for their withdrew from the petrochemistry business petrochemical businesses and exited the across the board and redirected their attention petrochemistry field, focusing instead on new to their refinery businesses. This left Chinese growth areas within the chemical sector, such state-controlled companies as the only players as pharmaceuticals. The transformations were pursuing broad-based petrochemical business, not always successful and several reputable a field in which they gained an alarmingly companies, such as Hoechst (Germany) and large presence. Meanwhile, around 2000, ICI (United Kingdom), did not survive the repeated rounds of capacity expansion in the process as standalone entities. Others, such as Middle East had virtually exhausted the DuPont and Bayer, sold off their regional supply of ethane derived from petrochemical businesses and looked for new associated petroleum gas (APG). Thereafter, opportunities in the agribusiness and local companies were forced to use LPG and pharmaceutical sectors, but were condensate, both originally export products, subsequently unable to regain their former as petrochemical feedstock. However, raw luster. Among the oil giants that had once materials prices were set considerably lower invested aggressively in the petrochemical than export prices. Since petrochemistry had field as downstream oil businesses, there was started out with APG-derived ethane set at a also a growing trend to significantly far lower price than the international price, downsize their petrochemical businesses in there was no choice but to reduce the price of tandem with a deterioration in earnings. raw materials for secondary plants relying on Meanwhile, investment funds proactively LPG and naphtha as feedstock, out of acquired petrochemical businesses and consideration for domestic circumstances. rapidly grew into major global petrochemical Although the Middle Eastern countries had enterprises. As petrochemical businesses long since grown beyond the phase of were being bought and sold based on cultivating new industries, their original comparatively short-term outlooks, policies were left unchanged. The technology development and other long-term petrochemical industry in the oil-producing activities lost further steam in Europe and the nations of the region had pursued growth as Unites States. its primary objective, and as part of this process had gradually broadened its range Table 5.11 Trends of expansion beyond from an exclusive focus on American-style petrochemistry by major Western chemical ethylene products to later also include all companies Japanese and European olefin-based and aromatic-based products. Faced with poor domestic demand and an inescapable reliance on exports, the Middle Eastern petrochemical industry entered a difficult phase of operations.

5.7.2 European and American oil companies attempt to break away from petrochemistry

The maturing of petrochemical technology that started in the 1970s and the subsequent technology transfer to developing 5.7.3 From petrochemistry to functional countries led to an emergence of new rivals. chemistry Against this backdrop, Japanese, American Not all Western petrochemical companies and European oil petrochemical companies chose to move away from petrochemicals. A started struggling with chronically excessive large number of companies streamlined their capacity and poor earnings. As illustrated in petrochemical businesses to a certain degree,

130 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) but kept them as the foundation of their operations while pivoting into functional chemistry. BASF and Dow Chemical are typical examples of this. Many Japanese petrochemical companies also followed this path. Examples of success include the world’s first commercial production of polyacrylic acid superabsorbent resin by Sanyo Chemical in 1978, and the commercialization of COP for optical resin by Zeon in 1990. The Fig. 5.12 Changes in the three largest added development of such technologies could not values in the Japanese chemical industry. have taken place without a foundation in petrochemical technology. 5.7.4 New trends in petrochemical However, functional chemistry extended technologies beyond the scope of conventional Petrochemical technologies are said to petrochemical operations. It entailed not only have matured in the 1970s. However, the developing functional polymers, but also Japanese petrochemical industry continued to concurrent molding technologies, and led to incorporate remarkable technologies into the introduction of functional polymer commercial production even after the 1990s, molded products on the market. This made it as illustrated in Table 5.12. The bulk of these more difficult for rivals to enter the sector, were developed by Japanese chemical and also lifted profitability. Even plant companies. Examples in Table 5.12 include engineering companies with strengths in cyclohexanol derived from a cyclohexene chemical engineering technology were unable process, optical resin COP, dimethyl to easily make the leap to molding carbonate derived from a low-pressure technologies leveraging the performance of gas-phase process, MMAs derived from a functional polymers. Reflecting this shift new acetone cyanohydrin (ACH) process, toward functional chemistry, the plastics acetic acid derived from a direct ethane molding industries became the center of oxidation process, polycarbonates derived Japan’s chemical industry in terms of added from a non-phosgene process, caprolactam value. As shown in Fig. 5.12, petrochemistry, derived from an ammonium-sulfate-free plastics molding and pharmaceuticals co-production process and acrylonitrile followed similar growth trajectories as three derived from a propane method. The Japanese industries that have supported the Japanese petrochemical industry continues to work on chemical industry from the 1970s to the the frontlines of the global development of 1990s. Thereafter, the added value growth in petrochemical technology today. In addition, petrochemistry turned from flat to negative, the unprecedented technological trends while plastics molding and pharmaceuticals observed in the 1990s increased more and both remained on an uptrend. Rather than the more in the 2000s. In this section, we have end of growth in petrochemistry, this only reviewed the circumstances that gave development should be interpreted as the rise to these new technology trends. For outcome of an expansion in the scope of details on the technologies in question, refer business by petrochemical companies to to Section 6.2. include plastics molding, in order to address new business opportunities. Functional Table 5.12 First production of petrochemical chemistry has since outgrown its traditional products in Japan from the 1990s to 2008 classification under petrochemistry, and now also includes polymer molding. Year Product Company, factory Cyclohexanone process 1990 Asahi Kasei, Mizushima for cyclohexanol Zeon Corporation, 1990 Optical resin COP Mizushika 1992 MTBE Kashima Oil, Kashima 1992 Low-pressure Ube Industries, Ube

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gas-phase process for the ethylene price, the price of propylene rose dimethyl carbonate to parity with ethylene by around 2010. Sumitomo Chemical, 1994 PES Ehime To address these changes in the Metallocene gas-phase environment, several new propylene process for linear 1995 Ube Industries, Chiba production methods were developed and low-density successively commercialized. polyethylene New ACH process for Mitsubishi Gas Chemical 1996 MMA Company, Niigata (2) Shift to monomer direct synthesis Ethylene direct technology from paraffin 1997 oxidation process for Showa Denko K.K., Oita From its onset, petrochemistry has been acetic acid built on two foundations: olefin chemistry Asahi Kasei, Chimei－ Non-phosgene process 2002 Asahi Corporation in and aromatic chemistry. Saturated for polycarbonate Taiwan* hydrocarbons (alkane or paraffin) such as Ammonium sulfate-free Sumitomo Chemical, methane, ethane and propane have poor 2003 co-production process Ehime reactivity and extremely limited direct for caprolactam Metathesis process for applications. Paraffin is mainly used as a raw 2004 Mitsui Chemicals, Osaka propylene material for steam cracking. However, Asahi Kasei Chemicals, Propane process for acrylonitrile gave rise to the development of 2007 Tongsuh Petrochemical acrylonitrile technology to create double-bond industrial Corporation in Korea* Note: The asterisk (*) denotes a technique that a chemical organic chemicals from paraffin, and several company of Japan has developed, but was produced first at other potential technologies also came into the joint venture overseas. being as a result. The ongoing development Source: Prepared with Reference [12] of technologies using paraffin as a raw material could alter the face of traditional (1) Technologies aiding the shift from petrochemical complexes. ethylene to propylene From the 1980s onwards, propylene (3) Metallocene and post-metallocene demand increased steadily on the back of the catalysts growth of PP. Around 1970, PP competed The polyolefin field saw the emergence with IPA, propylene oxide, acrylonitrile and of metallocene catalysts in the 1980s, which other compounds, and only accounted for attracted attention by virtue of their highly some 15% of propylene demand. By 2010, superior performance compared with the however, that percentage had increased to traditional Ziegler-Natta catalysts. The new over 60%. This shows the remarkably strong catalysts were first deployed in the field of growth PP has enjoyed among propylene polyethylene. However, they were unable to derivatives. Meanwhile, following exert a profound impact on the petrochemical commercial production of acetic acid using market in the way the Ziegler-Natta catalysts the methanol process in the late 1970s, the had in the 1950s and the commercial production volume of acetaldehyde dropped production of L-LDPE had in the 1980s. considerably from the 1980s, while the Demand for petrochemical products had demand for ethylene in developed countries matured, and minor improvements in declined compared with propylene. Still, productivity and performance proved unable petrochemical companies that focused to easily outdo existing product markets. exclusively on ethylene production emerged However, this was not the end of the and expanded in the Middle East, and they metallocene catalyst technology story. A flooded global export markets with ethylene series of post-metallocene catalysts that products, further narrowing the scope for surpassed the original metallocene catalysts developed countries to establish naphtha have been successively announced since the steam cracking plants. Accordingly, late 1990s. propylene shortages became apparent from the 1990s. The price of propylene rose gradually compared with that of ethylene. While it had once hovered at around half of

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Bibliography Industry Association, 1971. [1] R. Guglielmo, “La Pétrochimie dans le [10] “Twenty-year history of the monde (Petrochemistry in the world),” M. petrochemical industry,” Japan Kadota, trans. Que sais-je Collection, Petrochemical Industry Association, ed., Hakusuisha, 1963. Japan Petrochemical Industry Association, [2] Y. Kawase, “The petrochemical industry 1981. in the world,” Saiwai Shobo, 1964. [11] “Thirty-year history of the [3] T. Takahashi, “The history of the petrochemical industry,” Japan chemical industry,” Sangyo Tosho, 1973. Petrochemical Industry Association, ed., [4] F. Aftalion, “A history of the Japan Petrochemical Industry Association, international chemical industry,” H. 1989. Yanagita, trans. Nikkei Science, 1993. [12] “Fifty years of petrochemistry—The [5] P. Spitz, “Petrochemicals: The rise of an half-century timeline,” Japan industry,” Wiley, 1988. Petrochemical Industry Association, ed., [6] A. Takehara, “Captivated by plastics Japan Petrochemical Industry Association, culture and design ,” Kojinsha, 1994. 2008. [7] L. Frost, “Revisiting the first cracker, in [13] “Plastic production, waste, recycling, West Virginia, as shale rekindles interest,” and disposal statistics for 2013,” Plastic IHS Chemical Week, September 9, 2014. Waste Management Institute. [8] T. Watanabe, “The petrochemical [14] “History of high pressure polyethylene” industry (1st ed.),” Iwanami Shoten, Japan Petrochemical Industry 1966. Association, ed., Japan Petrochemical [9] “Ten-year history of the petrochemical Industry Association, 1998. industry,” Japan Petrochemical Industry Association, ed., Japan Petrochemical

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6 Technological system and systematization of petrochemistry

We have already outlined the 6.1.1 Technological system of basic petrochemical products by the number of petrochemicals carbon atoms in Chapter 3, as well as briefly As shown in Fig. 6.2, the technological touching on some of the production system of basic petrochemicals from natural technologies for each product. In this chapter, gas and petroleum is classified into we shall discuss the modern petrochemical manufacturing technologies for syngas, olefin technology system, taking a cross-sectional and aromatic hydrocarbon. view of the technology. We shall also

examine new trends in petrochemical technology that have emerged in the 1990s and since, as well as discussing the history of petrochemical technology on the basis of the technology system, examine the essence of petrochemical technology amidst the large number of mass-producing chemical technologies that predated petrochemistry, Fig. 6.2 Technology system of basic and introduce epoch-making technologies. petrochemicals. Finally, we shall systematize petrochemical technology and discussed its future prospects. As shown in Fig. 6.3, the manufacturing technologies for olefin are classified into technologies for lower and higher olefins. 6.1 Technological system and The former technologies are further classified characteristics of petrochemistry into technologies for C2 olefin, C3 propylene, The technological system of C4 butadiene having a conjugated double petrochemistry as well as the categories of bond and C4 butylenes having one double petrochemical products can roughly be bond. Many of these technologies were classified into three areas: basic originally petroleum refining technologies petrochemicals, industrial organic chemicals that subsequently flowed over into and polymers (Fig. 6.1). A great variety of petrochemistry and were further developed. petrochemical processes are available, The latter processes are further classified into because processes developed before the technologies for higher linear olefins and creation of petrochemistry and petroleum branched-chain higher olefins.

refining processes have flowed over into petrochemistry and been developed. This section summarizes the technological system of current petrochemistry.

Fig. 6.3 Olefin production technology system.

Fig. 6.1 Technology system of (1) Ethylene manufacturing technologies petrochemistry. As described in Chapter 4, industrial organic chemicals and polymers were already being manufactured all around the world

134 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) before the creation of petrochemistry, using they are not detailed here. raw materials that were available nearby. Figure 6.4 summarizes the technologies for manufacturing ethylene prior to the establishment of petrochemistry. A method of collecting ethylene as a byproduct involved separating ethylene from coke oven gas at low temperature. This method was commonly used in Germany. Another method involved obtaining small quantities of ethylene as a byproduct during the manufacture of Fig. 6.4 Ethylene production technology acetylene from natural gas using the arc predating petrochemistry. process. Catalytic technologies were also used for the production of ethylene. Ethylene Steam cracking was developed as an was produced from fermentation ethanol by extension of thermal cracking of petroleum. gas phase dehydration in the presence of acid This started with the production of ethylene clay or other catalyst at various places around by steam cracking of ethane by U.S. Carbide the world. This technology was essential for & Carbon Chemical in 1920. Subsequently, early polyethylene production, because it U.S. Standard Oil (NJ) industrialized yielded ethylene with higher purity more production of ethylene by steam cracking of easily than other technologies. Ethylene was propane in the first half of the 1920s and by produced by partial hydrogenation of steam cracking of naphtha in 1941. An acetylene during the Second World War in outline of steam cracking is given in Section Germany. The development of catalysts was 3.3.3. Steam was added in order to improve the key to the success of this process. Thus, the conversion rate by lowering the partial ethylene production technology had its roots pressure of naphtha or ethane as a raw in the forests of coal chemistry and even material to make the thermal cracking fermentation chemistry. equilibrium reaction progress towards the Meanwhile, ethylene production cracking side, to reduce the accumulation of technology was the first of the lower olefin carbon on the internal wall of the reaction manufacturing technologies using petroleum tube and to control a thermal as raw materials to be developed, in the form cracking-induced temperature fall through the of thermal cracking of heavy oil (Fig 6.5). heat of the steam. Heavy oil was thermally cracked to give As shown in Table 5.3, in addition to waste gas containing ethylene and other tube-type steam cracking that was developed lower olefins, from which the ethylene and as an extension of thermal cracking of propylene were collected. To obtain gasoline petroleum in the United States, various fractions, heavy oil is thermally cracked at ethylene manufacturing technologies were high temperature and high pressure in the suddenly developed and industrialized after absence of a catalyst. This is purely a the Second World War, competing with each petroleum refining technology. The Burton other from the late 1940s to around the 1960s. process developed in 1913 was the first These technologies included the Catarole thermal cracking technology for petroleum. It process using a copper-iron catalyst (Shell was industrialized by Standard Oil (Indiana) Chemicals 1947), the moving bed cracking in 1913. The Dubbs process developed in process using sand as a medium (TPC process, 1914 involved the cracking of petroleum by Socony-Vacuum 1947, sand-cracking process, partial combustion of heavy oil. Subsequently, Lurgi 1955) and high-temperature steam many petroleum thermal cracking cracking aimed at the co-production of technologies were developed from the 1910s acetylene (BASF process, 1960, Hoechst to the 1920s. However, because these were process, 1960). petroleum refining technologies rather than Ultimately, only exothermic tube type steam petrochemical technologies to obtain gasoline, cracking survived the competition in the

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1970s. Various exothermic tube type steam From the 1950s to the 1960s, of all the cracking processes have been developed, olefins made by steam cracking of naphtha, depending on the type of cracking furnace propylene tended to be being produced in and the method of separating/refining basic excess. Therefore, the triolefin process petrochemicals, and have been competing producing ethylene and n-butylene by with each other. At present, the Stone & disproportionation in the presence of a solid Webster process and the Lummus process, catalyst was developed by Philips in 1960. among others, are widely used all around the This process was only industrialized in world. Exothermic tube type steam cracking Canada in 1966. However, because a has gone through the following technological subsequent expansion in the demand for developments and improvements. In the first propylene solved the problem of excessive half of the 1960s, the retention time in the propylene, the use of this process was tube was shortened from 0.7–1.5 seconds to discontinued within less than 10 years. 0.2–0.4 seconds. This was due to the Although the mechanism of the reaction was discovery of the mechanism underlying the unclear at the time, it was subsequently found adherence of coke to the pipe wall. As a to be metathesis reaction via a carbene metal result, the yield of ethylene increased. In the complex. As mentioned in Section 6.2, due to 1960s, the installation of the tube was a change in the propylene supply-demand changed from horizontal to vertical. In the environment, the reverse reaction was revived 1960s, a quench heat exchanger (TLE) and a as a process for manufacturing propylene by centrifugal compressor were introduced, the metathesis reaction in the 1990s. resulting in energy saving as well as an increase in the size of the equipment.

Fig. 6.5 Ethylene production technology system.

(2) Propylene manufacturing technologies catalytic cracking. Houdry (France) Figure 6.6 summarizes the system of developed the fixed-bed cracking process propylene manufacturing technologies. using a silica-alumina catalyst in 1927 and Propylene as well as ethylene is made from the U.S. Sun Oil industrialized it in 1938. In waste gas obtained by the thermal cracking of 1938, Kellogge developed the catalytic heavy oil. However, petroleum refining cracking process using a fluidized bed technologies to obtain gasoline fractions from catalyst. Standard Oil (NJ) further developed heavy oil did not develop towards the process by joint studies with Kellogge. It non-catalytic thermal cracking, but towards developed the fluidized catalytic cracking

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(FCC) process in 1940 and industrialized it in secondary supply source and classified as 1942. Meanwhile, Socony-Vacuum complementary. However, the steam cracking developed moving bed TCC as a modification of ethane produces ethylene and only very of the Houdry process and industrialized it in small quantities of propylene. Therefore, the 1943. FCC plants are important propylene supply Waste gas is obtained in larger quantities sources in the United States where ethane is by the catalytic cracking of heavy oil than by used in larger quantities as a material for the thermal cracking of heavy oil. Since it ethylene. contains small amounts of ethylene and large Meanwhile, in the 1990s, the supply of amounts of propylene and butylenes, it propylene from the above two byproduct became a large-scale supply source of technologies (steam cracking of naphtha and propylene. This is because thermal cracking the FCC process) became insufficient. is a radical reaction, while catalytic cracking Therefore, technologies for producing is an ionic reaction. propylene as the main product, such as the When gaseous raw materials with C3 or reinforced fluidized catalytic cracking C4 and liquid raw materials such as naphtha process, propane dehydrogenation and the are steam cracked to obtain ethylene, metathesis process, were developed and propylene is also produced in approximately industrialized. These technologies are half the amount of ethylene. This process is a described in Section 6.2, “New trends in major propylene supply source. Especially in petrochemical technology.” Japan, Asia, Europe, etc. where ethylene is Unlike ethylene, propylene has never produced from naphtha by steam cracking, been synthesized from raw materials other the steam cracking process is the most than petroleum to give propylene products important propylene supply source, while since the creation of petrochemistry. waste gas from FCC plants is no more than a

Fig. 6.6 Propylene production technology system. (No propylene production technology predating petrochemistry)

(3) Butadiene manufacturing technologies butadiene was produced in these countries by Since the production of synthetic rubber the processes shown in Fig. 6.7. These were was a very important national issue in coal chemistry and fermentation chemistry Western countries during the Second World technologies. War, importance was attached to the production of butadiene. However, because it was not until after the Second World War that steam cracking of naphtha became widely used in Europe and Japan, during the war

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dehydrogenation process shown in Fig. 6.8 was developed and industrialized on a large scale during the Second World War. The raw material for butylene was obtained from waste gas produced from the catalytic cracking of heavy oil. Although this process is not as competitive as the byproduct process Fig. 6.7 Butadiene production technology from steam cracking, it is still presently used predating petrochemistry in Europe and to cover a shortage of butadiene in the United Japan. States.

The first process is condensation of acetaldehyde. Acetaldehyde was produced from acetylene or fermentation ethanol. Acetaldehyde is condensed and then hydrogenated to give 1,3-butanediol, which is then dehydrated to give butadiene. Fig. 6.8 Butadiene production technology The second process is dimerization of system. acetylene. Under atmospheric pressure, acetylene is dimerized into monovinyl Butadiene is also obtained by acetylene, which is then hydrogenated to give dehydrogenation of n-butane from waste gas butadiene. produced by catalytic cracking of heavy oil or The third process is ethynylation of natural gas (Houdry process). This process acetylene. It is one of the Reppe reactions. was used during the Second World War, but Under pressure, acetylene is reacted with has not been used since then due to its high formaldehyde to give butadiene via cost. 1,4-butynediol and 1,4-butanediol. However, because the third process was developed at (4) Butylenes manufacturing technologies the end of the Second World War, it was only As with propylene, butylenes have never industrialized on a very small scale. produced from raw materials other than The fourth process is petroleum before the creation of dehydration/dehydrogenation of ethanol. In petrochemistry. Butylene manufacturing 1928, it was developed and industrialized in technologies were established only through the Soviet Union. During the Second World petrochemistry. War, it was also industrialized in the United As shown in Fig. 6.9, butylenes are States. According to a modification of this mainly produced from the C4 fraction process, ethanol is oxidized to acetaldehyde, produced by steam cracking of naphtha or and butadiene is obtained by the dehydration waste gas produced by catalytic cracking of reaction of acetaldehyde with ethanol. This petroleum. Butylenes are obtained as process is described above in Section 5.2.5. byproducts in both processes. To obtain At present, as shown in Fig. 6.8 the most specific butylenes, Sasol in South Africa important butadiene supply source is a separates 1-butylene from synthetic byproduct of ethylene production by steam petroleum by the Fisher-Tropsch process. cracking of naphtha. However, in this case, a 1-Butylene is used as an ethylene comonomer hydrocarbon having more carbon atoms than in manufacture of L-LDPE. butane must be used as a raw material, Due to the fact that the demand for because butadiene cannot be obtained by the butylenes is generally not as strong as that for steam cracking of ethane or propane. propylene, processes to produce butylenes as On the other hand, in the United States the main product are not widely used. Some where butane and butylene could be obtained examples are as follows. In reinforced in large quantities, the butylene fluidized bed catalytic cracking to produce

138 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) propylene as the main product, butylenes are production of MTBE. Since isobutylene also produced together with propylene. In could not be adequately supplied from the Saudi Arabia, 1-butylene is produced by byproducts of steam cracking of naphtha and dimerization of ethylene. It is used as an catalytic cracking of petroleum, it was auxiliary raw material for L-LDPE. In Saudi produced in large quantities by Arabia, n-butylene is produced to obtain dehydrogenation of isobutane. However, propylene by the metathesis reaction of from the 2000s onwards, the addition of ethylene with n-butylene obtained by MTBE to gasoline was prohibited and as a dimerization of ethylene. In the 1990s, the result, the dehydrogenation of isobutane demand for MTBE rapidly increased in the declined. United States due to its use as an additive to gasoline. Isobutylene is needed for the

Fig. 6.9 Butylene production technology system.

(5) Higher linear olefin to produce a higher linear olefin mixture with manufacturing technologiesHigher linear internal or terminal double bonds. Other olefin manufacturing technologies originated α-olefin producing technologies include in oleochemistry before the dawn of separation from synthetic oil using the petrochemistry. These technologies are used Fisher-Tropsch process, Ziegler to produce fatty alcohols by the methyl oligomerization of ethylene, SHOP-method esterification and high-pressure reduction of oligomerization of ethylene and catalytic fats and oils, and then dehydrate the alcohol dehydrogenation of n-paraffin. to produce α-olefins (Section 4.3.2). Once it became possible to produce alkylbenzenesulfonic acid soda from dodecene by the tetramerization of propylene, it was then possible to produce higher olefins in large quantities. However, this dodecene was often branched rather than linear, resulting in issues of foam pollution (Section 5.5.2 (3) 1). Accordingly, technologies to manufacture higher linear olefins from fats and oils have come to be utilized again. Meanwhile, several technologies have been developed to produce higher linear olefins Fig. 6.10 Higher linear olefins production using petrochemistry, as shown in Fig. 6.10. technology system. Once n-paraffin has been adsorption separated using a zeolite from the kerosene (6) Aromatic hydrocarbon manufacturing fraction, the n-paraffin can be steam cracked technologies

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Manufacturing processes for aromatic extraction, paraffin and cycloparaffin with hydrocarbons as well as those for olefins are many branched chains are left in the very important manufacturing processes for reformate. These paraffins are useful gasoline basic petrochemicals. Since before the ingredients. For solvent extraction, various creation of petrochemistry, benzene, toluene, polar solvents such as ethylene glycols/water, naphthalene, anthracene, etc. were produced sulfolane, N-methylpyrrolidone/water, by distillation/separation of coal tar obtained Dimethyl sulfoxide (DMSO)/water and by retorting phase of coal. Even now, this is a N-formylmorpholine/water have been used significant process for the manufacture of and many processes such as the Udex process naphthalene. However, it is difficult to obtain have been developed and industrialized. xylene from coal tar. As shown in Fig. 6.11, benzene is The main supply sources for aromatic refined/separated from the above aromatic hydrocarbons from petroleum are cracked hydrocarbon fractions by azeotropic gasoline obtained by steam cracking of distillation and extractive distillation. Apart naphtha for the production of ethylene and a from that, hydrogenating dealkylation of reformate obtained by catalytic reforming of toluene and disproportionation of toluene are petroleum for the production of high octane mainly used for producing benzene. Benzene gasoline. Since cracked gasoline contains and methane are obtained using the former many aromatic hydrocarbons, benzene can be reaction, while benzene and xylene are refined by azeotropic distillation. It is also obtained using the latter reaction. possible to refine benzene, toluene, etc. after Although toluene is useful as a gasoline further increasing the concentration of fraction, there is little chemical demand for it. aromatic hydrocarbons by extractive Therefore, it is rare for toluene to be obtained distillation. As the concentration of aromatic from a reformate. It is exclusively obtained from hydrocarbon is lower in a reformate than in cracked gasoline produced by steam cracking cracked gasoline, first only the aromatic (Fig. 6.12). hydrocarbons are extracted from the reformate by solvent extraction. After

Fig. 6.11 Benzene production technology system.

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Fig. 6.12 Toluene production technology system.

Xylene has three isomers, namely, ortho-, Crystallization has long been performed metha- and para-xylenes. Ethylbenzene is for the manufacture of p-xylene, which has also a C8 aromatic hydrocarbon. Since the the greatest demand (Fig. 6.14). The boiling boiling points of these four aromatic point of each component of mixed xylene is hydrocarbons are similar, it is difficult to similar, while the melting point is different, separate them by distillation. A mixture of being -95°C, -48°C, -25°C, and 13°C for these three xylene isomers, or a mixture of C8 ethylbenzene, m-xylene, o-xylene and aromatic hydrocarbons with ethylbenzene p-xylene, respectively. Consequently, added, is called mixed xylene. Meanwhile, p-xylene can be obtained if mixed xylene is there is greater demand for o-xylene and cooled and crystallized. However, the p-xylene. Ethylbenzene is used as a raw crystallization process consumes much material for styrene. However, in this case, it energy. Therefore, once the adsorption is not refined/separated from mixed xylene, process using solid adsorbents such as zeolite because high purity ethylbenzene is and molecular sieves (Aromax process by synthesized by the reaction of ethylene with Toray, Parex process by UOP) was developed, benzene. it completely replaced the existing process As shown in Fig. 6.13, mixed xylene is from the 1970s onwards. mainly obtained by naphtha steam cracking M-xylene has the smallest demand of the and reforming. Both processes are byproduct three xylene isomers; it is the resulting processes. One process that is used primarily product once an equilibrium mixture of for the production of xylene is mixed xylene has been made by disproportionation of toluene. Benzene is also isomerization and then o-xylene and p-xylene produced in this process. have been separated from the mixture. As industrial processes, the octafining process (Arco/Engelhard) was developed in the 1960s, followed by the isomer process (UOP), the LTI process (Mobil Chemical), etc. In the 1990s, the HTI process (Mobil), in which ZSM-5 zeolite was partially replaced by platinum, was developed and widely used. This process makes use of the phenomenon whereby the equilibrium reaction is further

Fig. 6.13 Xylene production technology progressed by the remaining m-xylene and system. o-xylene because they cannot escape through

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the empty holes in the zeolite as easily as significant as the reaction technologies for p-xylene, making the yield of p-xylene higher basic petrochemicals, while the reaction than the equilibrium concentration. technologies are very significant for the industrial organic chemicals and polymers mentioned below. In terms of separation/refining technologies, in addition to distillation that is generally performed in chemical technologies, solvent extraction and extractive distillation are performed for the separation of butadiene Fig. 6.14 p-Xylene production technology and aromatics, while adsorption is performed system. for the separation of n-paraffin and p-xylene. (7) Syngas manufacturing technologies Recrystallization was performed for the Syngas was originally manufactured from separation of p-xylene, but was later replaced coke. It was at first manufactured for by adsorption because it was expensive. production of city gas in the latter half of the Furthermore, in case of difficulty in 19th century and for ammonia, methanol and separation by physical procedures, separation synthetic petroleum in the first half of the can also be done using differences in 20th century. It is a very old process. Since it reactivity. Some examples are the separation became possible to obtain large amounts of of isobutylene by utilizing differences in petroleum and natural gas after the Second hydration reactivity in the presence of a solid World War, syngas then began to be acid catalyst and the separation of manufactured from these materials. As shown cyclopentadiene from C5 fraction by using in Fig. 6.2, there are two manufacturing differences in dimerization reactivity. technologies. One is exothermic steam Meanwhile, the reaction system is reforming in the presence of a nickel catalyst. broadly classified into non-catalytic and It is often applied to natural gas. The other is catalytic technologies. Steam cracking as a steam reforming by non-catalytic partial non-catalytic technologies and catalytic combustion. A great variety of raw materials cracking of heavy oil and catalytic reforming ranging from natural gas to heavy oil can be of naphtha as catalytic technologies supply used. far greater amounts of basic petrochemicals. There are many other catalytic technologies, (8) Summary primarily for producing specific basic The system of technologies for basic petrochemicals other than ethylene petrochemicals has been described for each (propylene by dehydrogenation of propane, product in subsections (1) to (7). Further, as butadiene by dehydrogenation of butylene, shown in Fig. 6.15, these technologies may α-olefin by oligomerization of ethylene, be cross-sectionally classified into reaction benzene by dealkylation of toluene, benzene technologies and separation/refining and xylene by disproportionation of toluene, technologies. It is characteristic that the p-xylene by isomerization of m-xylene, etc.). separation/refining technologies are just as

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Fig. 6.15 Technology system of basic petrochemicals (summary) chemistry, fermentation acetone/butanol chemistry and other fields that developed 6.1.2 Technological system of industrial before the creation of petrochemistry. organic chemicals There are a great number of industrial Furthermore, there are no derivatives with the organic chemicals and their intermediates; potential to progress to the next stage of there are also a great number of processes for industrial organic chemicals, like manufacturing these products. As shown in acetaldehyde in acetylene chemistry. In Fig. 6.16, the technological system of these acetylene chemistry, not only C2 products, chemicals is made up of C1 chemistry such as acetic acid, but also various [Footnote 1], olefin chemistry, aromatic compounds, such as C3 acetone, C4 butyl hydrocarbon chemistry, cycloparaffin alcohol and butadiene, were obtained from chemistry and other synthetic organic C2 acetaldehyde. This was because C2 chemistry. acetylene was the only basic chemical in acetylene chemistry. In petrochemistry, as mentioned in Chapter 3, ethylene oxide, acetone, acrylonitrile, acrolein, phenol, etc. are important derivatives from which further development of various products is expectable, but none of them have as yet grown to a key material comparable to acetaldehyde in acetylene chemistry. In Fig. 6.16 Technology system of industrial petrochemistry, derivatives with organic chemicals. corresponding carbon number atoms are often manufactured from the starting materials of The reactivity of olefins is not as strong as various olefins and aromatic hydrocarbons that of acetylene but not as weak as that of obtained as basic petrochemicals. Moreover, paraffin (alkane). Moreover, olefin chemistry importance is often attached not to the has also developed in many areas due to the development of processes for production of fact that not only ethylene but also various expected industrial organic chemicals via other olefins, such as propylene, butylenes several industrial organic chemicals, but to and butadiene, are simultaneously produced the development of processes that can by the steam cracking of naphtha, one of the produce expected industrial organic olefin manufacturing processes. On this point, chemicals from basic petrochemicals, either olefin chemistry is clearly different from directly or in as few steps as possible. acetylene chemistry, fermentation ethanol Furthermore, rather than stoichiometric reactions, petrochemistry often aims at [Footnote 1] The system of processes for manufacturing C1 or more industrial organic chemicals from C1 methane and syngas and the catalytic reactions, using the cheapest categories of such products are called C1 chemistry.

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possible secondary raw materials, such as acid by the stoichiometric reaction of oxygen, ammonia or water. In particular, it propylene with sulfuric acid and then often aims at reactions that can replace hydrolyzed it to make IPA and started reactions that use elements that are not industrial production. This process triggered contained in the final expected product (for off petrochemistry. Similarly, in 1923, example, addition of hypochlorous acid and Sharpless Solvent produced amyl alcohol by oxidation by nitric acid). In green chemistry the reaction of isopentene with sulfuric acid, terms, these are reactions with good atom followed by hydrolysis. In 1930, Carbide & utilization efficiency. Carbon Chemical produced ethyl sulfuric acid from ethylene and sulfuric acid and then hydrolyzed it to make synthetic ethanol and (1) Olefin chemistry: addition to started industrial production. In the same year, double bonds Shell Chemicals started industrial production As shown in Fig. 6.17, olefin chemistry is of sec-butyl alcohol from n-butylene using classified as addition reactions to the double the sulfuric acid process. However, since bond of olefins, reactions to places other than production of alcohol by the sulfuric acid the double bond, and special reactions. Of process is associated with production of large these, special reactions are further classified amounts of dilute sulfuric acid, it must be into the oxychlorination process and olefin concentrated for reuse. Consequently, once metathesis reactions. Oxychlorination and the catalytic process for directly producing metathesis reactions are described in (3) of alcohols by adding water (direct hydration) to this section and in Section 6.2.1, respectively. the double bond of olefins was developed, this method soon replaced the sulfuric acid process. In 1947, Shell Chemicals developed a process for directly synthesizing ethanol from ethylene and steam in the presence of a phosphoric acid catalyst and industrialized it the following year. In 1951, ICI started Fig. 6.17 System of olefin chemistry. industrial production of IPA by direct hydration of propylene in the presence of a The addition reaction to the double bond tungsten oxide-titanium oxide-iron oxide of olefins is the core of olefin chemistry. It is catalyst at 250 atm and 270˚C. Ether is similar to addition reactions to the triple bond directly manufactured by this process if in acetylene chemistry. However, as shown in alcohol is added to the double bond in place Fig. 6.18, olefin chemistry is much more of water. This process was used for diverse than acetylene chemistry. production of diethyl ether. The MTBE developed in the late 1970s was the first ether 1) Addition of sulfuric acid, water and to be produced on a large scale. MTBE was alcohol produced from isobutylene and methanol in The addition of sulfuric acid to the the presence of a solid acid catalyst, such as double bond of olefins is the oldest acid ion exchange resin. At present, petrochemical process. As described in ethyl-t-butyl ether (ETBE) is produced from Chapter 5, History of petrochemistry, in 1920, isobutylene and ethanol. Standard Oil (NJ) produced isopropyl sulfuric

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Fig. 6.18 Olefin chemistry; System of technology on addition to double bond.

2) Addition of hypochlorous acid and chemistry developed early in the 1930s oxygen because a process was developed for The addition of hypochlorous acid to the manufacturing ethylene oxide at a low price. double bond of olefins is one of the oldest In 1937, IG Farben released polyoxyethylene stoichiometric reactions, along with the ether of alkyl phenol as a nonionic surfactant. addition of sulfuric acid. In 1920, Carbide & In addition, fatty acid, fatty acid amide and Carbon Chemical produced ethylene fatty alcohol polyoxyethylene ether were chlorohydrin by the reaction of ethylene with industrialized. In 1944, U.S. company Atlas hypochlorous acid. This process also Powder released an ester of sorbit and fatty triggered off petrochemistry. Ethylene oxide acid and its polyoxyethylene compound as is obtained when ethylene chlorohydrin is nonionic surfactants named Span and Tween, dehydrochlorinated with sodium hydroxide or respectively. Ethylene oxide chemistry calcium hydroxide. Since this reaction is already started before petrochemistry had stoichiometric, large amounts of sodium fully flourished. chloride and calcium chloride are produced as As with ethylene, propylene chlorohydrin byproducts. is produced by the stoichiometric reaction of Ethylene oxide is reacted with water to propylene with hypochlorous acid and then give EG, diethylene glycol and triethylene dehydrogenated with calcium hydroxide to glycol. In the 1930s, ethylene cyanohydrin give propylene oxide. In 1929, UCC was made from ethylene oxide and hydrogen industrialized this process. However, unlike cyanide and then thermally cracked to give the case with ethylene, catalytic technologies acrylonitrile. EG can also be made by for directly epoxidizing propylene with hydrolysis of ethylene chlorohydrin with oxygen have not yet been developed and sodium hydroxide solution (BASF, 1919). therefore, the propylene chlorohydrin process However, the chlorohydrin process is still used as the main manufacturing wastes chlorine and sodium hydroxide. In process for propylene oxide. 1937, UCC industrialized a process for Oxirane Chemical developed the Halcon directly producing ethylene oxide by process in 1968 and industrialized it in 1970. epoxidizing ethylene by air oxidation (10–30 According to this process, a peroxide atm, 230–325°C) in the presence of a silver (hydroperoxide) is made from isobutane, catalyst. After the development of this ethylbenzene, cumene, etc. and is then catalytic process, the ethylene chlorohydrin reacted with propylene in the presence of a process declined. catalyst to give propylene oxide (see Section It is worth noting that ethylene oxide 3.4.3 (4)). In the 2000s, it became possible to

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produce hydrogen peroxide cheaply on a EDC-oxychlorination process became large scale, resulting in the industrialization exclusively used (see Section 5.4.2 (2) 4)). of a process for producing propylene oxide by According to the ethylene oxychlorination the reaction of propylene with hydrogen process, ethylene, hydrogen chloride and peroxide. Since only water is produced as a oxygen (or air) are reacted to give EDC in the byproduct in this case, the production of presence of a copper chloride/potassium propylene oxide is not influenced by the chloride catalyst. The key point of this demand for byproducts. process is that hydrogen chloride obtained as a byproduct of thermal cracking of EDC is 3) Addition of chlorine reacted with ethylene to give EDC. The addition of chlorine to the double The development of industrial processes bond is also an old process. In 1925, Carbide for manufacturing chlorine from hydrogen & Carbon Chemical added chlorine to chloride started a long time ago. In the 1820s, ethylene to give ethylene dichloride (EDC) the Leblanc process as the first method of and started production of it. EDC was manufacturing soda (patented in 1791 in dehydrochlorinated to give vinyl chloride. France) was actively used in the United However, in 1932, Griesheim Electron in Kingdom. However, the hydrogen chloride Germany developed a new process for byproduct of this process was released into directly synthesizing vinyl chloride from the air and rivers, leading to the enactment of acetylene and hydrogen chloride in the the Alkali Act in the United Kingdom in 1863. presence of a mercuric chloride-impregnated Investigations were conducted to collect silica gel catalyst; as a result, the EDC hydrogen chloride and make it into chlorine process was not widely used for the and then into bleaching powder. As a result, production of vinyl chloride. the Weldon process (a liquid-phase process After the Second World War, as ethylene using a manganese dioxide catalyst) and the became supplied cheaply in large quantities Deacon process (a gas phase process using a by steam cracking, the EDC process revived. cuprous chloride-impregnated brick catalyst, Initially, the dehydrochlorination reaction to the world’s first heterogeneous gas phase produce vinyl chloride from EDC was a process) were developed in 1866 and 1868, liquid-phase stoichiometric reaction using an respectively. Since the Weldon process alkaline solution. However, in this case, half produced thick gas, it was industrialized of the chlorine was wasted as alkali salt. After immediately. Meanwhile, since the Deacon that, gas phase cracking in the presence of a process produced dilute gas, it was not until pumice stone or activated charcoal catalyst the 1880s that the process came into wide use, was developed. In this case, half of the after Hurter conducted fundamental studies chlorine could be collected as hydrogen on the absorption of hydrogen chloride. In chloride. However, this had the disadvantage 1932, Raschig developed an oxychlorination in that the life time of each catalyst was short; process for producing chlorobenzene from as a result, the noncatalytic thermal cracking benzene, hydrogen chloride and oxygen in the process was widely used, in which EDC was presence of a copper oxide-cobalt passed at high speed through a high oxide-alumina catalyst or a copper oxide-iron temperature and pressure pipe. Since the EDC oxide-alumina catalyst. This process was an was thermally cracked to give vinyl chloride important constituent of the Raschig process and equimolar hydrogen chloride, the (formation of phenol and hydrogen chloride combined ethylene-acetylene process was from chlorobenzene and water) by gas phase developed for producing vinyl chloride by the hydrolysis of chlorobenzene, industrialized in reaction of hydrogen chloride thus obtained 1935 (see Section 4.6.1). This Raschig with acetylene. However, after the ethylene process became a model for the ethylene oxychlorination process was developed in oxychlorination process. 1965, the acetylene process and the combined A process in which hydrogen chloride as acetylene-ethylene process both declined a byproduct of thermal cracking of EDC was rapidly, while the combined made into chlorine using a method similar to

146 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) the Deacon process and reused was also started production of ethylbenzene using the developed and industrialized. However, the gas phase process in the presence of a EDC production process by reproduction of phosphoric acid-silica/alumina catalyst. In chlorine was short-lived. This was because 1958, UOP developed a gas phase process the ethylene oxychlorination process was using a boron trifluoride-hydrogen fluoride industrialized immediately after the catalyst. This was followed by the development of this process. Chlorine is not development and industrialization of the produced by the ethylene oxychlorination Mobil-Badger process, which uses a zeolite process, because ethylene is chlorinated in the ZSM-5 catalyst, in 1980. It was subsequently presence of a copper oxide catalyst and the widely used around the world. To improve reduced catalyst is reproduced by air and manufacturing processes for ethylbenzene, hydrogen chloride. attempts have been made to control higher The application of the oxychlorination order alkylated substances, to improve the process has not yet been extended to conversion rate, to decrease the corrosiveness compounds other than EDC and of catalysts and to prolong the life time of chlorobenzene. In 1975, a process for catalysts. manufacturing chloromethane from methane, Benzene is added to the double-bond of hydrogen chloride and oxygen in the presence propylene to give cumene. Cumene is of a copper chloride/potassium chloride fused exclusively used for the production of phenol salt catalyst was industrialized. However, this and acetone by the oxidation/cleavage process did not create any major applications reaction. This phenol/acetone co-production for oxychlorination. process using the cumene process was developed by Hock and Lang in 1944 and 4) Addition of aromatic hydrocarbon, was then industrialized by Hercules (United isobutane and olefins States) and Distillers (United Kingdom) in The addition of aromatic hydrocarbons 1953. Cumene is synthesized in the presence [Footnote 2], isobutane and olefins to double of a sulfuric acid/aluminum bonds is a petroleum refining technology that chloride/hydrogen fluoride catalyst in the developed in the 1930s. Petroleum waste gas liquid-phase process, while it is synthesized containing olefins is reacted with benzene in by addition of steam in the presence of a the presence of an aluminum chloride catalyst phosphoric acid-silica catalyst in the gas to give ethylbenzene and cumene. Polymer phase process. Subsequent improvement of gasoline is obtained by dimerization or catalysts resulted in the use of a zeolite trimerization of olefins in the presence of a catalyst, as was used for ethylbenzene. Use of phosphoric acid catalyst, while alkylate the zeolite catalyst has spread rapidly since its gasoline is obtained by the reaction of olefins industrialization in 1996. with isobutane. The third most important addition Of these compounds, ethylbenzene and reaction of aromatic hydrocarbons to the cumene obtained by the addition reaction of double bond of olefins is the production of aromatic hydrocarbons to double bonds are higher alkylbenzene from higher olefins and important raw materials for petrochemical benzene. The sulfonate of higher products. Ethylbenzene is dehydrogenated to alkylbenzene is an important anionic give styrene. In 1930, styrene was surfactant and is used in large quantities for industrialized by IG Farben. Ethylbenzene detergents. The addition of benzene to higher was produced by the liquid-phase process in olefins is often performed by liquid-phase the presence of an aluminum chloride catalyst process in the presence of hydrogen fluoride, [Footnote 3]. In 1953, Koppers Chemical aluminum chloride, etc. as a catalyst.

[Footnote 2] This reaction is usually classified as an alkyl-group 5) Hydroformylation (oxo process) substituention reaction into aromatic hydrocarbons (alkylation). However, it is described here, because it can formally be considered an aromatic hydrocarbon addition reactionfrom the olefin in the presence of an aluminum chloride catalyst to give perspective. ethylbenzene without going through ethylene. This route was [Footnote 3] Ethyl chloride that is made by the reaction of selected in countries where fermentation ethanol could be obtained fermentation ethanol with hydrogen chloride is reacted with benzene more easily than ethylene. This is a typical Friedel-Crafts reaction.

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In the hydroformylation of olefins, catalyst. Adiponitrile is hydrogen reduced to hydrogen and a formyl group (-CHO) are give hexamethylenediamine, which is then added to the double bond to give aldehyde used as a raw material for 6,6-nylon. with one more carbon atom than the original olefin. Aldehyde is made into various (2) Olefin chemistry: Reaction to places derivatives by reduction (alcohol), oxidation other than double bonds (carboxylic acid) and aldol condensation. In Like ethynylation (reaction acetylene of 1938, Roelen (Ruhr-Chemie) discovered that to hydrogen) as one of the Reppe reactions in propionaldehyde is produced when ethylene acetylene chemistry, the reaction to hydrogen is reacted with carbon monoxide and adjacent to the double bond and the reaction hydrogen in the presence of a cobalt catalyst to hydrogen in the methyl group adjacent to (HCo(CO)4). When propylene is reacted in the double bond (hydrogen at the allylic the above manner, the main product is position) were successively developed in n-butyraldehyde, although isobutyraldehyde olefin chemistry from the latter half of the is also obtained. n-butyraldehyde is 1950s onwards (Fig. 6.19). As a result, the hydrogenated as it is to give n-butanol, or demand for olefin chemistry using propylene hydrogenated after aldol condensation to give and butylene as starting materials expanded 2-ethylhexanol. These alcohols were reacted dramatically, despite it once having a lower with phthalic anhydride to give phthalate demand than ethylene. esters, which were used as plasticizers for polyvinyl chloride. Since 2-ethylhexanol in particular is used in large quantities even now, n-butyraldehyde is in great demand, although there is an excess of isobutyraldehyde. In 1975, UCC and other companies succeeded in the industrialization of the

hydroformylation process using the Fig. 6.19 Olefin chemistry; System of Wilkinson catalyst (triphenyl reactions to places other than double bonds. phosphine-coordinated rhodium catalyst). This process can makes a significantly higher 1) Direct synthesis of acetaldehyde from n-aldehyde/isoaldehyde ratio than the cobalt ethylene catalyst process. Hydroformylation is applied In acetylene chemistry, acetaldehyde was not only to ethylene and propylene, but also made by the addition of water to acetylene, to C7–C12 olefin oligomers, such as from which important derivatives such as isoheptene, diisobutylene and tripropylene. acetic acid, acetone and butadiene were C8–C13 oxoalcohols produced by this produced. However, the process for reaction are made into phthalate esters and producing acetaldehyde from ethylene is then used as plasticizers. C11–C18 α-olefins time-consuming, because ethanol must be undergo hydroformylation to give C12–C19 synthesized first and then oxidized to give linear higher alcohols. These are used for the acetaldehyde. In 1930, UCC industrialized production of surfactants and fiber this process using ethylene from petroleum auxiliaries. waste gas as a raw material; many U.S. chemical companies later produced 6) Addition of hydrogen cyanide acetaldehyde by this process. The addition reaction of hydrogen In 1894, F.C.Phillips found out that cyanide to double bonds is important for the ethylene was stoichiometrically oxidized by production of adiponitrile in petrochemistry. palladium metal salt to give acetaldehyde. Among several presently available methods This reaction is very unique in that hydrogen of manufacturing adiponitrile, the most of ethylene is replaced by the palladium metal common is the addition of two hydrogen salt hydroxy group derived from water. The cyanide molecules in two stages to butadiene resulting vinyl alcohol becomes acetaldehyde in the presence of a nickel-triallyl phosphite as a tautomer. More than 60 years later, this

148 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) reaction was converted to a catalytic reaction process by gas phase reaction in the presence and used as a petrochemical process. In 1956, of a solid catalyst composed of Schimidt (Wacker Chemie) discovered a silica-impregnated palladium salt. This reaction to synthesize acetaldehyde from process also replaced the method of ethylene and oxygen in the presence of a manufacturing vinyl acetate from acetylene redox catalyst that was an aqueous solution of and acetic acid. copper chloride containing a small amount of palladium chloride [Footnote 4]. In 1959, 3) Ammoxidation of propylene Wacker Chemical, jointly with Hoechst, In the 1930s, the demand for acrylonitrile completed an industrial process using this as a raw material for synthetic rubber (NBR) reaction. In the one-stage process (Hoechst expanded; as a result, an ethylene process), the oxidation of ethylene and cyanohydrin process was developed using the reproduction of palladium salt take place at stoichiometric reaction of ethylene oxide with the same time in the same reactor. Since the hydrogen cyanide, and production of conversion rate of ethylene is 35–45% under acrylonitrile started. Around the 1950s, conditions of 3 atm, 120–130°C and production of acrylic fiber also started in the liquid-phase reaction, it requires the United States, resulting in a rapid increase in circulation of unreacted gas. Therefore, the demand for acrylonitrile. To increase the highly purified ethylene and oxygen are used. supply, American Cyanamid developed a In contrast, in the two-stage process (Wacker process for adding hydrogen cyanide to process), oxidation of ethylene and acetylene and industrialized it in 1955. In reproduction of palladium are performed 1957, Knapsack-Griesheim developed a separately. As the conversion rate of ethylene process for manufacturing acrylonitrile, in is nearly 100% under conditions of 10–12 which lactonitrile made by the reaction of acetaldehyde with hydrogen cyanide was atm, 100°C and liquid-phase reaction, dehydrated to give acrylonitrile. Due to the circulation of unreacted gas is not needed and fact that a process for directly synthesizing reproduction of palladium can be performed acetaldehyde from ethylene (Hoechst-Wacker with air. The idea of the redox catalyst as an process mentioned above) was developed aqueous copper solution containing palladium simultaneously, acrylonitrile production was chloride was truly epoch-making. expected to become a large-scale consumer of As mentioned in Section 5.3.2 (3), one of acetaldehyde. the two core products in acetylene chemistry However, in 1958, the U.S. Sohio (acetaldehyde and vinyl chloride) declined developed a propylene ammoxidation process. due to the development of this reaction early According to this process, propylene, in the 1960s. This prompted rapid progress in ammonia and air are reacted in the presence petrochemistry. of a bismuth molybdate catalyst in a fluidized

bed at 450˚C. At almost the same time, 2) Acetoxylation of ethylene Distillers (the United Kingdom) also When ethylene and air are passed through developed a manufacturing process using a an acetic acid solution in the presence of bismuth molybdate catalyst. In the sodium acetate using a palladium ammoxidation of propylene, it is the methyl chloride-cupric chloride solution catalyst, group (hydrogen at the allylic position) rather acetoxylation of ethylene occurs to give vinyl than the double bond of propylene that reacts acetate. In the 1960s, ICI and Celanese to give a nitrile group. This was quite an industrialized this process by liquid-phase epoch-making reaction that had previously reaction. However, both companies been unknown. The development of this discontinued it within a few years, because process meant a decline in the hydrogen corrosion occurred. Bayer and Hoechst cyanide addition process using acetylene as a succeeded in the industrialization of this raw material as well as the acetaldehyde process using ethylene as a raw material, and [Footnote 4] The mechanism of this reaction has been investigated in propylene became a raw material for detail, showing that the oxygen of acetaldehyde is not from air, but from water used as a solvent. acrylonitrile.

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Catalysts for ammoxidation were world-first process. Only one of the methyl subsequently improved by the addition of groups of isobutylene is oxidized. In 1982, various promoters to bismuth-molybdenum Nippon Shokubai became the first in the complex oxides. In addition, various world to industrialize it. The following year, industrial catalysts were developed, such as a Mitsubishi Rayon also industrialized it using bismuthic acid-uranium catalyst containing its own technology. Isobutylene is at first depleted uranium. In the Sohio process, the made into t-butyl alcohol in the presence of yield of acrylonitrile was initially not so high an acid catalyst, such as ion exchange resin, due to the production of hydrogen cyanide, and then into methacrolein by oxygen acetonitrile and other byproducts. Catalysts oxidation/dehydration in the presence of a have subsequently continuously been molybdenum/iron/nickel-based catalyst. improved to increase the yield of acrylonitrile Therefore, while the double bond of and to decrease the formation of byproducts. isobutylene is retained, the methyl group is not necessarily partially oxidized. A 4) Partial oxidation of the methyl group heteropolyacid catalyst is used for oxygen adjacent to the double bond of olefins oxidation of methacrolein into methacrylic Following the ammoxidation process, acid. production of acrolein by partial oxidation of MMA has been produced by the acetone the methyl group of propylene to aldehyde cyanohydrin process, in which acetone is was industrialized using a bismuth molybdate stoichiometrically reacted with hydrogen or bismuth phosphomolybdate catalyst that cyanide, since the 1930s. The isobutylene was also used for acrylonitrile. Acrolein is process developed by several Japanese further oxidized to give acrylic acid, which is companies is now replacing the acetone then esterified to give acrylic acid esters. cyanohydrin process all around the world. Acrolein was also used as a starting material for synthetic glycerin. 5) Chlorination of propylene at the allylic Production of acrolein began with the position industrialization of a gas phase condensation While the addition of chlorine to reaction of acetaldehyde with formaldehyde propylene is easy, the resulting by Degussa in the early 1940s, in the period dichloropropane is not industrially important, of coal chemistry. In 1958, Shell Chemical unlike EDC, because it is not in demand. On industrialized a process for manufacturing the other hand, at 300°C or higher, acrolein by the oxidation of propylene in the substitution reaction of chlorine to hydrogen presence of a cuprous oxide catalyst, while at the allylic position of propylene occurs in Distillers developed a propylene oxidation place of addition reaction. By using this process using a copper oxide-silica catalyst. reaction, Shell Chemical developed a method However, once the above bismuth molybdate of manufacturing allyl chloride in 1937 (see catalyst was developed, it was the main Section 3.4.3 (9)). process used. When n-butylene is air oxidized in the (3) Aromatic hydrocarbon chemistry presence of a vanadium oxide catalyst, both In the middle of the 19th century, of the methyl groups are oxidized to give aromatic hydrocarbon chemistry bore fruit in maleic anhydride and maleic acid. In 1962, the synthetic dye industry using coal tar as a the U.S. Petro-Tex Chem industrialized this raw material. In particular, substitution process. In 1970, Mitsubishi Chemical reactions of aromatic rings, such as industrialized a fluidized bed process using a chlorination (e.g. chlorobenzene), nitration vanadium pentoxide-phosphoric acid catalyst. (nitrobenzene) and sulfonation This method was outstanding in terms of heat (benzenesulfonic acid), and reactions of their removal. functional groups to introduce various The method of manufacturing MMA substituents, such as amine (aniline), diazo from isobutylene developed by many and hydroxyl (phenol) groups, were almost Japanese companies is a significant, all completed in the latter half of the 19th

150 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) century. Furthermore, the chlorination of oxidation of o-xylene in the presence of a side-chain methyl groups, the synthesis of vanadium oxide-based catalyst. In coal tar derivatives of the resulting chlorinated chemistry, a method of manufacturing substances, such as benzyl alcohol and phthalic anhydride from naphthalene by air benzoic acid, and the production of phthalic oxidation of naphthalene in the presence of a anhydride, maleic anhydride, etc. by partial vanadium oxide-based catalyst had been oxidation of naphthalene and benzene rings industrialized in 1916 (see Section 4.6.2). were also completed under the umbrella of Therefore, it may be said that air oxidation of aromatic hydrocarbon chemistry before the o-xylene was developed as an extension of creation of petrochemistry. In 1941, IG coal tar chemistry. Farben started production of polyurethane Meanwhile, terephthalic acid as a raw foam composed of TDI. In 1958, DuPont material for polyester developed together started production of MDI. TDI and MDI with petrochemistry, since production of were manufactured by the process for polyester started around 1950. In air synthesizing aromatic isocyanate using the oxidation of p-xylene, one of the two methyl reaction of aromatic amine with phosgene. groups can be oxidized to give paratoluic acid, As mentioned above, the technological but the second methyl group cannot be system of large-scale aromatic industrial oxidized as readily as in o-xylene. In 1951, organic chemicals was already nearly DuPont industrialized a stoichiometric completed under coal tar chemistry. process for oxidizing p-xylene with nitric Meanwhile, dehydroalkylation of toluene, acid in two stages, and started producing disproportionation of toluene, isomerization terephthalic acid. Oxidation with nitric acid is of xylene, alkylation of aromatic more costly than air oxidation and oxygen hydrocarbons, etc. were developed in oxidation. Subsequently, aiming at cost petroleum refining chemistry in the 1930s. reduction, ICI developed a manufacturing Aromatic hydrocarbon chemistry, which process in which air oxidation and nitric acid developed in the fields of coal tar chemistry oxidation were performed in the first and and petroleum refining chemistry flowed over second stages, respectively. into petrochemistry. Accordingly, as shown In 1952, Henkel developed the first in Fig. 6.20, the direct oxidation of side chain Henkel process, in which potassium methyl groups and the oxidation of hydrogen orthophthalate that could be manufactured by at the α-position of side chain alkyl groups air oxidation of o-xylene was isomerized with are the only processes of aromatic a cadmium catalyst in carbon dioxide under hydrocarbon chemistry that were developed conditions of 1–8 atm and approximately as new petrochemical processes after 400°C to give potassium terephthalate. In petrochemistry began to fully develop in the 1958, this process was industrialized for the 1950s. first time in the world by Kawasaki Kasei Chemicals in Japan. Henkel developed the second Henkel process for producing potassium terephthalate and benzene by disproportionation of potassium benzoate. In 1963, this process was industrialized for the first time in the world by Mitsubishi Kasei in Japan. In this case, benzoic acid was produced by air oxidation of toluene (direct Fig. 6.20 System of of aromatic hydrocarbon oxidation of the side chain methyl group in chemistry. the presence of a cobalt salt catalyst), a process that was not available in the period of 1) Direct oxidation of side chain methyl coal tar chemistry (toluene side-chain groups chlorination process). In 1969, BASF developed a process for In 1950, Imhausen in Germany developed manufacturing phthalic anhydride by air a very sophisticated process for

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manufacturing DMT. According to this oxidized by the same process as was used for process, one of the methyl groups of p-xylene p-xylene to give isophthalic acid. Isophthalic is air oxidized into p-toluic acid in the acid industrialized by Oronite Chemical in presence of a cobalt naphtenate catalyst; after 1955 was used as an auxiliary raw material it is methylesterified, another methyl group is for alkyd resin and unsaturated polyester. air oxidized and the resulting substance is methylesterified again. This DMT process 2) Oxidation of hydrogen at the was industrialized by Hercules in the United α-position of side chain alkyl groups States and many other companies around the Hydrogen at the α-position of the side world. It has the advantage that the purity of chain alkyl group of ethylbenzene or cumene DMT, unlike that of terephthalic acid, can be is oxidized to give a peroxide. This process is increased by distillation. In polymerization, it important for manufacturing intermediates of is also advantageous that the reaction styrene and phenol. proceeds by transesterification between DMT Phenol is an important raw material, not and EG. However, because methanol is only for fine chemicals, such as dyes, produced as a byproduct, it must be returned pharmaceuticals, pesticides and explosives, but to DMT plants for reuse. also for phenol resin. As an industrial organic In 1955, Scientific Design developed a chemical, it has been produced on a large process for manufacturing terephthalic acid scale since the period of coal tar chemistry. In by oxidizing p-xylene in an acetic acid petrochemistry, it was initially used as a raw solvent in the presence of a cobalt acetate or material for nylon. It then became manganese acetate catalyst and a bromine increasingly important as a raw material for compound promotor. This process was tested synthetic detergents, bisphenol A (epoxy for industrialization at Amoco Chemical and resin, polycarbonate resin), etc. was then industrialized by Mitsui In 1890, phenol was industrialized by Petrochemical Industries and Maruzen sulfonation process of benzene. As mentioned Petrochemical in 1958 and 1960, respectively. in Section 4.6.1, the chlorobenzene and It was subsequently widely used all around Raschig processes were subsequently the world. industrialized in 1925 and 1935, respectively. Following the Amoco process, a process The process for manufacturing cumene is for manufacturing chloromethylbenzene from described in Section 6.1.2 (1) 4). When toluene, formaldehyde and hydrogen chloride cumene is air oxidized at 130°C in the and a process for manufacturing presence of an aqueous alkali solution, diisopropylbenzene from benzene and hydrogen at the α-position is oxidized to give propylene were developed in 1960. cumene hydroperoxide. After unreacted As mentioned above, the method of cumene is removed by distillation, cumene manufacturing terephthalic acid went through hydroperoxide is concentrated and the various changes, but the Amoco process concentrate is then treated with 10% sulfuric finally gained global precedence as the means acid at 50°C to give phenol and acetone. of direct oxidation of p-xylene. According to Production of phenol by the cumene process this process, terephthalic acid is polymerized has the advantage that the reaction conditions with EG to give polyester. Because water is are much milder than for the existing the only byproduct, unlike the DMT process, processes and moreover, there are no wasted it does not require the collection of methanol. auxiliary raw materials. Meanwhile, synthesis The Amoco process developed to a process of phenol by direct oxidation of benzene still for manufacturing highly purified terephthalic remains one of the dreams of chemical acid in the 1970s and the production scale of researchers. Although many attempts have this process increased further from the 1990s been made to realize this dream, none of them onwards. have have had the driving success of the Oxidation of the second methyl group of cumene process in industrialization. m-xylene was as difficult as it was for When ethylbenzene is air oxidized, p-xylene. However, m-xylene was air hydrogen at the α-position is oxidized to give

152 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) ethylbenzene hydroperoxide. This substance The process for manufacturing is reacted with propylene to give propylene caprolactam can be roughly divided into two oxide and α-phenylethyl alcohol. Styrene is halves. In the first half, cyclohexanone oxime obtained by dehydration of the latter is produced. In the second half, compound. This method co-produces cyclohexanone oxime is allowed to undergo propylene oxide and styrene. Beckmann rearrangement to give caprolactam. This process yields approximately 4.5 times (4) Cycloparaffin chemistry more ammonium sulfate than caprolactam, Throughout the technology system of because ammonium sulfate is obtained as a industrial organic chemicals as shown in Fig byproduct in the stages of manufacturing 6.16, cycloparaffin chemistry has flourished hydroxylamine, manufacturing oxime and little. Beckmann rearrangement. This is a serious Adipic acid and ε-caprolactam are the disadvantage with this process. Accordingly, only industrial organic chemicals that are various methods have been developed to produced on a large scale from cyclohexane. control the amount of ammonium sulfate Both of them are C6 compounds. The byproduct. However, there are few processes reactivity of cycloparaffin is lower than that that are still used to counter the oxime of olefins, but is higher than that of paraffin. process. One of them is photonitrosation Cyclohexane produced by the hydrogen developed by Toray. It is a unique process in reduction of benzene is the only cycloparaffin which cyclohexane, nitrosyl chloride and that is easily obtained in large quantities. It is hydrogen chloride are reacted under very costly to synthesize other cycloparaffins photoirradiation to give cyclohexanone oxime or to separate them from petroleum. hydrochloride. This is one of the rare Adipic acid and caprolactam were examples in which a photochemical reaction industrialized by DuPont and IG Farben in is used for large-scale production of industrial 1938 and 1940, respectively, during the coal organic chemicals. Since hydroxylamine is tar chemistry era. Phenol was used as a raw not used in this process, the amountof material in both cases. Phenol is reduced with ammonium sulfate byproduct can be hydrogen to give cyclohexanol, which is decreased. However, it is still obtained as a oxidized with nitric acid to give adipic acid. byproduct of the Beckmann rearrangement Caprolactam was produced by Beckmann process. rearrangement from cyclohexanol via In 1994, Enichem developed a process in cyclohexanone and cyclohexanone oxime. which cyclohexanone oxime is directly The process from hexanol onwards was a produced from ammonia and cyclohexanone combination of stoichiometric reactions for using hydrogen peroxide without using adipic acid and caprolactam, which hydroxylamine in the presence of an subsequently remained unchanged for a long MFI-type zeolite titanosilicate (TS-1 zeolite) period of time. catalyst (ammoximation process). Water is At the beginning of the 1960s, it became the only byproduct of this process. possible to make large quantities of Meanwhile, Sumitomo Chemical developed cyclohexane from benzene, and cycloparaffin high-silica MFI zeolite, a heterogeneous chemistry started bearing fruit. As shown in catalyst causing Beckmann rearrangement in Fig. 6.16, air oxidation and photonitrosation the gas phase; the company industrialized a of cyclohexanone were industrialized on a manufacturing process in which large scale in the area of cycloparaffin ammoxidation was combined with gas phase chemistry. Beckmann rearrangement in 2003. Sumitomo As a result, the raw material changed Chemical became the first in the world in the from phenol to cyclohexane. Since a mixture 60-year history of caprolactam production to of cyclohexanol and cyclohexanone is successfully produce caprolactam without obtained by air oxidation of cyclohexane, any ammonium sulfate byproduct. adipic acid and caprolactam are both Meanwhile, Asahi Kasei developed an produced from the mixture. outstanding process for manufacturing

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cyclohexene by partial hydrogenation of introduction of centrifugal compressors. benzene. Cyclohexanol is easily produced by However, in the 1960s, ICI developed a the addition reaction of water to the double low-pressure process (50–100 atm) using a bond of cyclohexene. The addition reaction of copper-zinc-aluminum oxide catalyst and water is a classic petrochemical process for industrialized it on a large scale of 310,000 alcohol production, mentioned in Section tons in 1972. Furthermore, Lurgi developed a 6.1.2 (1). Asahi Kasei industrialized it in process for manufacturing methanol by using 1990. a multitubular reactor in the presence of a copper oxide-zinc oxide catalyst. At present, (5) C1 chemistry large methanol plants are being built that are Chemistry stemming from C1 methane capable of producing 2 million tons annually. and syngas is called C1 chemistry. Following The industrial production of the oil crises, much attention was focused on formaldehyde from methanol by air oxidation potential oil depletion in the future. C1 in the presence of a copper or silver catalyst chemistry has been actively studied since was already being performed at the end of the then. Figure 6.21 shows the current 19th century. Hydroformylation is described technology system. Many of these above in Section 6.1.2 (1) 5). The industrial technologies have been available since before manufacture of phosgene from carbon oxide the creation of C1 chemistry. and chlorine in the presence of an activated charcoal catalyst was already established in the 19th century. The manufacture of isocyanate from phosgene and amine was also already performed in the coal chemistry era, having started when the manufacture of polyurethane foam from TDI began in 1941. Since C1 phosgene is a bi-functional compound, it is reacted with different bi-functional compounds to give polymers. The industrialization of polycarbonate by condensation polymerization of phosgene and Fig. 6.21 System of C1 chemistry. BPA was performed by Bayer and GE in 1957. 1) C1 chemistry from syngas However, phosgene is toxic. Furthermore, C1 chemistry from syngas includes many neither isocyanate nor polycarbonate contains processes that have been available since chlorine in the final product, as it is before the creation of petrochemistry. In 1925, eliminated during production. As a result, BASF industrialized production of methanol expensive chlorine obtained by electrolysis is from carbon monoxide and hydrogen by wasted. Accordingly, one of the most high-pressure reaction (approximately 300 pressing goals for green chemistry from the atm) in the presence of a zinc 1990s onwards was the technological oxide-chromium oxide catalyst. Subsequently, development of non-phosgene processes. The it was also industrialized in the United subsequent course of events is described in Kingdom and the United States in the 1920s. Section 5.6.3(2). In Japan, it was industrialized in 1932 based In acetylene chemistry, carbonylation on studies by the Temporary Nitrogen using carbon monoxide as one of the Reppe Research Institute (formerly the Tokyo reactions under high pressure was important Industrial Research Institute, now the for the synthesis of acrylic acid, acrylic acid National Institute of Advanced Science and ester, acrylamide, acrylic acid amide, etc. In Technology) at the Hikoshima Factory of olefin chemistry (see Section 4.5.2 (5)), Gosei Kogyo (now Mitsui Chemicals). After BASF industrialized the synthesis of the Second World War, methanol was propionic acid from ethylene, carbon produced by fundamentally the same process, monoxide and water in 1952. However, it was but on a much larger scale owing to the

154 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) not a large-scale product. BASF has increased. continued studies on the method of manufacturing acetic acid by carbonylation of (6) Other organic synthetic chemistry methanol since the company industrialized (reactions of derivatives) methanol in the 1920s. BASF developed In addition to the above products directly molybdenum-nickel alloy (Hastelloy) produced from basic petrochemicals in olefin resistant to corrosion and an industrial chemistry, aromatic hydrocarbon chemistry, process using cobalt iodine as a catalyst in the cycloparaffin chemistry and C1 chemistry, 1960s. Meanwhile, Monsanto developed a petrochemistry also involves the production metal carbonyl catalyst composed of rhodium of many industrial organic chemicals by and iodine in the 1960s and built the first organic synthesis from primary derivatives 150,000 ton class plant in 1970. After that, made from basic petrochemicals. For the Monsanto process became the main example, there are many industrial organic process for manufacturing acetic acid by chemicals made from ethylene oxide, carbonylation of methanol. This process is the ethylene dichloride/vinyl chloride, acetone, greatest successful example of C1 chemistry butyraldehyde, acrylonitrile, acrolein, phenol, developed after the Second World War. nitrobenzene, cyclohexanone, etc. Technologies used for the synthesis of these 2) C1 chemistry from hydrogen cyanide chemicals should not simply be classified as One large-scale petrochemical process petrochemical technologies, but as more using hydrogen cyanide is the synthesis of comprehensive organic synthetic technologies. acetone cyanhydrin by adding hydrogen Detailed descriptions of these cyanide to the carbonyl group of acetone. It is technologieshave been omitted here, because the first process for manufacturing MMA;it they are much older than petrochemical has long been used and is widely used even technologies, dating back to the creation of now. However, because the production of organic chemistry in the 18th century. MMA by the acetone cyanhydrin process is classified as (6) “Other organic synthetic 6.1.3 Technological system of polymers chemistry,” it is not detailed here. Also, the As shown in Fig. 6.22, the system of addition of hydrogen cyanide to butadiene is polymer manufacturing processes can be an important process for synthesizing roughly classified into chain polymerization adiponitrile. It has already been described in and sequential polymerization. In chain Section 6.1.2 (1) 6). polymerization, it is actually impossible to remove a substance that is changing to a 3) C1 Chemistry from chloromethanes polymer in the process of polymerization. Methyl chloride is used as a methylating Once chain polymerization starts in a agent for the synthesis of methyl cellulose, low-molecular-weight raw material, only the etc. It is also used for the synthesis of unreacted monomer and the resulting polymer methylchlorosilanes by reaction with silicon can be obtained, even if the polymerization in the presence of a copper catalyst. This process is discontinued partway through. process was developed by Rochow in 1941. Methylchlorosilanes are important raw materials for silicone. However, these polymers are not synthesized by C1 chemistry, because the methyl group of silicone is a side chain and its skeleton is composed of silicon and oxygen. Fluorocarbons are synthesized from Fig. 6.22 System of polymer production chloromethanes and hydrogen fluoride. technology. However, the production of fluorocarbons has decreased as the number of substances Chain polymerization is classified into regulated by the Ozone Protection Law has radical polymerization and ionic

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polymerization. In radical polymerization, molecule (macromolecule) in 1922. This polymerization is performed using a theory was not accepted by the academic radical-generating polymerization initiator. societies the day, giving rise to hot The radical initiator is partially bound to the discussions. However, the idea rapidly end of the resulting polymer. In ionic penetrated into the academic societies in the polymerization, polymerization is started by early 1930s as a result of studies based on ions. It is further classified into cationic X-ray diffraction in the late 1920s, the polymerization, anionic polymerization, proposal of a viscosity formula for polymer coordination anionic (metal complex) solutions by Staudinger-Ryusaburo Nozu in polymerization and metal oxide 1930, etc. polymerization. Chain polymerization is In 1928, supporting the macromolecule applicable to compounds containing double theory, W.H. Carothers started fundamental bonds, such as olefins and vinyl compounds, studies on the synthesis and physical heterocyclic compounds, such as ethylene properties of condensation polymers at oxide [Footnote 5], and aldehydes, such as DuPont. In 1934, P.J. Flory and Carothers formaldehyde. independently advanced a theory of By contrast, in sequential polymerization, polycondensation. In 1937, Flory and G.V. a low-molecular-weight raw material reacts Schulz independently advanced “a theoretical as a whole to give a substance of a slightly system of radical polymerization.” In the higher molecular weight, which then further 1930s, the concept of polymers was reacts to finally give a polymer. If sequential established and the theoretical system of polymerization is discontinued partway polymerization was completed. The through, a substance of molecular weight in background of polymerization processes was the intermediate stage of polymerization is completed. obtained as an intermediate. Like reactions between low-molecular-weight substances Table 6.1 Typical synthetic polymers with functional groups (such as esterification industrialized before and during the Second and amidation), sequential polymerization World War starts between monomers with at least two functional groups in a molecule and then intermediates continue reacting with each other. However, as the reaction proceeds, it becomes necessary for molecules with higher molecular weight to react with each other. As a result, viscosity is increased, thereby disturbing thesmooth progression of the reaction. Various modifications are needed for the industrial production of polymers. As shown in Table 6.1, the Carothers not only advanced a theory, but industrialization of synthetic polymers started also carried out synthesis and with phenol resin in 1909. Synthetic polymers industrialization of polymers. In 1931, were industrialized later than industrial Carothers developed chloroprene rubber. This organic chemicals. Although new synthetic became the first monumental product to be polymers were industrialized from the 1910s industrialized based on the theory of to the 1920s, the concept of polymer had not macromolecules. Furthermore, DuPont yet been established. In 1920, based on the announced the invention of 6,6-nylon in 1938 results of studies on natural rubber, etc., H. and industrialized it in the following year. Staudinger insisted that a great number of An interesting anecdote exists about the small molecules are combined to form a large development of 6,6-nylon. In 1934, Carothers molecule; he advanced the concept of a giant synthesized 5,10-nylon and suggested to his company superior that it would be a practical [Footnote 5] Cyclic compounds containing atoms other than carbon synthetic fiber. 5,10-Nylon is a polyamide in in the ring.

156 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) which C5 aliphatic diamine and C10 aliphatic Table 6.2 Typical synthetic polymers dicarboxylic acid are polymerized. The raw industrialized before and during the Second material for C10 aliphatic dicarboxylic acid World War was castor oil. The company superior rejected his suggestion, because he considered that there could be a shortage of raw materials if nylon fiber were to meet with success in the future. Therefore, Carothers synthesized many other polyamides in which diamine was combined with carboxylic acid and from among these polyamides, he selected 6,6-nylon made from coal (phenol in those days). Obviously, he selected it based on the idea that molecular design not only includes methods of polymerization and performance of polymers, but also their profitability. A great variety of polymer-manufacturing Nylon was an epoch-making polymer, technologies, including those industrialized because the idea of molecular design was before the creation of petrochemistry, form a applied ahead of not only wholly aromatic substantial pillar of petrochemical polyamides, but also super engineering technology. plastics and thermoplastic elastomers that were developed later. (1) Chain polymerization After the Second World War, the Engineering technologies for chain consumption of polymers as materials for polymerization are described first, following fibers, packages and daily necessities for by explanations of radical polymerization and consumer use showed a dramatic increase, ionic polymerization reaction forms. starting in the United States (see Section 5.3.1 (4)). In particular, LDPE and polystyrene 1) Manipulation technologies for chain were supplied in large quantities by polymerization petrochemistry. In the 1950s, the trend Polymerization is generally a large-scale toward domestic production of exothermic reaction. Removal of the reaction petrochemicals and the polymer revolution heat is important especially in chain spread to Europe and Japan. At that time, polymerization, because once polymerization polymer science also spread to the industrial has been initiated, the reaction will rapidly world, and full scale technological progress while generating heat. As shown in development based on scientific theories Fig. 6.23, manipulation technologies for commenced. As shown in Table 6.2, chain polymerization are classified as bulk large-scale polymers such as ABS resin, polymerization, solution polymerization, acrylic fiber, polyester fiber, PET resin, slurry polymerization, suspension HDPE, PP, polycarbonate, polyacetal, BR polymerization and emulsion polymerization. and EPDM emerged one after another over a period of 15 years between the late 1940s and the 1960s, resulting in an acceleration of the development of the petrochemical industry.

Fig. 6.23 System of manipulation technologies for chain polymerization.

Bulk polymerization is performed using a monomer alone in the absence of a solvent. This process is used for both radical

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polymerization and ionic polymerization. As polymerization is often used for the a matter of course, removal of heat is production of synthetic rubber, resin for important. Various processes have been coatings (emulsion coatings) and adhesives. developed, such as the bulk process, in which None of these polymerization a monomer is used in large quantities as a manipulation technologies can be deemed as solvent, and the fluidized bed process, in the best, because it varies with each polymer. which a catalyst, etc. is added to an air stream For example, LDPE has always been of a monomer so that polymer particles are manufactured by bulk polymerization since formed in the gas phase. HDPE, L-LDPE and this process was developed. The method of PP have been actively manufactured by the manufacturing polyvinyl chloride changed gas phase process since the 1980s, chiefly from emulsion polymerization to suspension because high performance catalysts for polymerization. HDPE and PP were initially coordination anionic polymerization were produced by solution polymerization and developed. slurry polymerization, but as catalysts In solution polymerization, the heat can improved, these processes were subsequently be removed with a solvent and viscosity can replaced by bulk polymerization using a be made lower than in bulk polymerization. monomer as a solvent and then by bulk However, the solvent must be separated from polymerization using a gas phase fluidized the polymer after polymerization. In the case bed. However, slurry polymerization, etc. are of solution products such as adhesives, the used even now for convenience in making solution after polymerization is used as it is. some grades. SBR is produced by emulsion This process can be used for both radical polymerization in radical polymerization, but polymerization and ionic polymerization. by solution polymerization in anionic Slurry polymerization is often used for polymerization. Simply, manipulation ionic polymerization. Since a catalyst is technologies vary with each type of suspended in a solvent and the resulting polymerization. As a result, the performance polymer is also suspended in it, the reaction of the product also varies accordingly. solution as a whole becomes slurry. Due to the fact that the heat is removed by the 2) Radical polymerization solvent, the viscosity can be made lower than Radical polymerization has a long history. in solution polymerization. At first, it was used for the production of Suspension polymerization is often used vinyl acetate resin, polyvinyl chloride and for radical polymerization. Water is usually other such products that were developed in used as a solvent. A monomer is suspended in the 1920s. It can be very widely applicable to a solvent and polymerization is started by both polar and nonpolar monomers. dissolving a polymerization initiator in the High-pressure polymerization of ethylene suspended monomer. Heat can easily be (formation of LDPE), discovered in the 1930s, removed, because polymerization proceeds is also radial polymerization. The widely while the monomer is suspended. This distributed molecular weight and large process is often used for the industrial branched structure of LDPE represent well production of vinyl polychloride. the characteristics of radical polymerization. Emulsion polymerization is also often used As shown in Table 6.1 and 6.2, most of the for radical polymerization. Since water is typical polymers produced by radical used as a solvent and since a monomer is polymerization, such as polyvinyl chloride, emulsified with a surfactant, droplets are at vinyl acetate resin, polystyrene, AS resin, least 1 unit smaller in size and heat can be ABS resin, LDPE, polymethyl methacrylate, removed more easily than in suspension chloroprene rubber, SBR, NBR, fluororesin polymerization. An initiator and a catalyst for and acrylic fiber, were already available polymerization are dissolved in a solvent and before 1950. These polymers did much made to enter the emulsified micelles to towards the full-scale development of initiate polymerization. After polymerization, petrochemistry from the 1950s onwards. an emulsion is formed. Emulsion However, prior to that, the development of

158 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) the basic technology for radical cocatalyst, etc.. Monomers that undergo polymerization had already been advanced by cationic polymerization are generally monomers made using coal chemistry. double-bond compounds with an Peroxides and azo compounds are often electron-donating group. The polymerization used as polymerization initiators. Since these of isobutylene is a typical industrial example compounds can generate radicals in response of this type of polymerization. to heat, light (including ultraviolet rays and electron beams) and a combination of oxidation and reduction (redox initiator), they can initiate polymerization under various conditions. These initiators are used not only for the manufacture of polymers at plants, but Fig. 6.24 System of ion polymerization. also for the formation of photosensitive polymers for dental use, etc., for which In anionic polymerization, the growth polymerization at the site of use is preferred. terminal of the polymer is an anion. Catalysts The termination of radical polymerization for anionic polymerization include alkali used to be uncontrollable, because it occurs metals, such as metal potassium and sodium, due to radical transfer (chain transfer) or metal alkyls, such as butyl lithium, alkali recombination. For this reason, polymers amides, such as sodium amide, Grignard produced by radical polymerization were reagents, etc. Monomers that undergo anionic characterized by wide molecular weight polymerization are generally double-bond distribution. However, living radical compounds with an electron attractive group. polymerization developed in the 1990s, Polymerization of styrene, butadiene, unlike in existing technologies using acrylonitrile, etc. can be performed by polymerization initiators, made it possible to anionic polymerization. Since cyanoacrylic generate all polymer terminals at the same acid esters used for instant adhesives have a probability owing to radical generation from strong electron-attractive group, anionic a stable covalent species (dormant species); polymerization is initiated by airborne moreover, radical concentrations can be kept moisture, resulting in solidification and low to control termination. Living radical adhesion. In this case, polymerization polymerization began to be used in the 2000s, commences with water acting as a base. but it has only been applied to a relatively Ring-opening polymerization of small amount of functional polymers. No new heterocyclic compounds, such as ethylene large-scale polymers have been developed oxide, is also one type of ionic using this method. polymerization. Formation of polyacetal by polymerization of formaldehyde and by 3) Ionic polymerization copolymerization of formaldehyde and As shown in Fig. 6.24, ionic ethylene oxide are also ionic polymerization polymerization is classified into cationic processes. polymerization, anionic polymerization, Unlike in radical polymerization, no metal oxide polymerization and coordination termination reaction due to recombination anionic polymerization. The molecular occurs in ionic polymerization, because the weight distribution range is narrower for polymer growth terminals with the same ionic polymerization than for radical electric charge repel each other. Also, polymerization. because there are counter ions at the growth In cationic polymerization, the growth terminals, termination reaction due to chain terminal of the polymer is a cation. Catalysts transfer is unlikely to occur. Therefore, living for cationic polymerization include Lewis polymerization can be performed. For acids, such as boron fluoride and aluminum example, on completion of ionic chloride, protonic acids, such as sulfuric acid polymerization of styrene, a block copolymer and phosphoric acid, Lewis acids combined can be made by polymerization of isoprene with a halogenated alkyl or water as a from the growth terminal of polystyrene. Styrene- and olefin-based thermoplastic

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elastomers are made using this technology. products and moreover, it has done much Metal oxide polymerization is used for towards the technological development of polymerization of ethylene under medium petrochemistry since the 1960s (Fig. 6.25). In pressure. In 1950, Standard Oil (Indiana) 1968, Mitsui Petrochemical Industries discovered the formation of HDPE when developed an alkyl aluminum-magnesium trying to perform oligomerization of ethylene chloride-supported titanium chloride catalyst. under moderate conditions in the presence of The activity of this catalyst was more than a silica-supported molybdenum oxide catalyst. 100 times higher than the first-generation At the same time, Phillips also obtained Ziegler-Natta catalyst. As a result of this HDPE by using a silica- or development, decalcification, which had been alumina-supported chromium oxide catalyst. essential for reactions with Ziegler-Natta This process of polymerization can produce catalysts, became unnecessary. Furthermore, polyethylene under milder conditions than the in 1975, Mitsui Petrochemical Industries and existing high-pressure radical polymerization Montedison jointly succeeded in selectively process for LDPE. It was industrialized in making highly stereospecific active sites by 1957 and has been used as a method of letting an electron donor, such as ethyl manufacturing HDPE ever since. However, benzoate, act on a catalyst. Since the metal oxide polymerization had no uses other Ziegler-Natta catalyst is a solid, its catalytic than ethylene. When it is applied to propylene, activity varies with each crystal surface approximately 10% solid PP is obtained, but (multisite). The active sites of this catalyst the remainder is a liquid polymer that is were selectively specified by using additives. useless. As a result, it became unnecessary to remove nonstereoregular PP formed during 4) Coordination anionic polymerization polymerization in the presence of the Coordination anionic polymerization is Ziegler-Natta catalyst. This highly active and one type of ionic polymerization. This highly stereoregular catalyst is called the process is described separately because it is second-generation Ziegler-Natta catalyst. As particularly important in petrochemistry. In a result of this development, the ranges of coordination anionic polymerization, the molecular weight distribution of HDPE and growth terminal of a polymer (anion) is PP have been dramatically narrowed, coordinated with a catalyst to form a complex. resulting in marked improvements in quality In 1953, this polymerization process began (see Section 5.6.3 (1)). with Ziegler’s successful polymerization of ethylene at ordinary temperature and atmospheric pressure in the presence of a triethyl aluminum-titanium tetrachloride catalyst. Like polyethylene obtained in the presence of a metal oxide catalyst, the resulting polymer was HDPE. In 1955, Natta succeeded in the formation of stereoregular Fig. 6.25 Change of coordination anionic polymers from α-olefins such as propylene polymerization catalyst. and styrene in the presence of triethyl aluminum combined with titanium trichloride. Manufacture of L-LDPE similar to LDPE Ziegler-Natta catalysts, shown in Table 6.2, by copolymerization of ethylene with α-olefin were subsequently widely used to was industrialized by DuPont Canada in 1960. industrialize HDPE in 1955, PP in 1957, However, the quality of the product was cis-1,4-polybutadiene (BR) and lower than existing LDPE. In contrast, cis-1,4-polyisoprene (IR) in 1960 and EPDM L-LDPE manufactured using the in 1961. second-generation Ziegler-Natta catalyst was Coordination anionic polymerization is a superior to LDPE in uniformity of representative petrochemical technology composition distribution and also in because it has been used to produce numerous performance. In 1979, UCC developed a

160 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) method of manufacturing L-LDPE by the gas Organometallic complex catalysts phase fluidized bed process. In the 1980s, foreshadowed by the Ziegler-Natta catalyst L-LDPE achieved rapid growth, taking over a began to attract much more attention after the considerable part of the LDPE market. Also, development of the metallocene catalyst. because construction costs and operation Many improvements and modifications are costs were both lower than for high-pressure being made to these catalysts even now. A LDPE facilities, the L-LDPE process was constrained geometry catalyst aimed at exclusively adopted by new petrochemical improving stereoregularity by controlling the industries in the Middle East and Asia. Due to structure around the active site has been the second-generation Ziegler-Natta catalyst, developed and industrialized as a it became possible to further increase the modification of the metallocene catalyst. amounts of comonomers; consequently, Figure 6.25 summarizes the status of VLDPE and ULDPE with much lower catalysts for coordination anionic density than LDPE were industrialized as polymerization. It can be expected that these new types of polyethylene. catalysts will develop further in the future. As an indication of future development, Table 6.3 Typical synthetic polymers post-metallocene catalysts have already industrialized from the 1960s begun to develop. These are mentioned in Section 6.2.

(2) Sequential polymerization As shown in Fig. 6.22, sequential polymerization is classified into condensation polymerization, polyaddition and addition condensation. The most typical reaction form of sequential polymerization is condensation polymerization (polycondensation). Condensation polymerization proceeds while

polyfunctional monomers are performing In 1980, Kaminsky found out that the condensation on each other by releasing a polymerization activity of a catalyst in which simple low-molecular-weight substance, such a reactant of triethyl aluminum with water as water or hydrogen chloride. Formation of (Methylalumoxane [MAO]) was combined polyurethane by the reaction of polyol with a with metallocene (cyclopentadienyl complex polyisocyanate compound is a modification of zirconium, titanium, etc.) was more than 1 of condensation polymerization. This reaction unit higher than the second-generation is also called polyaddition, because no simple Ziegler-Natta catalyst. This became known as low-molecular-weight substance is eliminated a metallocene catalyst (Kaminsky catalyst) and a urethane bond is formed by the reaction (see Section 5.7.4 (3)). The metallocene between the hydroxyl and isocyanate groups. catalyst is a single-structure metal complex Meanwhile, if phenol resin, urea resin or having a single active site (single site). melamine resin is formed, the reaction is Accordingly, the range of molecular weight called addition condensation. In this case, distribution is narrower than the polymerization proceeds as follows: second-generation Ziegler-Natta catalyst. formaldehyde is added to active hydrogen at However, because improvements were also the ortho or para position of phenol or to being made to the second-generation active hydrogen of the amino group of urea or Ziegler-Natta catalyst, the metallocene melamine to give a methylol group (-CH2OH), catalyst was not used in the industrialization which is then reacted with active hydrogen of polyethylene until 1991. Due to its and then dehydrated (condensed) to give a superior merits, the metallocene catalyst is methylene bond (-CH2-). It also proceeds if used in the production of elastomers, such as the methylol groups dehydrate (condense) EPR and EPDM. each other to give an ether bond

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(-CH2OCH2-). If addition and condensation on from nylon, unsaturated polyester, are repeated, a two-dimensional prepolymer polyurethane, silicone and epoxy resin, which will be formed depending on the conditions, were developed before the full-scale followed by the formation of a development of petrochemistry. Since the three-dimensional crosslinked polymer by 1950s when petrochemistry started coming heating or pH change. into fruition, large-scale polymers have also As shown in Table 6.1, addition been developed, such as polyester (PET), condensation is the oldest method of which is at present comparable in production polymerization, created before the period of to the four major general-purpose resins (PE, petrochemistry. By this process, phenol resin PP, PVC and PS), and polycarbonate, used as - the first synthetic polymer, urea resin and a more general application of an engineering melamine resin were industrialized in 1909, plastic from the 1990s onwards. From the 1928 and 1935, respectively. Phenol resin 1960s onwards, to meet the needs of the was probably the first synthetic polymer to market for strong, heat-resistant polymers, as familiarize people with plastics, during the shown in Fig. 6.26, engineering plastics, such coal chemistry period before the creation of as polyphenylene oxide (PPO) and PBT, petrochemistry. Since phenol resin had the super engineering plastics, such as polyimide, drawback of turning brown, it was colored PES, PEEK, polyether imide, and liquid black and used mainly for black telephones crystal polymers and metha- and para-based and bulb sockets. As urea resin showed no aramid fibers were developed by such discoloration, it was used in large condensation polymerization. In particular, quantities for white or colored tableware, super engineering plastics are polymers buttons and electrical parts. In Japan, phenol whose molecules are designed so that they resin and celluloid resin were typical plastics have both high strength/high heat resistance of the time before the Second World War. and high forming processability required for Urea resin became a typical plastic after the thermoplastics. Condensation polymerization Second World War until the mid-1950s (see has the advantage of easy molecular design. Section 5.3.3 (1)). Transparent and heat-resistant melamine resin was often used for decorating the surfaces of laminated plates made of phenol resin. However, it was time-consuming to mold phenol, urea and melamine resins to thermosetting resins by

addition condensation; accordingly, the Fig. 6.26 Technology system of high-strength practice of using these resins as raw materials and high-heat resistance condensation for molding daily necessaries and electrical polymerization polymers. parts was discontinued in the 1950s, when thermoplastic resins, such as polyethylene In terms of manipulation technology for and polystyrene, began to be supplied in large condensation polymerization, the monomer quantities. However, even now these resin and resulting polymer are usually heated products still play an important role in above their melting points to perform manufacture of adhesives for plywood and polymerization in a molten state. This process laminates. corresponds to bulk polymerization in chain Nylon (polyamide), industrialized in polymerization. Since condensation reaction 1939, was the first polymer made by is reversible, it is important to immediately condensation polymerization and remove the resulting condensed polyaddition. As described above, nylon low-molecular-weight substance, such as played a significant role in verifying and water, from the reaction system. For this establishing the concept of polymers. Tables reason, polymerization is often carried out 6.1 and 6.2 show the polymers made by the under reduced pressure. The molecular industrialization of condensation weight of PET may be insufficient for many polymerization and polyaddition, following uses if it is produced by normal condensation

162 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) polymerization in a molten state under development, although not so strikingly as reduced pressure. Therefore, its molecular was observed in the 1950s and 1960s. One weight is further increased by solid-phase such technology was olefin chemistry from polymerization. In the case of polyester, C4 and C5 compounds that were not condensation polymerization may be previously in demand. Another example was performed by transesterification between a energy-saving low-pollution manufacturing diester monomer and polyol. Since technologies (see Section 5.6.3). low-molecular-weight monool is eliminated, Technological innovations continued in it must be removed. polymer technology as follows: the Meanwhile, aromatic polyamide fibers second-generation Ziegler-Natta catalyst was are made by low-temperature solution industrialized in the 1970s, L-LDPE as a polycondensation in the presence of a polar large-scale new product in the 1980s and the solvent, such as DMF and metallocene catalyst in the 1990s; many super N-methylpyrrolidone. This technology engineering plastics, high performance fibers corresponds to solution polymerization in and functional resins were developed. chain polymerization. In this case, it is Meanwhile, due to the steady accumulation of important to increase the degree of technological modifications, such as living polymerization as much as possible by polymerization and block polymerization, PP dissolving the resulting polymer. After achieved marked growth in the 1980s and as polymerization, spinning can also be carried a result, the demand for olefins was corrected out. Interfacial polymerization is also from monopolar concentration on ethylene performed, in which condensation that had continued up until the 1960s. The polymerization is carried out on the demand for isobutylene (a raw material for intersurface of two solvents that are insoluble MMA and MTBE) and the demand for in each other. For example, BPA is dissolved 1-butylene (an auxiliary raw material for in sodium hydroxide solution, while L-LDPE) also increased. The use of olefins phosgene is dissolved in methylene chloride. overall was accelerated, and the Since methylene chloride and water are petrochemical industry became very insoluble in each other, two phases are comprehensive, as discussed in Chapter 3. formed. Condensation polymerization Meanwhile, the two oil crises in the proceeds on the intersurface of the two phases 1970s meant that subsequent attention was to give polycarbonate. focused on the need to develop technology to counter the depletion of petroleum resources. 6.2 New technological trends in While coal is reserved in large quantities petrochemistry under ground, its handling is difficult. Therefore, studies have been conducted to As mentioned in Section 5.5, it is said develop chemical reactions directly that petrochemistry technologically matured producing industrial organic chemicals from in the late 1970s. The superiority of steam methane or other alkanes as natural gas, cracking was established in the manufacture which have the second greatest reserve after of olefins. Subsequently, because coal and are easy to handle. Under these improvements were only made to increase the circumstances, many technological scale of production, investigations in pursuit innovations have occurred in the of technological varieties decreased petrochemical industry since the 1990s, significantly in number. Since coal and although their historical value has not yet fermentation chemicals were completely been established. This technology has the replaced by industrial organic chemicals, it potential to create new types of became difficult to develop new technologies petrochemistry with product categories and leading to any dramatic increase in the scale forms of production that differ from existing of productivity. However, from the 1970s petrochemistry that has been prevalent around onwards, technologies for manufacturing the world since the 1950s, that is, technology industrial organic chemicals showed steady in which basic petrochemicals are produced

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by steam cracking and then transported by presence of a catalyst composed of WCl6 and pipeline to petrochemical complexes EtAlCl2. This confirmation made the manufacturing industrial organic chemicals metathesis reaction well known. In 1971, and polymers. Chauvin suggested a mechanism for this reaction. Around that time, the reaction began 6.2.1 Metathesis reaction of olefins to be utilized as a petrochemical process in The metathesis reaction of olefins was the presence of a Ziegler-type catalyst found and developed as a triolefin process composed of tungsten or molybdenum during the Sturm und Drang period of combined with alkyl aluminum, etc. In the petrochemistry in the 1960s, but its value was 1990s, Schrock and Grubbs et al. developed a unknown. Subsequently, the mechanism of highly active alkylidene complex catalyst of the reaction was elucidated. It was found to molybdenum and ruthenium that could be a reaction of double bonds, although the tolerate functional groups with high polarity. form of the reaction was unknown (see Since then, this catalyst has been widely used, Section 6.1.2 (1)). Recombination of bonds not only for petrochemistry, but also for occurs between two kinds of olefins. It is organic synthetic reactions. induced by a transition metal alkylidene As shown in Fig. 6.27, there are three complex catalyst (carbene complex). In 1967, successful examples of the application of Calderon et al. confirmed that a double-bond metathesis reactions in petrochemistry. was cleaved to give a new double bond in the

Fig. 6.27 Examples of metathesis reactions utilized in petrochemistry.

(1) Synthesis of propylene metathesis process have been built in Japan. The production of propylene by the The production of propylene at these plants is metathesis reaction of ethylene with significant, comparable to the amount of 2-butylene was industrialized for the first propylene obtainable from plants producing time in 1970. However, it was not until the 300,000 tons of ethylene by steam cracking mid-1980s that this reaction became used on of naphtha. In the Middle East, where a fully-fledged scale. In the 1990s, this propylene cannot be obtained because ethane process was used for the large-scale is used as a raw material, plants have been production of propylene. Due to the increased built at which ethylene is dimerized to give demand for propylene, propylene also began n-butylene, which is then subjected to to be actively manufactured at petrochemical metathesis reaction with ethylene to give complexes in Japan by steam cracking of propylene. naphtha from 2-butylene, for which there was little demand. Several plants producing (2) Metathesis polymerization 150,000 tons of propylene a year by the The second typical example of metathesis

164 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) reaction application in petrochemistry is stilbene formed by dimerization of toluene by metathesis polymerization. Cyclic olefin is oxidative dehydrogenation with ethylene. subjected to ring-opening metathesis Monoolefins and dienes with slightly polymerization (ROMP) in the presence of a complicated molecular structures have been Ziegler-type catalyst to give a polymer, which produced by metathesis reaction and have is then hydrogenated to give an optical already been industrialized as intermediates material outstanding in transparency, heat for fine chemicals. resistance and size stability. Many chemical companies have been actively seeking a new 6.2.2 Propylene-targeted production market for this area. If a Grubbs catalyst that technology is highly resistant to polar functional groups As mentioned in Section 5.7.4 (1), the is used, various functional groups can be demand for propylene increased relative to introduced and living polymerization can also that for ethylene in the 1980s. A shortage of be performed. Accordingly, attempts have propylene became apparent in the United been made to make use of this process for the States, where it was obtained as a byproduct synthesis of functional polymers. of the fluidized catalytic cracking (FCC) process mainly for producing gasoline, and (3) Efficient synthesis of α-olefins also in countries where propylene was Metathesis reaction was also applied to a obtained as a byproduct of ethylene method of efficiently synthesizing α-olefins production by steam cracking of naphtha. (see Section 3.4.2 (7)). This is the synthetic Accordingly, the 1990s saw the start of higher olefin process (SHOP) developed by large-scale production of propylene by Shell. Ethylene is oligomerized to give metathesis reaction, as mentioned in the α-olefins with various numbers of carbon preceding section. In the 1990s, production of atoms. There are limited higher alcohols with propylene by catalytic dehydrogenation of carbon numbers that are useful for surfactants, propane also started. Although this process lubricants, etc. In contrast, the SHOP is a was at first not considered to be able to rival sophisticated process in which metathesis the byproduct processes, steady reaction and isomerization/hydroformylation improvements have been made with respect in the presence of a cobalt catalyst take place to catalysts and processes. repeatedly to avoid the formation of useless In contrast to FCC, deep catalytic α-olefins. After an α-olefin with a useful cracking (DCC), which aims at increasing the carbon number atom is removed, the yield of propylene rather than decreasing the remaining olefins with longer and shorter yield of gasoline, was developed and carbon chains are isomerized (into internal industrialized in China. Subsequently, this olefins). Reorganization is then performed by process has also been developed in many metathesis reaction in such a way so that the countries other than China. It is also known olefin carbon atoms are added and then as reinforced fluidized catalytic cracking. divided by two. From this, internal olefins In China, the petrochemical industry with useful numbers of carbon atoms are experienced a sudden rise due to technology separated again. The resulting internal olefin imports and capital injection from other is hydroformylated in the presence of a cobalt countries from the 1990s onwards. To prevent catalyst to give terminal aldehyde. This is an increase in the dependence on other reduced to give alcohol, which is then countries for petroleum, China planned to dehydrated to give an α-olefin with a useful build plants for industrial chemical products number of carbon atoms. If this procedure is from coal, mainly in inland areas such as repeated, only α-olefins with necessary Inner Mongolia. One example was the MTP carbon numbers are obtained. process for manufacturing propylene from It is also expected that metathesis methanol derived from coal. In 2010, a reaction will be further applied to 500,000-ton class MTP plant was built using petrochemical processes, such as the imported technology and used for synthesis of styrene by metathesis reaction of manufacturing PP. However, because it was

Systematic Survey on Petrochemical Technology 165

built as part of the economical security This process was industrialized in 1978. policies of China, there is little likelihood of Recently, many plants producing EG by this this plant immediately realizing process have been built in China. These competitiveness. Since oil refining companies Chinese plants use carbon monoxide from and plant engineering companies in coal. Ube Industries also synthesized developed countries originally made dimethyl carbonate by the same process. The strenuous efforts to develop the MTP process, importance of dimethyl carbonate has been its industrialization in the inland areas of increasing as an electrolyte for lithium ion China should be regarded as experimental in secondary batteries and also as an alternative a special market with only a few rival for phosgene (a starting material for companies. However, because methanol can manufacturing polycarbonate by the be produced much more cheaply and on a nonphosgene process). much larger scale from natural gas than from coal in natural gas-producing countries, the 6.2.4 Paraffin chemistry development of the MTP process to use cheap Paraffins (alkanes) other than methane, methanol as a raw material is, in itself, an such as ethane, propane and butane, have interesting part of C1 chemistry, mentioned been converted to olefins by steam cracking, below. etc. before use due to their markedly low reactivity. However, because paraffin is 6.2.3 C1 chemistry cheaper than olefins, attempts have been Before the Second World War, syngas made to develop a method of directly was exclusively made from coal. Since the manufacturing industrial organic chemicals end of the war, it has been made from from paraffin. petroleum and natural gas. Unlike petroleum, The first successful example of paraffin natural gas is produced at remote places far chemistry was the synthesis of acetic acid by from consumption areas; accordingly, its liquid-phase oxidation of propane, butane and development is often difficult due to pentane, developed by Celanese in 1952. difficulty in transportation. To solve this According to this process, acetic acid is problem, there has been a growing trend to manufactured by dissolving a catalyst, such manufacture syngas and produce methanol as cobalt acetate or chromium acetate, in an and ammonia on a large scale at production acetic acid solvent and then blowing raw sites for natural gas. material gas and air into the solution. In As already mentioned in Section 6.1.2 (5) addition to acetic acid, byproducts obtained 1), one of the consumers of cheap methanol include acetaldehyde, acetone, MEK, ethyl produced as described above was a process acetate, formic acid and propionic acid. More for manufacturing acetic acid by byproducts are obtained in paraffin chemistry carbonylation of methanol, industrialized in than in olefin chemistry, because the 1970. Due to the major success of this conditions for reaction are severer for process, and due to the petroleum crises of paraffin chemistry. the 1970s, research and development of C1 In 1962, Distillers industrialized chemistry were actively conducted from the processes for synthesizing acetic acid from 1970s to the 1980s. However, for the time light naphtha in the presence of a manganese being, the only outcome has been to prove naphthenate catalyst. However, these thedifficulty of C1 chemistry. processes for manufacturing acetic acid Meanwhile, attention has been focused on competed with oxidation of acetaldehyde the synthesis of dimethyl oxalate by oxidative from ethylene in the 1960s and were carbonylation of carbon monoxide, methanol overwhelmed by carbonylation of methanol and oxygen (Section 3.4.1 (3)), developed by from the 1970s onwards. Ube Industries in the 1970s as a method of The second successful example was the synthesizing C2 compounds by coupling production of maleic anhydride by oxidation carbon monoxide. Dimethyl oxalate is of n-butane. Maleic anhydride is a mid-scale hydrogen reduced to give EG and methanol. industrial organic chemical that is used as a

166 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) raw material for unsaturated polyester and Following on from the ammoxidation of also for synthesis of fumaric acid and malic propane, processes have been rapidly acid. In the coal chemistry period, it was developed for direct oxidation of propane for already produced in small quantities manufacture of acrylic acid and direct exclusively by air oxidation of benzene in the oxidation of ethane for manufacture of acetic presence of a vanadium pentoxide catalyst. acid. The oxychlorination process, in which This reaction was similar to the process for vinyl chloride is directly obtained from manufacturing phthalic anhydride from ethane, chlorine and oxygen, is also naphthalene (see Section 4.6.2), and maleic undergoing development. Although these anhydride was also obtained as a byproduct processes were expected to be industrialized of phthalic anhydride. Oxidation of benzene in the 2000s, none of them have been was a wasteful process, because two carbon industrialized as yet. The issue lies with the atoms of benzene were made into carbon large amounts of chlorinated hydrocarbon dioxide. Therefore, a method of byproducts. manufacturing maleic anhydride from BP/UCC developed a process for n-butylene was developed in 1962. Vanadium manufacturing aromatic hydrocarbons by pentoxide-phosphoric acid was used as a cyclodehydrogenation of propane and butane. catalyst. However, after Monsanto developed In 1999, this process, also known as the a method of manufacturing maleic anhydride Cyclar process, was industrialized in Saudi from n-butane in 1974, the benzene and Arabia on a benzene production scale of n-butylene processes were both rapidly 350,000 tons and a p-xylene production scale replaced by the butane process. Vanadium of 300,000 tons. Thus commenced production pentoxide-phosphoric acid was also used as a of aromatic hydrocarbons from paraffins with catalyst for this method. six or less carbon atoms. The third successful example of paraffin As mentioned above, it was not until chemistry was the co-production of t-butyl approximately 50 years after the synthesis of peroxide and t-butyl alcohol by oxygen acetic acid by liquid-phase oxidation that oxidation of isobutene. t-Butyl peroxide is paraffin chemistry began to rival olefin used for oxidation of propylene to give chemistry in any way. propylene oxide and t-butyl alcohol. t-Butyl alcohol was in great demand from the 1980s 6.2.5 Post-metallocene catalysts to the 1990s. This was due to MTBE being With the industrialization of the used as a gasoline additive. However, the single-site metallocene catalyst in contrast to demand for t-butyl alcohol decreased rapidly the multi-site Ziegler-Natta catalyst in the after adding MTBE to gasoline was 1990s, coordination anionic polymerization prohibited in the early 2000s, meaning there began to attract much attention again in the was no longer any use for this technology. 1990s. As a result, various single-site As mentioned above, the only successful non-metallocene catalysts and late transition examples of paraffin chemistry had been for metal catalysts were successively developed paraffins with four or more carbon atoms. as post-metallocene catalysts in the latter half However, in the 2000s, promising processes of the 1990s (Fig. 6.25). The former catalysts for paraffins with C2 or C3 were developed use ligands other than cyclopentadienyl, one after another. This was pioneered by the which is used in metallocene catalysts. Unlike direct synthesis of acrylonitrile by the metallocene catalyst using early transition ammoxidation of propane developed by metals such as zirconium and titanium, the Asahi Kasei. Industrial production was latter catalysts use late transition metals such started by a subsidiary of Asahi Kasei in as iron, nickel and palladium. Korea in 2007 and after that in Thailand. A Many post-metallocene catalysts that are plan is also being pushed forward to more active than the Ziegler-Natta and industrialize it in Saudi Arabia. The catalyst metallocene catalysts have been developed. It for this process is a complex oxide of is especially promising that these catalysts are molybdenum, vanadium, niobium, etc. not easily fractured by water or polar

Systematic Survey on Petrochemical Technology 167

monomers. The applicable monomers and the technological innovation in lowering the conditions used to be limited to a large extent partial pressure of hydrocarbon by the for ionic polymerization than for radical addition of steam. The application of steam polymerization. It is expected that new cracking was extended to include propane in large-scale polymers will be created by the 1930s and naphtha in the 1940s. It took copolymerization of olefins with polar quite some time to widen the range of monomers. applications; this was because the types of basic petrochemicals produced by steam 6.3 History of petrochemical cracking rapidly increased with each increase technology and epoch-making in the number of carbon atoms in the raw technologies material hydrocarbon, which meant it then became necessary to develop technologies for Since petrochemistry has long been separating/refining them. Both production closely related to industrial organic chemicals technologies and separation and refining and polymers since even before its creation, it technologies are important for basic is considerably difficult to identify purely petrochemicals, as mentioned in Section 6.1.1 petrochemical processes using natural gas and (8). Steam cracking has been the most petroleum as raw materials (petrochemical important manufacturing technology for processes in the narrow sense). However, ethylene since the 1920s. Although since Section 6.5 discusses the manufacture of ethylene by catalytic cracking systematization of petrochemical processes, of hydrocarbon has long been studied, it has in this section we shall only review the not been industrialized yet. history of petrochemical technology The steam cracking of naphtha in according to the narrow sense, using natural petrochemistry has become a major supply gas and petroleum as raw materials, and source of not only ethylene but also introduce those epoch-making technologies propylene, butylene, butadiene, benzene and for petrochemistry. p-xylene. It is also worth noting that this process led to the started of production of 6.3.1 History of petrochemical basic petrochemicals not only in the United technology States, but all around the world, as mentioned To review the history of petrochemical in Section 5.3.2 (2). Steam cracking of technology, petrochemicals can also be naphtha was widely used in the 1950s in classified three ways; namely, basic Europe and Japan, from the 1970s onwards in petrochemicals, industrial organic chemicals Asia and Latin America and in the 2000s in and polymers. China. Meanwhile, steam cracking of ethane was only widely used in the Middle East in (1) Technologies for basic petrochemicals the 1980s. Production of basic petrochemicals Thermal cracking and catalytic cracking started at in the early 1920s with the of heavy oil are petroleum refining production of ethylene by steam cracking of technologies, because the main purpose is ethane in the United States. The ethane was production of gasoline. These cracking separated from natural gas. This separation technologies are associated with the process was an application of the cryogenic generation of large amounts of waste distillation process developed in the industrial hydrocarbon gas containing propylene and gas industry in the 1900s. The thermal butylene. cracking process for hydrocarbons was based Since there has long been less demand for on the thermal cracking technology for heavy propylene than for ethylene, the main supply oil that had been developed in the oil refining source for it has been waste gas from steam industry in the 1910s. However, unlike cracking of naphtha, mainly for producing thermal cracking technology for heavy oil, ethylene; in the United States and other the steam cracking process progressed from countries, it has been waste gas from catalytic petroleum refining to petrochemistry due to cracking of heavy oil, mainly for producing

168 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) gasoline. In other words, propylene has been by solid adsorption (1970s), separation of supplied by byproducts. However, from the m-xylene by complex formation (1960s), etc., 1990s onwards, the supply of propylene in addition to various distillation technologies, became insufficient; consequently, propane including extractive distillation and dehydrogenation and metathesis reaction azeotropic distillation. (ethylene and n-butylene) were industrialized. A technology for producing syngas was The only main purpose of these technologies originally developed in the 1910s as a syngas was the production of propylene. reaction of coke. Since the main purpose of Butadiene is mainly supplied by solvent this technology was to obtain hydrogen in extraction and extractive distillation from the order to synthesize ammonia, a water gas C4 fraction produced by steam cracking of reaction was also carried out. In this water naphtha. This process was developed in the gas reaction, carbon monoxide was reacted 1940s; modifications to it were developed with steam to give hydrogen and carbon one after another in the 1950s and the 1960s dioxide. Syngas was made in large quantities and have been used until now. In the United to produce methanol in the 1920s and States, butadiene has also been produced artificial petroleum by the FT process in the since the 1930s by dehydrogenation of 1930s. In petrochemistry, production of butylene from waste gas obtained by catalytic syngas from hydrocarbons such as natural gas, cracking of heavy oil. This technology may propanone/butane, naphtha and crude oil also be classified as a petrochemical went into full swing in the 1950s. technology. As mentioned above, the basic Meanwhile, catalytic reforming of petrochemical product technologies naphtha is a petroleum refining technology, manufactured from petroleum or natural gas mainly for producing high-octane gasoline. became fully industrialized in the 1920s for Catalytic reforming was widespread in the ethylene, the 1940s for butadiene and the United States in the 1950s, followed by 1950s for propylene and aromatic Europe and Japan. The technology for hydrocarbon/syngas (Fig. 6.28). extracting aromatic hydrocarbons from reformate is a petrochemical technology that (2) Technologies for industrial organic was developed in the 1950s. The production chemicals of aromatic hydrocarbons was industrialized As shown in Fig. 6.29, there are a large using the distillation of coal tar in the number of major industrial organic mid-19th century. In the 1950s and the 1960s, chemicals; furthermore, many of them have approximately 100 years later, the main been industrially produced since before the aromatic hydrocarbon supplier shifted from creation of petrochemistry. Therefore, it is coal tar to petrochemistry, due to the difficult to gain a sense of the overall flow of development of two petrochemical petrochemical technologies in the narrow technologies. These were the distillation of definition. For this reason, the history of cracked gasoline by steam cracking of industrial organic chemicals is reviewed here naphtha and the extraction of aromatic according to the system of technologies used hydrocarbons from reformate. Further, in Section 6.1.2 Technological system of petrochemical processes for producing industrial organic chemicals. individual aromatic hydrocarbon products Addition reactions to the double bond of came to include dealkylation of toluene olefins by the sulfuric acid process began (benzene), developed in the 1950s, and with the production of IPA in the 1920s and disproportionation of toluene (benzene and the production of butanol and ethanol in the xylene) and isomerization of m-xylene 1930s. Also in the 1920s, the production of (xylene), developed in the 1960s. ethylene oxide, EG and propylene oxide Petrochemical technologies for separating began by the chlorohydrin process. The individual aromatic hydrocarbon products production of EDC by addition of chlorine came to include separation of p-xylene by was also performed in the 1920s, although it crystallization (1940s), separation of p-xylene soon came to nothing. These processes were

Systematic Survey on Petrochemical Technology 169

all stoichiometric reactions using highly reactive chemicals. In the 1930s, addition reactions using catalysts were developed one after another. For example, ethylene oxide was made by epoxy-addition of oxygen to ethylene; ethylbenzene and cumene were made by addition of benzene to ethylene; polymer gasoline was made by addition of olefins to olefins; alkylate gasoline was made by addition of isobutane to olefins and butyraldehyde was made by the oxo process with propylene. From the 1940s to the 1950s, alcohol was produced by direct hydration reaction to the double bond of olefins, while ether was produced by direct addition reaction of alcohol to the double bond of olefins. Development of the epoxy addition process to the double bond of propylene was substantially delayed. In the 1960s, the Halcon process was developed, using peroxide. However, this process was not convenient, as the stoichiometric reaction produced propylene oxide along with byproducts (styrene, t-butyl alcohol, etc.). In the 1990s, the hydrogen peroxide process was developed, with water as a byproduct, and the above problem was solved. However, direct addition reaction with oxygen has not yet been industrialized.

170 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Product Before 1900 1900s 1910s 1920s 1930s 1940s Syngas reaction of Syngas Coke oven gas coke Hydrogen Castner process (metal Na, coke and Formamide process cyanide ammonia) Acetylene Carbide process Arc process of natural gas

→ Waste gas Thermal cracking of heavy oil Coke oven gas separation utilization Dehydration of Ethylene Ethane steam fermentation ethanol Pipe-type steam cracking of naphtha cracking Pipe-type steam cracking of naphtha Thermal decomposition of Propylene → Waste gas heavy oil Heavy oil fixed-bed catalytic cracking utilization Pipe-type steam cracking of naphtha Acetaldehyde Butadiene Butylene dehydrogenation process condensation process Butane dehydrogenation process

Thermal decomposition of → Waste gas Heavy oil fixed-bed catalytic cracking Butylene heavy oil utilization Pipe type steam cracking of naphtha

Higher olefin

Benzene Coal tar distillation Pipe-type steam cracking of naphtha

Mixed xylene Pipe-type steam cracking of naphtha

p-Xylene Crystallization separation process

Fig. 6.28 Technological history of basic petrochemicals (before 1900 – 1940s).

Systematic Survey on Petrochemical Technology 171

Product 1950s 1960s 1970s 1980s After 1990s Steam reforming of natural gas by partial Syngas combustion, steam reforming Hydrogen The Andrussow process using natural gas as AN byproduct of Sohio

cyanide raw material process High-temperature steam Byproduct by steam cracking of ethane and Acetylene cracking process of naphtha naphtha and crude oil High-temperature steam Trial for various naphtha cracking processes cracking process of naphtha Ethylene and crude oil

Metathesis process Strengthening fluidized-bed catalytic Heavy oil fluidized-bed catalytic cracking Propylene cracking Propane dehydrogenation process

MTP process

Butadiene

Heavy oil fluidized-bed catalytic cracking Isobutane Separation from FT artificial Butylene dehydrogenation petroleum Ethylene dimerization Separation from FT artificial Higher Propylene tetramerization Pyrolysis of n-paraffin petroleum olefin Ethylene oligomerization

Catalytic reforming oil extraction of

naphtha Benzene Toluene disproportionation Cyclode-hydrogenation of Toluene dealkylation process process propane/butane Mixed Catalytic reforming oil extraction of Toluene disproportionation xylene naphtha m-Xylene isomerization Solid adsorption separation p-Xylene m-Xylene isomerization HTI process Octafining process process Fig. 6.28 Technological history of basic petrochemicals (1950s – after 1990s).

172 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Product Before 1900 1900s 1910s 1920s 1930s 1940s Ethylbenzene Aluminum chloride catalytic process EB dehydrogenation process by

alumina-chromia catalyst Styrene EB side chain chlorination, dehydrochlorination process Acetophenone process Methanol Wood carbonization process Coke-based syngas process Direct hydration Ethanol Fermentation process Sulfuric acid and hydration process of ethylene process of ethylene Sulfuric acid and hydration IPA process of propylene n Product by n Product by condensation sec and tert Product from sulfuric acid and acetone-butanol and reduction process of hydration process of n-butylene and Butanol fermentation process acetaldehyde isobutylene n and iso Product from Co catalyst oxo reaction and reduction process of propylene High-pressure hydrogen Higher alcohol n-Paraffin oxidation process reduction of oils and fats EO Chlorohydrin process Silver catalyst direct oxidation process EDC process and chlorohydrin EG EO water addition process process PO Chlorohydrin process

Hydrolysis process of oils and Epichlorohydrin Glycerin fats process Decomposition process of Acetone-butanol Dehydrogenation process of Acetone wood carbonization Acetate Acetylene/steam process fermentation process IPA of lime Acrylonitrile Ethylene cyanohydrin process Ethylene cyanohydrin process Acrylic acid

Fig. 6.29 Technological history of major industrial organic chemicals. (Ethylbenzene – Acrylic acid before 1900 – 1940s)

Systematic Survey on Petrochemical Technology 173

Product Before 1900 1900s 1910s 1920s 1930s 1940s Acetone cyanohydrin process

MMA Propylene, chloroacetic acid

process Mercury sulfate catalyst Acetaldehyde hydration process of Ethanol oxidation process acetylene Oxygen oxidation of Acetic acid Wood carbonization process acetaldehyde Liquid-phase acetic acid Gas-phase acetic acid Vinyl acetate addition process to addition process to acetylene acetylene Alkali dehydrochlorination HCl addition process to acetylene by Mercury Vinyl chloride process of EDC chloride catalyst Coal tar distillation Phenol Sulfuric acid process of Chlorobenzene process Raschig process benzene Phenol - cyclohexanol - nitric acid oxidation Adipic acid process Phenol - anon - oxime - Beckmann

Caprolactam rearrangement process

Terephthalic

acid

Phthalic Fuming sulfuric acid oxidation Catalytic oxidation process anhydride of naphthalene of naphthalene Maleic Phthalic anhydride Catalytic oxidation process of benzene anhydride byproduct recovery process Fig. 6.29 Technological history of major industrial organic chemicals. (MMA – Maleic anhydride before 1900 – 1940s)

174 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Product 1950s 1960s 1970s 1980s After 1990s Ethylbenzene Phosphoric acid catalytic process BF3-HF catalytic process ZSM-5 catalyst process EB dehydrogenation process of steam dilution by iron oxide Styrene catalyst

Halcon process (PO co-production process) Methanol Natural gas-based syngas process Ethanol Direct hydration process of IPA propylene tert Product from Halcon tert Product from direct hydration process by process (PO co-production acidic IM catalyst of isobutylene Butanol process) n and iso Product from Reppe n Product from Rh catalyst oxo reaction (CO,

process (CO, water) of propylene hydrogen) and reduction process of propylene Oxo reaction and reduction process of higher Higher alcohol Ziegler-Alfol process olefin EO EG Dimethyl oxalate reduction process Halcon process (oxidation by Direct oxidation by hydrogen PO peroxide) peroxide Allyl alcohol Glycerin Biodiesel byproduct process Wacker atmospheric oxidation Acetone Cumene process process of propylene Sohio process (ammoxidation of Ammoxidation process of Acrylonitrile HCN addition process to acetylene propylene) propane Modified Reppe process Propylene oxidation process (via acrolein) (carbonylation of acetylene) Acrylic acid Ketene - propiolactone process

AN hydrolysis process Fig. 6.29 Technological history of major industrial organic chemicals. (Ethylbenzene – Acrylic acid in 1950s – after 1990s)

Systematic Survey on Petrochemical Technology 175

Product 1950s 1960s 1970s 1980s After 1990s Isobutylene oxidation process MGC process (via methacrolein)

t-Butanol oxidation process (via MMA Direct meta process of isobutylene methacrolein) Ethylene raw material process Hydroxylation of ethylene (Hoechst-Wacker Acetaldehyde process) Oxygen oxidation of ethylene process Carbonylation process Acetic acid Oxygen oxidation process of naphtha Direct oxidation process of ethylene acetaldehyde of methanol Acetic acid oxidation of ethylene (Hoechst-Wacker Vinyl acetate process) Chlorine addition to ethylene, de-HCl Oxychlorination process Vinyl chloride process (EDC process) Acetylene-ethylene combination process Cumene process Oxidation process of cyclohexane Phenol Benzoic acid process Cyclohexane - cyclohexanol - nitric acid oxidation Adipic acid process Photonitrosation process (cyclohexane - Cyclohexane - Anon - ammoximation - Cyclohexane - Anon - oxime - Beckmann oxime hydrochloride - Beckmann gas phase Beckmann rearrangement rearrangement process rearrangement) process Caprolactam Cyclohexane - nitric acid nitration - oxime Peracetic acid process (cyclohexane - Anon - hydrogen reduction and rearrangement caprolactone - lactam) process Two-stage nitric acid oxidation process of PX Air oxidation and nitric acid oxidation process of

PX Terephthalic The 1st Henkel process (o-phthalic acid The 2nd Henkel process (benzoic acid acid isomerization) disproportionation) DMT process Amoco - mid-century process Phthalic Catalytic oxidation process of o-xylene anhydride Maleic Catalytic oxidation Catalytic oxidation process of butylene anhydride process of n-butane Fig. 6.29 Technological history of major industrial organic chemicals. (MMA – Maleic anhydride in 1950s – after 1990s)

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Technology Before 1900 1900s 1910s 1920s 1930s Celluloid Nitrocellulose lacquer

Nitrification cotton

process rayon Viscose process Utilization of natural polymer (viscose) cellophane rayon Acetate fiber, coating

Synthetic polymer

(Addition condensation) Phenolic resin Urea resin Melamine resin

(condensation polymerization,

thermosetting) (condensation polymerization, thermal Nylon

plasticity) (Oxidative polymerization) Dry oil paint Alkyd resin

(radical polymerization) Vinyl acetate resin Polystyrene

Vinyl chloride resin PMMA

LDPE

Chloroprene rubber

SBR

NBR

(Ion polymerization)

(Metathesis)

Fig. 6.30 History of major polymer technology (before 1900 – 1930s)

Systematic Survey on Petrochemical Technology 177

Technology 1940s 1950s 1960s 1970s 1980s After 1990s Utilization of natural

polymer (acetate) Photographic film (acetate) Cigarette filters (acetate) Liquid crystal polarizing film

Synthetic polymer

(Addition

condensation) (condensation Unsaturated polyester polymerization, thermosetting) Polyurethane Polyimide

Epoxy resin

Silicone

PPO

(condensation Polyurethane-type Polyester PET PBT PEEK polymerization, thermoplastic rubber thermal plasticity) PET film Polysulfone PES Polyetherimide

Para-aromatic Polycarbonate Meta-aromatic aramid Liquid crystal polymer aramid (Oxidative PPO polymerization) (radical polymerization) Vinylon Acrylic

AS resin

ABS resin

Fluororesin

Styrene-type thermoplastic (Ion polymerization) Butyl rubber Low-pressure process HDPE L-LDPE Metallocene PE (Post-metallocene PE) rubber Medium-pressure process HDPE

Polyacetal

Polypropylene

EPDM rubber

Polyisoprene rubber

cis-1,4-Butadiene-based

rubber (Metathesis) COP

Fig. 6.30 History of major polymer technology (1940s – after 1990s)

178 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

Development of technologies using of the cumeme process superceding the reactions to places other than olefin double existing coal chemistry technology., The bonds took considerably longer than the cyclohexane process was also developed in technologies using additions to olefin double the 1950s for manufacture of adipic acid and bonds. These technologies are all catalytic caprolactam, replacing the phenol process, reactions. Allyl chloride was made from which had been used since the coal chemistry propylene in the 1940s, followed by the period. Manufacture of pthalic anhydride by Hoechst-Wacker process (acetaldehyde from catalytic oxidation of o-xylene was developed ethylene) in the 1950s, vinyl acetate by in the late 1960s. This technology acetoxylation of ethylene, acrylonitrile by superceded the oxidation of naphthalene from ammoxidation of propylene and maleic coal tar. It may be said that terephthalic acid anhydride by oxidation of butylene in the as a raw material for polyester is an industrial 1960s, acrolein and acrylic acid by direct organic chemical that was developed between oxidation of propylene in the 1970s, MMA the periods of coal chemistry and petroleum by oxidation of isobutylene in the 1980s, and chemistry, because it has been in demand so on. since petroleum chemistry became In the 1920s, production of vinyl chloride widespread to Europe and Japan in the 1950s. started with the formation of EDC by an Accordingly, in the 1950s, coal chemistry addition reaction of chlorine to ethylene, technologies (first and second Henkel followed by dehydrogenation with an alkali. processes) and petrochemistry technologies However, due to the fact that this process (air oxidation/nitric acid oxidation of wasted hydrogen chloride, it came to be p-xylene, DMT process and Amoco process) replaced by the acetylene process. In the were both developed one after another, 1950s, the EDC process revived as a result of competing with each other. a cheap supply of ethylene and the hydrogen Of the technologies for manufacturing chloride being collected by thermal cracking industrial organic chemicals with syngas, of EDC. However, this process was really only the manufacture of acetic acid by only applicable when there was a consumer carbonylation of methanol, developed in the with a demand for the collected hydrogen 1970s, may be classified as a petrochemical chloride. One such consumer was the technology in the narrow sense. The bases for ethylene/acetylene coproduction process, in production technologies for methanol, which hydrogen chloride was added to formaldehyde, etc. had already formed in the acetylene. For this purpose, even processes coal chemistry period. for manufacturing basic petrochemicals As mentioned above, among the (co-production of acetylene and ethylene) by technologies for manufacturing industrial flame cracking of naphtha and organic chemicals by petroleum chemistry in high-temperature steam cracking of crude oil the narrow sense, addition reaction to the were developed. In the 1970s, the ethylene double bond of olefins began with oxychlorination process was developed, and stoichiometric reactions in the 1920s, later vinyl chloride was subsequently only replaced by catalytic reactions in many cases produced using the from the 1930s onwards. Reaction processes EDC process combined with the to places other than olefin double bonds were oxychlorination process. developed in the 1950s and have since then Although some manufacturing been extending the range of olefin chemistry. technologies for aromatic industrial organic Manufacturing technologies for aromatic chemicals had long been used in coal tar industrial organic chemicals by chemistry, most of the petrochemical petrochemistry bore fruit based on coal tar technologies in the narrow sense were chemistry in the 1950s. However, the main developed between the 1950s and 1960s, technologies for many products including coming after the manufacturing processes for caprolactam and adipic acid, were established olefins. In the 1950s, phenol became a during the period of coal chemistry. petrochemical product, with the development

Systematic Survey on Petrochemical Technology 179

(3) Polymer technology the technological development of The history of polymer technologies has petrochemistry since it was created to the been mentioned in some detail in Section present can be considered to be olefin 6.1.3. It is summarized in Fig. 6.30. In the manufacturing processes for basic 1940s, 1920s petrochemistry combined with petrochemicals, olefin chemistry for polymerization for the first time in the United industrial organic chemicals and olefin States; at that time, large amounts of polymerization processes for polymers synthetic rubber (SBR) were being produced Of the processes for manufacturing basic from butadiene in line with United States petrochemicals (Fig. 6.2), the technologies national policy. This triggered dramatic for manufacturing syngas and aromatic developments in petroleum chemistry from hydrocarbons supplement the technologies the 1950s onwards. However, perhaps for manufacturing olefins. Syngas unexpectedly, the basic technology of manufacturing technologies were essentially sequential polymerization was formed in the established in coal chemistry; the same is true coal chemistry era before the 1940s, as shown of aromatic hydrocarbon technology in in Fig. 6.30. Nevertheless, sequential petroleum refining technologies. These prior polymerization has also created many new technologies flowed over into petrochemistry. polymers in petrochemistry since the 1960s, Of the manufacturing technologies for such as the recently developed functional industrial organic chemicals (Fig. 6.16), polymers. aromatic hydrocarbon chemistry, Meanwhile, in chain polymerization, cycloparaffin chemistry, C1 chemistry and radical polymerization has produced many other organic synthetic chemistry supplement significant polymers (polyvinyl chloride, olefin chemistry. Aromatic hydrocarbon vinyl acetate resin, poly (methyl chemistry, C1 chemistry and other types of methacrylate), polystyrene, chloroprene organic synthetic chemistry were developed rubber, SBR, NBR, ABS resin, acrylic fiber, in coal chemistry or fermentation chemistry LDPE, etc.). The main monomers for radical and then flowed over into petrochemistry. polymerization were produced and Cycloparaffin chemistry came into being in industrialized in coal chemistry (acetylene petrochemistry but has not flourished, other chemistry and coal tar chemistry) and than for cyclohexane. fermentation chemistry (ethanol). These basic Of the polymer manufacturing technologies technologies were established independently (Figs. 6.22 and 6.24), coordination anionic of petrochemistry. In the 1940s, ionic polymerization, included in ionic polymerization produced butyl rubber, BR, polymerization of chain polymerization, has etc. mainly from petrochemical raw materials. played a central role. On the olefin As mentioned above, monomers for polymerization technologies, radical many polymerization technologies were polymerization (LDPE) in the 1930s, anionic developed and industrialized independently and cationic polymerization (polybutadiene of petrochemistry. In contrast, coordination and butyl rubber) in the 1940s and metal anionic polymerization was only created in oxide polymerization (HDPE) were petrochemistry in the 1950s. This technology developed. Since the 1950s, coordination subsequently made a substantial contribution anionic polymerization has been a main to the dramatic development of stream of the technological development of petrochemistry. As this technology is already polymers. Sequential polymerization and described in detail in Section 6.1.3 (1) 4), any radical polymerization technology, whose further explanation of it is omitted here. foundation was already laid before the creation of petrochemistry, flowed over into (4) Essence of petrochemical technology petrochemistry, thus supplementing the As discussed above, when reviewing the technologies for manufacturing polymers in history of petrochemical technology in the petrochemistry. However, the importance of narrow sense, the petrochemical technologies sequential polymerization revived from the that have played the most important role in 1980s onwards, because petrochemistry

180 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) began aiming towards functional chemistry. the creation of petrochemistry in Europe and Japan in the 1950s. 6.3.2 Epoch-making petrochemical Production technology for ethylene oxide technology in the presence of a silver catalyst was Table 6.4 summarizes the epoch-making invented in France in the early 1930s and technologies that made substantial industrialized in the late 1930s. This contributions to the progress of technology was the first to be industrialized petrochemistry in its history of more than 100 using a solid-supported catalyst in the history years. of petrochemistry. It is also very significant that the reaction associated with high risk of Table 6.4 Epoch-making technologies in the explosion, in which ethylene was mixed with history of petrochemistry oxygen or air to directly synthesize ethylene oxide, was successfully industrialized early in the history of petrochemistry. Production technology for acetaldehyde by the Hoechst-Wacker process and production technology for acrylonitrile by ammoxidation in the 1950s and production technology for EDC by oxychlorination process in the 1960s markedly widened the range of olefin chemistry. These were epoch-making technologies, because they

provided petrochemistry with a basis for It is well known that petrochemistry completely dominating coal chemistry. In the began with the production of isopropyl 1980s, the metathesis reaction was developed, alcohol by the sulfuric acid process from following on from the above three types of waste gas obtained by thermal cracking of olefin chemistry. It, too, extended the range heavy oil in 1920. However, this process is of olefin chemistry. only part of the organic synthetic processes In the 1950s, the Ziegler-Natta catalyst that have been accumulated since the 19th was developed in the period of century, because thermal cracking of heavy petrochemistry. This catalyst became a oil is a petroleum refining process for starting point for coordination anionic producing gasoline, and because the sulfuric polymerization, which is still making acid process is a stoichiometric reaction using advances to this day. It was also propylene and sulfuric acid. Therefore, it epoch-making in that it produced large-scale cannot be classified as an epoch-making petrochemical products (polyethylene, PP and petrochemical process. It is not well known various synthetic rubbers). that the steam cracking of ethane separated The zeolite ZSM-5 process developed in from natural gas was also industrialized in the 1960s is a solid catalyst/adsorptive 1920. This process, however, can be said to separation technology that utilizes steric be the first epoch-making technology in structure-controlled empty holes. This petrochemistry, because it subsequently technology was widely used in various areas played a very important role in the of petrochemistry and, moreover, it became a petrochemical industry, due to the fact that its starting point for the utilization of steric main purpose was the production of ethylene structure-controlled empty holes other than as a raw material for chemicals, and the fact those of ZSM-5. that a decrease of partial pressure by addition of steam was a versatile technology that was applicable to the production of other 6.4 Japanese petrochemical technology petrochemicals. Nevertheless, the process for steam cracking of naphtha and separation of This section discusses Japanese products developed in the 1940s was still petrochemical technology in the context of important, because it laid the foundation for the history of petrochemical technology

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worldwide. Currently, Japanese companies tar chemical products, as shown in Table 6.5. are leading the world in the development of The technology developed by Japan Gas some petrochemical technologies, including Chemical was one such example. technology utilizing C4 olefins, post-metallocene catalysts and paraffin Table 6.5 In-house technology of industrial chemicals. Japan’s new initiatives in organic chemicals and polymers developed functional chemistry are also dramatically after the Second World War and up to the changing the existing concepts of first half of the 1950s petrochemistry. Year Company Product Toshiba 6.4.1 The history of Japanese Start of production of Corporation 1946 acetylene-process vinyl petrochemical technology Shonan, chloride resin Prior to petrochemistry, Japan already Yokahama Rubber Production resumed on had a long history in developing The Nippon acetylene-process vinyl mass-producing chemical industries, such as 1947 Synthetic acetate (Start of production Chemical Industry coal chemistry. Although these chemical in 1936) industries were dealt a devastating blow by 1948 Tekkosha, Denki Start of production of the Second World War, the technology was to Kagaku Kogyo and acetylene-process vinyl not lost. When adopting Western 1951 others chloride resin Start of production of 1950 Kurashiki Rayon petrochemical technology in the 1950s, Japan polyvinyl alcohol and vinylon drew on its existing technological expertise, Completion of a plant to quickly absorbing petrochemical technology 1951 Toyo Rayon produce nylon with a 5t and moving on to being an active player in daily production capacity Toagosei Completion of caprolactam the Sturm und Drang period of 1951 Chemical Industry synthesis technology petrochemistry. This laid the foundation for Completion of maleic Japanese companies to become frontrunners anhydride facility of 1952 Nippon Shokubai in functional chemistry from the 1980s benzene gas-phase onwards, and to spark new trends in oxidation process Japan Gas Completion of steam petrochemical technology. 1952 Chemical, Japan catalytic reforming Gasoline technology of natural gas (1) The 1950s: Japanese petrochemistry Start of anthraquinone launches on domestically-produced 1953 Nippon Shokubai production by anthracene gas-phase oxidation technology Kureha Chemical Start of production of 1953 As discussed in Section 5.3.3 (2), Industry vinylidene chloride resin petrochemistry in Japan started in 1952 with Source: Prepared from reference [5] and each company's the production of syngas and methanol by homepage

Japan Gas Chemical using natural gas from Of course, not all such technology Niigata as a raw material. Methanol had been developments were necessarily successful. produced in Japan since the start of the 20th “On the Petroleum-Based Synthetic Chemical century by the wood retorting industry; Industry,” published by the Ministry of syngas had been produced since the 1930s International Trade and Industry, Organic using coal as a raw material. Accordingly, Division on June 1, 1951, noted the research Japan already had the technology to produce by Japan Gas Chemical, as well as methanol from syngas since before the experiments by Gas Denko Bunkai to Second World War. The technology to produce acetylene gas and hydrogen by arc produce syngas from natural gas had been cracking natural gas. It stated that there were developed through joint research between plans to industrialize acetylene-process vinyl Japan Gas Chemical and Japan Gasoline chloride and vinyl acetate based on this (Table 6.5). Leading up to the early 1950s, success. However, domestic technological there were a number of instances of Japanese development of the arc method ultimately companies using their own technology never came to fruition. developed before and during the war to With oil refineries reaching a certain produce acetylene chemical products and coal

182 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) level of development, as mentioned in technology gap with the West that had sprung Section 5.3.3 (3), Nippon Petro Chemicals up during the information blackout period in produced isopropyl alcohol and acetone from the Second World War. Japan started petroleum waste-gas propylene in 1957, increasing its imports of PVC, polystyrene, while Maruzen Petrochemical produced polyethylene and other polymers. This sec-butyl alcohol and MEK from n-butylene, presented a significant problem, given the also found in petroleum waste gas. This is foreign currency situation at the time. generally regarded as the start of Accordingly, Japan immediately set about petrochemistry in Japan. While Nippon Petro licensing the petrochemical and related Chemicals was using introduced technology, technologies that were lacking in Japan, and Maruzen Petrochemical had developed its aimed towards creating a petrochemical own. We must not forget that Japanese industry in Japan, starting with the petrochemistry did not start out on introduced steam-cracking of naphtha. The Japanese technology alone, but with a wealth of government pushed and supported this. As independently-developed technology as well. shown in Table 6.6, the vast majority of the petrochemical products initially produced by (2) The 1960s: The introduced technology Japan in the last 1950s were achieved through rush and domestically-produced introduced technology. Later, as the Japanese petrochemical technology petrochemical industry began to become In the 1950s, Japan was on the receiving more established through more technology end of an influx of information about major licensing from the West in the 1960s, the idea petrochemical developments in the West, not began to take hold in Japanese society that only within the field of petrochemistry, but almost all petrochemical technology in Japan also in petrochemistry-related technology was introduced technology. Delegations of a fields that were new to the pre-war chemical number of Japanese chemical companies industries (chemical engineering, flocked to Italian company Montecatini, instrumentation and control technology, which developed PP, in the hope of instrumental analysis and plastic molding, as establishing technology licenses; this is discussed in Chapter 2). The Japanese jokingly referred to as the “Monte visit.” chemical industry was shocked by the major

Table 6.6 The earliest stage of petrochemical products and technologies in Japan

However, as mentioned in Chapter 5, as

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the United States petrochemical technology ethylene and to produce vinyl chloride by the transferred to Europe in the 1950s, it blended EDC process and the acetylene process at the with European chemical technology. Many same time. significant petrochemical technologies had In those early days of petrochemistry, their origins in Europe, while the United when Japan was caught up in introduced States began to import these European technology, the industrialization of oxo technologies in return. From the 1950s alcohols by Mitsubishi Kasei in 1960 using onwards, petrochemical technology began to its own technology is worth noting. This is spread beyond borders, unlike the situation said to have been the result of research before the Second World War. This was part undertaken with reference to the post-war PB of the international spread of petrochemical Reports researched and published by the technology; it was not necessary to humiliate United States on wartime German science itself for licensing. As a result, Japan’s and technology. introduced technology rush from the late As shown in Table 6.7, although 1950s to the early 1960s saw Japan opt for technologies were developed in the West technology licensing instead of the time, costs from the late 1950s to the early 1960s, Japan and various risks involved in in-house was often the first or among the first to development. One typical example is the industrialize them. In several cases, Japanese licensing of nylon technology by Toyo Rayon companies played a very significant role in (now Toray). Toray had started researching finishing off industrial technologies for nylon before the war and started production Western technological development in 1951 using its own in-house technology, as companies. Examples of this include HDPE shown in Table 6.5. Prior to that, it had by Mitsui Petrochemical Industries, PP by developed the market with products such as Mitsui Chemicals, and acrylonitrile by Asahi fishing lines and fish nets at the protoype Kasei. Each of these is a very significant field stage, which boosted its business of technology in the global history of performance immediately after the war. petrochemistry. Nevertheless, it outlaid significant capital and took the plunge into introduced technology. Table 6.7 Examples of world first or very This was due to wanting to secure the market early industrialization in Japan of at an early stage using technologies that petrochemical technology would develop the market for clothing Industrial- Industrial- applications, such as weaving and dyeing, as Product Technology ization ization company year well as polymerization, spinning and other Mitsui Low-pressure Ziegler nylon production technologies; avoiding Petrochemic 1958 polyethylene process patent disputes with DuPont was also a al Industries The 1st Kawasaki factor. Terephthalic Henkel Kasei 1958 acid There was one field of petrochemical process Chemicals technology in which Japan had absolutely no Mitsui Terephthalic Mid-century Petrochemic 1958 prior underlying experience: steam-cracking acid process technology, developed from petroleum al Industries Medium- Furukawa Standard refining technology. There were similar pressure Kagaku 1959 process situations in Europe; Japan was not the only polyethylene Kogyo place to heavily rely on introduced Montedison Mitsui Polypropylene 1962 technology. However, Zeon and Kureha process Chemicals Sohio Chemical Industry developed and Acrylonitrile Asahi Kasei 1962 process industrialized high temperature steam Naphtha steam Esso type Tonen Sekiyu 1962 cracking for naphtha and crude oil in this cracking furnace Kagaku The 2nd Mitsubishi very field, just as Europe was attempting Terephthalic Henkel Chemical 1963 crude oil cracking and naphtha catalytic acid process Industries cracking. The aim of this steam-cracking Wacker Daikyowa Acetone 1964 technology was to co-produce acetylene and process Sekiyu

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Kagaku Crude oil high Solution Nippon Alfin temperature Kureha Alfin rubber 1970 processSBR Rubber 1970 Vinyl chloride decomposition Chemical Source: Prepared from reference [5] of Kureha Industry process Furthermore, as shown in Table 6.8, a Source: Prepared from reference [5] and each company's number of significant petrochemical homepage technologies were developed in Japan as In the late 1960s, a very large number of early as the mid-1960s. Some of this plants started up through domestically technology was produced in Japan and produced technology, as shown in Table 6.9. exported to the West, such as the GPB Surprisingly, within only 5–10 years of process by Zeon. The GPB process has since petrochemistry taking hold in Japan with been exported to 49 plants in 19 countries. introduced technology at its core, a large

number of latecomer companies were Table 6.8 Important petrochemical entering the market with their own technology developed in Japan in the 1950s independent technology in every to the 1960s Industriali- petrochemical product field. This also Development zation Product Technology suggests that newcomers to the Japanese company year petrochemical market in the late 1950s were Methyl ethyl FCCwaste gas Maruzen 1957 eager to industrialize their products through ketone utilization Petroleum introduced technology and were first trying to Ethylene Ethylene Nippon 1959 oxidation take a firm hold of the market. oxide Shokubai process Maruzen Table 6.9 Examples of industrialization by Circulation Petroleum, domestic technology in the second half of 1960 p-Xylene treatment Resources process Research 1960s Start of Institute Name of company Product Mitsubishi production Propylene oxo 1960 Oxoalcohol Chemical Daicel Chemical process Alkylamine 1965 Industries Industries 1963 Caprolactam PNC process Toyo Rayon Denki Kagaku Kogyo Polystyrene 1965* Naphtha high Kureha Showa Denko K.K. Isophthalonitrile 1966 temperature Chemical Showa Denko K.K. Xylylenediamine 1966 Mitsui Toatsu 1964 Vinyl chloride decomposition Industry, Polystyrene 1966 of Kureha Chiyoda Chemical process Corporation Mitsui Petrochemical Polypropylene 1967 Ammoxidation Nippon Industries 1964 Phthalonitrile process Shokubai Daicel Chemical Acrolein 1967 Japan Industries Synthetic Vinyl chloride by 1965 Polybutadiene JSR process Rubber, Tokuyama Soda oxychlorination 1967 Bridgestone process Zeon Sumitomo Chemical Meta-, para-cresol 1967 1965 Butadiene GPB process Corporation Toyo Soda Ethyleneamine 1967 Oxychlorination Toyo Soda Manufacturing 1966 Vinyl chloride process Manufacturing Mitsubishi Chemical Medium-pressure 1968 Urea adduct Industries polyethylene 1967 n-Paraffin Nippon Mining process Daicel Chemical ABS resin 1968 Dealkylation of Mitsubishi Industries 1967 Benzene MHCprocess Petrochemical Chlorinated Showa Denko K.K. 1968 Zeon polyethylene 1967 Vinyl chloride GPA process Corporation Vinyl chloride by Mitsui Toatsu m-Xylene oxychlorination 1968 Chemical extraction Japan Gas process 1968 Mixed xylene isomerization Chemical Idemitsu Polycarbonate 1968 process Petrochemical Propylene Idemitsu Acrylic acid Nippon Polystyrene 1968 1970 oxidation Petrochemical ester Shokubai process Nippon Petroleum resin 1968

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Petrochemicals the petrochemical industry in the 1970s, air Daicel Chemical Synthetic glycerin 1969 pollution, water pollution and other negative Industries Showa Denko K.K. Polypropylene 1969 aspects began to manifest. Overseas Dainippon Ink Polystyrene 1969* introduced technology could not be relied Mitsubishi upon to combat air and water pollution; this Ethylene 1969* Petrochemical was resolved within a relatively short space Mitsubishi Chemical Maleic anhydride 1970 of time through domestically-produced Industries Mitsui Petrochemical technology. Japanese chemical companies EPR 1970 Industries were quick to respond, having already put Mitsui Petrochemical Meta, paracresol 1970 high-pressure fat reduction technology, which Industries produces straight-chain higher alcohols, to Tokuyama Soda Polypropylene 1970 Tokuyama Soda Chloromethanes 1970 use since before the war; this technology was High-pressure used to combat the issue of foam pollution Sumitomo Chemical 1970* polyethylene from synthetic detergents in the mid-1960s. Medium-pressure Asahi Kasei 1970 The petrochemical technology to extract polyethylene n-paraffin, a starting material for obtaining Idemitsu Styrene 1970 Petrochemical higher alcohols from kerosene, was also Denki Kagaku Kogyo ABS resin 1970* developed by Nippon Mining in 1967 (Table Note: The asterisk (*) denotes the technology development 6.8). year. Having caught up with the West in the Source: Prepared from reference [6] 1970s, Japan was no longer lagging behind Nevertheless, even at this time there were Western companies in its technological still some fields that were highly dependent developments, even with the emergence of on introduced technology. These were fields several negative aspects of petrochemistry of technology that had been established in the from the 1970s onwards, as discussed in 1920s–1940s, when the petrochemical Section 5.5. Japan developed PCB processing, industry only existed in the United States chlorofluorocarbon alternatives, processing (steam cracking, LDPE, styrene, synthetic for nitrous oxide produced in the course of rubber SBR). This was the point of difference making the raw materials for nylon and afforded by a history of technology countermeasures for plastic waste issues. accumulation. By contrast, the petrochemical technologies that had come about in the (4) The 1980s: Increased research and 1950s era of fused Western technology were development expenses for Japanese successively being developed as domestically chemical companies produced technology. These included HDPE, In the 1980s, Japanese chemical PP, styrenic polymers and oxychlorination companies were increasingly very active in process for vinyl chloride. research and development, as shown in Fig. While Japan came in towards the end of 6.31. Petrochemical companies are shown in the Sturm und Drang period of Fig. 6.31 as “Diversified Chemicals / petrochemistry, it was just in time to imbibe Chemical Fibers.” While petrochemistry had the atmosphere of that era. Not only did it a lower R&D/sales ratio than other industries simply adopt technologies developed in the such as pharmaceuticals, the expense of West, it also became an active player in the research and development increased in the Sturm und Drang period. Japanese 1980s, and the R&D/sales ratio plateaued petrochemistry had the good fortune to start throughout the 1990s and 2000s. out in a completely different era from many developing nations from the 1970s onwards. [Footnote 6]

(3) The 1970s: Technologies developed in response to negative aspects emerging With major developments taking place in

186 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016)

properties of the material itself, such as heat-resistant or high-tensile engineering plastics, or superabsorbent polymers. However, the Japanese petrochemistry business model from the 1990s onwards went beyond the boundaries of petrochemistry (basic petrochemicals, industrial organic chemicals and polymers), the scope of the present study, even incorporating the parts/products stage of products made from

Fig. 6.31 Change of the ratio of research and polymers. Accordingly, the scope of research development expenses to sales of Japanese and development went beyond the boundaries chemical companies. of polymerization, even incorporating polymer processing technology and Research and development by parts/products assessment technology, which petrochemical companies in the 1980s tended generated much added value. Table 6.10 towards propylene/butylene chemistry, shows the functional polymer materials and developing polymer structural materials, functional chemical products focused on by energy-conserving technologies and Japanese petrochemical companies from the low-polluting technologies. At the same time, 1990s onwards. Japanese chemical companies functional chemistry was being explored in lead the world in one of these fields, developed nations, as the mass-produced functional film, shown in Table 6.11. We petrochemical market was obviously cannot forget that petrochemical technology, well-developed. This resulted in the early particularly polymer technology, provided the appearance of engineering plastics utilizing basis for the technology to develop these polymer technology, semiconductor resists functional chemistry products. and photosensitive resins for print Meanwhile, Japanese petrochemical platemaking and other applications. companies have also been markedly active in the fields of petrochemistry that fall within (5) From the 1990s onwards: Functional the scope of this study, even while many chemistry comes into full bloom Western companies have been withdrawing While functional polymer development from petrochemistry. A number of Japanese continued to be at the core, the expansion into companies have contributed to the new functional chemistry by Japanese chemical synthesis technology for acrylic acid and companies in the 1990s followed a different methacrylic acid. This is the field of olefin business model from the conventional chemistry, hydrocarbons with three or more petrochemistry in the West, namely, the carbon atoms and paraffin chemistry. development of functional chemical products Japanese companies have also played a key through the integration of polymer processing. role worldwide in the development of The expansion into polymer structural post-metallocene catalysts. materials in the 1980s had still centered on technological developments focused on the

Table 6.10 Functional polymer materials and molding products developed since the 1990s

Systematic Survey on Petrochemical Technology 187

Table 6.11 Functional film and its utilization area

have already mentioned some of these: the 6.4.2 World-class Japanese oxo process by Mitsubishi Chemical (Section petrochemical technologies 5.4.2 (2) 1)); butadiene extraction by Zeon Tables 6.7 and 6.8 show the (Section 6.4.1 (2)); highly active catalysts for petrochemical technologies developed by PP by Mitsui Chemicals (Section 6.1.3 (1) Japanese chemical companies in the 1950s– 4)); nitrite process by Ube Industries (Section 1960s. As a great many Japanese companies 6.2.3); the others we shall mention briefly. developed their own technology from the

1970s onwards, not all of them can be shown Table 6.12 World-class Japanese in these tables. Table 6.12 shows some of these independently-developed, world-class petrochemical technology Industrial- Company Technology Japanese petrochemical technologies. We ization year

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Nippon Ethylene oxide production 1959 Mitsubishi Gas Chemical was another Shokubai technology Japanese petrochemical company like Nippon Mitsubishi 1960 Oxo reaction technology Chemical Shokubai that used its own technology to Caprolactam production expand into unique areas of business. Its Toray 1962 technology of photonitrosation Industries predecessor, Japan Gas Chemical, was the process first to embark on petrochemistry in Japan Zeon 1965 Butadiene extraction technology Corporation with the industrial production of syngas and Mitsubishi methanol from natural gas in 1952. m-Xylene separation, Gas 1968 derivatives production Mitsubishi Gas Chemical was the first in the Chemical technology world to successfully isolate high-purity Company m-xylene from mixed xylenes in 1968, using Acrylic acid production Nippon 1970 technology of propylene direct its mastery of super-acid HF-BF3. It has Shokubai oxidation process expanded into product categories that are Mitsui High activity catalyst technology 1977 unique worldwide: high-purity isophthalic Chemicals for polypropylene acid (a raw material for PET denaturation and Sanyo Superabsorbent polyacrylic acid 1978 Chemical resin production technology meta-aramid fiber) and m-xylenediamine (a Mitsubishi raw material for aliphatic diisocyanates and Methyl methacrylate production Rayon and 1982 technology of isobutylene MX nylon) from m-xylene. Nippon process There are two types of noteworthy Shokubai Mitsubishi Acrylamide production caprolactam production technology: the 1984 Rayon technology bio process photonitrosation method developed by Toray Ube Oxidative carbonylation 1992 in 1962, and a method developed by Industries technology (nitrite technology) Sumitomo Chemical in 2003 that produces no Polycarbonate production 2002 Asahi Kasei technology of carbon dioxide as ammonium sulfate byproduct (developed raw materials from gas phase Beckmann rearrangement Caprolactam production technology). Both technologies are truly Sumitomo technology that produces no 2003 notable in the history of caprolactam Chemical ammonium sulfate as a byproduct technology worldwide. Further details on Acrylonitrile production these technologies are discussed in Section 2007 Asahi Kasei technology of propane process 6.1.2 (4). Note: The company names are the current ones, not the The photonitrosation method developed names that were in use at the time of industrialization. by Toray is the only instance in the world of producing industrial organic chemicals using Nippon Shokubai successfully photoreaction. Similarly, Mitsubishi Rayon industrialized the production of phthalic (Nitto Chemical Industry at the time, merged anhydride by oxidation of naphthalene, in 1998) developed a bio method for maleic anhydride by the oxidation of benzene producing acrylamide through hydration of and anthraquinone by oxidation of anthracene acrylonitrile using microorganisms as a in the coal chemistry era, which is around the catalyst. A little later, Mitsui Chemicals also Second World War. In 1959, the company developed a bio method for acrylamide developed its own technology to produce production, industrializing it in Korea and ethylene oxide by direct oxidation of ethylene, licensing the technology to Finland in 2013 and industrialized this in an industrial (see Section 3.4.3 (7)). While bio methods are complex in Kawasaki. Along with Mitsubishi used to produce small quantities of chemical Kasei’s oxo process, this was one of the products, such as amino acids, vitamins, pinnacle achievements in early Japanese pharmaceutical intermediates and optically petrochemistry. The company also active substances, there are no other instances successfully industrialized the production of worldwide of such methods being used in acrylic acid by direct oxidation of propylene mass production other than in petrochemistry. in 1970, and MMA by direct oxidation of Asahi Kasei developed a non-phosgene isobutylene in 1982. It has continued to polycarbonate production method using pursue the development of oxidation carbon dioxide as a raw material, and technology.

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industrialized it through a joint venture in in the 1920s. The wood retorting industry has Taiwan in 2002. This technology was later disappeared, unable to compete with exported to Korea, Russia, Saudi Arabia and carbide/acetylene chemistry and syngas other countries. Since it uses carbon dioxide chemistry in the 1930s. While oleochemistry as a raw material for the polymer and also was created in the 1900s, it was in the 1920s does not use phosgene, it has received many that higher alcohol production technology awards in Japan as a low-emission (high-pressure hydrogen reduction technology, and also received an award from technology for fats and oils) emerged, which the American Chemical Society in 2014. would later have strong ties with We have already discussed petrochemistry; it was in the 1930s that propane-based acrylonitrile production production technology emerged for higher technique, also developed by Asahi Kasei and alcohol sulfuric acid ester salts, the first industrialized by a Korean subsidiary neutral detergent. Fermentation chemistry company, in Section 6.2.4. This is an was created as a mass-producing chemical innovative technology with the potential to industry in the 1920s. break away from the conventional framework Polymer manufacturing technology also of olefin-focused petrochemistry. The originated prior to petrochemistry; cellulose propylene ammoxidation production method chemistry (celluloid, rayon, cellophane, for acrylonitrile is a world-dominating acetate) was created between the end of the technology held by British company BP. It 19th century and the 1920s, using natural was thought that BP would also develop a polymers in chemistry, and greatly flourished. propane ammoxidation production method Meanwhile, production technology for phenol for acrylonitrile; Asahi Kasei took the world resin, the first synthetic polymer, started in by surprise by doing it first. Section 6.3.2 the 1910s through coal chemistry. A introduced nine epoch-making petrochemical succession of polymers emerged in the 1920s technologies. Asahi Kasei’s propane-based and 1930s through radical polymerization; the acrylonitrile production technology should be monomers usedas the raw materials for these the tenth on this list, with the potential to were produced by acetylene chemistry. In the open up a new field of petrochemistry, 1940s, industrial production of LDPE by namely, paraffin chemistry. It was not radical polymerization commenced. Ethylene, included in Section 6.3.2, as its historical the raw material for LDPE, was mainly significance is not yet known. produced by dehydration of fermentation ethanol, as high purity was required. 6.5 Systematization of petrochemical By contrast, in the United States, technology and discussion industrial organic chemicals (IPA, EG, ethylene oxide) were being produced from Figure 6.32 shows a systematization of basic petrochemicals (propylene from waste petrochemical technology summarizing the gas from heavy oil cracking, ethylene from contents of this report, including technology steam cracking ethane) in the 1920s. This from the mass-producing chemical industries technology was purely petrochemical in that had developed prior to the creation of origin. By the 1930s, petrochemistry had petrochemistry. expanded to include various alcohols, As previously mentioned at length, tetraethyl lead and other products; however, petrochemical technology consists of three petrochemistry only existed as a supply for areas: basic petrochemicals, industrial organic industrial organic chemicals, alongside coal chemicals and polymers. Industrial organic chemistry, fermentation chemistry and chemical technology has origins as early as oleochemistry, according to the technological the 18th century wood retorting industry; strengths of each industry. Petrochemistry as other industrial organic chemical technology yet had no connection with polymers. dates back to coal tar chemistry in the late Restrictions on raw materials also meant that 19th century, carbide/acetylene chemistry in petrochemical technology had yet to spread the 1910s and coke-based syngas chemistry beyond the borders of the United States.

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In the 1940s, the production of synthetic range olefin polymer products expanded, rubber SBR from butadiene was promoted almost all of the polymers produced by strongly in the policies of the United States, radical and sequential polymerization shifted triggering a connection between to petrochemistry, where they had previously petrochemistry and polymers. Butadiene was been made from monomers supplied by being produced in the United States by acetylene chemistry and coal tar chemistry. butylene dehydrogenation; new developments Consequently, monomers became cheaper, in petrochemistry were beginning to bud. which in turn markedly increased the demand However, the United States butadiene for polymers from radical and sequential production by butylene dehydration could not polymerization. Conversely, cellulose match that of fermentation ethanol; even for chemistry quickly fell into decline at this time, butadiene petrochemistry could not take the under pressure from synthetic polymers. title on its own. The trends in the 1950s and 1960s show a In the late 1940s, after the end of the near disappearance of acetylene chemistry Second World War, the U.S. petrochemical due to the rise of olefin chemistry, while industry suddenly expanded significantly, aromatic chemistry was incorporated into driven by a raid growth in consumer demand petrochemistry as the source of aromatic for polymers. Production of PVC and hydrocarbons changed almost completely polyvinyl acetate rapidly increased in from coal tar to petroleum. Coke-based acetylene chemistry, as did in nylon and syngas chemistry was also incorporated into phenol resin in coal tar chemistry, urea resin petrochemistry due to the near complete in syngas chemistry and LDPE and change to natural gas and petroleum-based polystyrene in petrochemistry. The surging syngas. Oleochemistry fell under the rise of demand for polymers spread to Europe and industrial organic chemicals (surfactants) then Japan in the 1950s. Naphtha produced by petrochemical technology. steam-cracking technology was transferred Cellulose chemistry fell under the rise of from the United States, prompting the start of polymers produced by petrochemical production of basic petrochemicals in Europe technology, and the industry decreased in the early 1950s, and in Japan in the late significantly. In the field of fermentation 1950s. An underlying factor to this may be chemistry, acetone and butanol fermentation the beginning of Middle Eastern crude oil disappeared as they were replaced by being exported around the world. petrochemical technology, while ethanol Petrochemical technology, which had fermentation also significantly reduced in been developed in the United States since the scale, only surviving in fields in which the 1920s, also spread to Europe in the 1950s and only demand is for fermentation products developed further, fusing with the chemical (vinegar feedstock, food preservatives, etc.). technologies there. This resulted in major Thus, by the 1970s, the industrial organic developments in olefin chemistry and olefin chemicals and polymers that had predated polymerization technology in the 1950s and petrochemistry had all completely switched 1960s within the field of production over to petrochemistry. Meanwhile, the era of technology for industrial organic chemicals high economic growth ended in the 1970s in and polymers. The quality and scale of steam Japan and in the West, and the rapid growth cracking technology also increased rapidly in demand for polymers also came to an end. during this time. In addition to olefins, the The continuing emergence of innovative supply of aromatic hydrocarbons shifted from petrochemical technologies in the 1950s and coal tar to cracked gasoline by naphtha 1960s also ended. Nevertheless, from the steam-cracking and reformate by naphtha 1970s onwards, the explosive increase in catalytic reforming. Industrial organic polymer demand and the internationalization chemicals, which had once been produced by of petrochemistry spread from the more fermentation chemistry and acetylene developed nations to the resource-rich nations chemistry, were almost exclusively switching of the Middle East, and then to Asia, and to olefin chemistry. Even for polymers, as the Central and South America, thus preventing

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the worldwide petrochemical industry from From the 1980s onwards, there has been a stagnating. New technological challenges push for functional chemistry in Japan and arose in responding to energy conservation other developed nations. For more than three and environmental pollution issues, as well as decades, Japan has furthered its functional meeting new demand from developed nations chemistry technology beyond the (sudden increased demand for propylene, conventional bounds of petrochemistry, even functional chemistry). Technological extending it as far as polymer molding development continued beyond the 1970s in technology. Petrochemistry continues to grow response to these issues. Steady progress was and change beyond its conventional also made in front-running petrochemical framework. technologies, such as acetic acid through methanol carbonylation, metathesis reactions, Bibliography metallocene catalysts and post-metallocene [1] T. Takahashi, “The history of the catalysts. The advent of paraffin chemistry chemical industry,” Sangyo Tosho, 1973. also attracted some attention in contrast to [2] K. Weissermel, H. J. Arpe, “Industrial conventional olefin-based petrochemical organic chemistry,” Tokyo Kagaku-dojin technology. Publishing Company, Inc., 5th edition, Due to the emergence of pollution 2004. problems from propylene tetramer synthetic [3] H. A. Wittcoff, B. G. Reuben, J. S. detergents with poor biodegradability in the Plotkin, “Industrial organic chemicals,” 1970s, synthetic detergents started being Wiley, 3rd edition, New York, 2013. produced using higher alcohols from fats and [4] I. Ogata, “Petrochemistry,” Kodansha, oils. Oleochemistry revived and continued 1980. alongside petrochemistry. In the 2000s, there [5] “Ten-year history of the petrochemical was a rapid increase in production of industry,”Japan Petrochemical Industry biodiesel oil made from fats and oils and Association, ed., Japan Petrochemical methanol. Oleochemistry and petrochemistry Industry Association, 1971. continue to coexist in biodiesel oil production. [6] “Twenty-year history of the Meanwhile, the 2000s also saw a rapid petrochemical industry,”Japan increase in fermentation ethanol from Petrochemical Industry Association, ed., agricultural produce in the United States. This Japan Petrochemical Industry was put to use as a substitute for gasoline Association, 1981. additive MTBE, which was regulated due to [7] “Thirty-year history of the petrochemical groundwater contamination issues. industry,” Japan Petrochemical Industry Production grew significantly in scope to Association, ed., Japan Petrochemical match the production of ethylene in the Industry Association, 1989. United States. Fermentation chemistry [8] “Fifty years of petrochemistry—The revived to reclaim one small foothold over half-century timeline,” Japan petrochemistry in response to global Petrochemical Industry Association, ed., environmental issues. Thus, various Japan Petrochemical Industry Association, environmental issues have had varying 2008. impacts on petrochemistry. However, [9] P. Spitz, “Petrochemicals: The rise of an petrochemistry can be expected to overcome industry,” Wiley, 1988. these various environmental issues, chemical [10] E.P. Moore, Jr, “Polypropylene safety issues and energy conservation issues Handbook,” Kogyo Chosakai, 1998. in future.

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Before 1900 1900s 1910s 1920s 1930s 1940s 1950s 1960s 1970s 1980s After 1990s BT, naphthalene by Acetylene by carbide Syngas from natural Syngas from coke distillation of coal tar process gas

Coal chemistry PL, BL by fixed-bed Propane PL, BL by thermal catalytic cracking of dehydrogenation cracking of heavy oil heavy oil process EL, PL, BD, BTX by EL by steam cracking PL by metathesis Basic product steam cracking of Enlarging of steam cracking facility of ethane process naphtha MTP

Early US petrochemistry Integrating Period of Sturm period Petrochemical EL by dehydration of und Petrochemistry in technology Butadiene with European Drang ethanol Progressive stage mature era New trends technology Petrochemistry US Petrochemistry Ethylene oxide by petrochemistry EG by chlorohydrin catalytic oxidation process process, EG by EO hydrolysis process IPA, butanol, ethanol Ethanol by catalytic IPA by catalytic by sulfuric acid Fermentation chemistry hydration process hydration process process

Ethanol by Ethanol by Revival of fermentation chemistry fermentation process fermentation process Acetone-butanol by fermentation process

Higher alcohol by Hydrogenated oil of high-pressure Higher alcohol sulfuric Higher fatty alcohol- Revival of oleochemistry Soap fats and oils by Oleochemistry Biodiesel oil hydrogen reduction of acid ester salt based surfactant hydrogenation process oils and fats Higher fatty acid of high-pressure Glycerin Industrial hydrolysis process of organic fats and oils chemical Wood carbonization chemistry Carbonylation process Artificial petroleum by Synthetic methanol acetic acid of FT process methanol Woodcarbonization Acetaldehyde, acetic Acetaldehyde, vinyl Vinyl acetate by methanol, acetic acid, acid by acetylene acetate by Hoechst- acetylene process acetone process Wacker process Vinyl chloride by Vinyl acetate by Vinyl chloride by EDC oxychlorination acetylene process process process Paraffin chemistry AN by ethylene AN by acetylene AN by propane process Coal chemistry AN by sohio process cyanohydrin process process Phenol by coal tar Phenol by distillation process, Phenol by Raschig Phenol by cumene chlorobenzene phenol by sulfuric acid process process process process

Phthalic anhydride by Phthalic anhydrideby Phthalic anhydride by naphthalene/fuming naphthalene/catalytic o-Xylene/catalytic sulfuric acid process oxidation process oxidation process

Celluloid Nitrocellulose lacquer Functional chemistry integrated Rayon by nitrification Rayon by viscose Cellulose-based polymer technology with cotton process process polymer molding

Cellophane Acetate PET Polyimide Para-aramid PEEK Polymer Phenolic resin Urea resin PES Liquid crystal polymer Alkyd resin Nylon Butadiene-based Polyvinyl chloride SBR, NBR HDPE L-LDPE Metallocene PE (Post-metallocene PE) rubber Polyvinyl acetate LDPE Polypropylene Thermoplastic rubber COP Polystyrene Unsaturated polyester Polycarbonate EPR Synthetic polymer technology from petrochemistry Synthetic polymer technology from coal chemistry and fermentation chemistry PMMA Polyurethane Acrylic fiber

List of product abbreviations Ac: acetylene, EL: ethylene, PL: propylene, BL: butylene, B: benzene, T: toluene, X: xylene, AN: acrylonitrile Fig. 6.32 Technology system of petrochemistry.

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Conclusion 7

It has been 60 years since the out into functional chemistry while still establishment of the petrochemical industry remaining focused on petrochemistry. in Japan. However, an “official history” of Noted chemical companies in the West the Japanese petrochemical industry is more are continuing to withdraw from than a mere “Ten-year history” or petrochemistry. British company ICI “Twenty-year history” such as those given in developed methyl methacrylate MMA and bibliographic references 5 and 6 of Chapter 6. LDPE in the 1930s, polyester fiber in the The “Thity-year history” in bibliographic 1940s, and engineering plastics PEEK and reference 7 is too brief; the “Fifty years” in PES in the 1960s and 70s. Showing no signs bibliographic reference 8 is little more than a of slowing in its technological prowess, it chronology. was the first to develop biodegradable The main reason an “official history” is plastics in the 1980s, and also developed lacking is probably because the industry has chlorofluorocarbon alternatives in the 1990s. trended from growth towards stagnation since Despite these successes, ICI started the 1980s and has lost its appeal as an withdrawing from the petrochemical industry industry. An even more significant reason in the 1990s and quickly lost its corporate probably lies in the fact that petrochemistry identity. It sold off its operations in has changed with the times, and even those in succession, and in 2008, the lauded company the industry cannot define exactly “what is name disappeared through a merger. German petrochemistry?” In 2013, the Japan company Hoechst AG, known for developing Petrochemical Industry Association invited the Hoechst-Wacker process, HDPE and submissions for a new name instead of various kinds of engineering plastics, “petrochemistry.” This is the extent to which followed a similar path. The company ceased we are unable to define “what is to exist once it lost the mainstay of its petrochemistry?” technological core, readily setting aside its Accordingly, we were at a loss, firstly in core business and advocating defining petrochemistry, and then how to non-petrochemistry. Many other major narrow down the study area, taking into Western players in the industry have similarly account the constraints of the investigation abandoned the petrochemical industry, many period. However, convinced that narrowing of them attempting to expand into down the topic into a single area of pharmaceuticals and agribusiness, with petrochemistry (e.g. ethylene production growing demand in developed nations, using technology) would not give adequate insight biotechnology, rapidly developed since the into the overarching picture of petrochemistry 1970s, as their new technological axis. as a whole, we commenced researching this However, in many cases they have later felt topic without narrowing down a specific on looking back that they have lost their study area. Rather than focusing solely on former vitality and development potential. Japan, we also decided to aim the Meanwhile, the companies that have explored investigation as globally as possible and then new areas of technology while remaining position Japan within that. As a result, we focused on petrochemistry have seen steady have boldly gone beyond the normal bounds progress. of petrochemistry in identifying trends in Japanese petrochemical companies have Japanese petrochemistry from the 1990s frequently been criticized for not having the onwards, even incorporating polymer same dynamic management as their molding. This has been the path taken by counterparts in the West. However, their Japanese petrochemical companies; they have operations, while not showy, are solid and not followed in the footsteps of steady, and they have expanded into petrochemistry overseas, but have branched functional chemistry without losing their core

194 National Museum of Nature and Science: Survey Reports on the Systemization of Technologies Vol.23 (March 2016) focus on petrochemistry. petrochemical industry; it is simply an This report has intentionally focused “unofficial history” (privately composed within the realms of petrochemistry, on basic history) written at will by the author as an petrochemicals, industrial organic chemicals individual. Given the present situation where and polymers, and avoided delving too deeply there is not even a consensus on “what is into functional chemistry. However, it is petrochemistry?” there will of course be interesting to note the number of new trends many counterarguments to the “unofficial in petrochemistry since the 1990s, even history” presented by the author. However, within that scope. We have now reached the this serves as an opportunity to start people plateauing of petrochemical technology that thinking about the history of petrochemistry we spoke about in the 1970s, and are on the again. History does not simply end with verge of breaking through into a new stage. It recording the past; it provides guidelines for is worth noting that Japanese petrochemical the future. The hope is that this survey report companies have played a major role in these will to some extent serve in such a role. trends. Finally, the author would like to express Since Japanese petrochemistry has long heartfelt thanks to those who made this lacked an “official history,” its history has not research opportunity possible, to the many been recorded. Consequently, this survey people who cooperated in this study and to report makes no attempt to summarize the those who shared their valuable insights. collective opinions of the Japanese

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Location Confirmation of Historical Technology Resource Items from the Petrochemical Industry (including mass-produced chemical product items predating petrochemistry) Date of No. Name Format Location, etc. Place Manufacturer Reason for selection manufacture 1 Rayon research On Prof. Itsuzo Hata Faculty of 1913 Prof. Itsuzo Itsuzo Hata produced the first successful materials from the display Memorial Room, Main Engineering, Hata rayon prototype in Japan. A rayon factory Former Yonezawa Building, Former Yamagata was set up in Yonezawa using this Higher Technical Yonezawa Higher University, technology, eventually leading to School (prototype, Technical School Yonezawa, present-day Teijin. These items were glass nozzle, wooden Yamagata discovered when the old research implements) building was being demolished. 2 Rayon thread, rayon On Prof. Itsuzo Hata Faculty of 1924-1930 Imperial Rayon thread and rayon ribbon straw ribbon straw display Memorial Room, Main Engineering, Artificial Silk manufactured during the period of stable Building, Former Yamagata Co., Ltd. operation of the Imperial Artificial Silk Yonezawa Higher University, Yonezawa Plant (1916-1934). One of the Technical School Yonezawa, few instances of early mass-produced Yamagata products being kept. 3 High-pressure In Clariant Catalysts Toyama, 1989 Toyo CCI Co., Methanol synthesis research started at the methanol synthesis storage Toyama Plant Toyama Ltd. Temporary Nitrogenous Fertilizer catalyst KMA Laboratory in 1925. A catalyst production method was patented in 1927; Toyo Gosei successfully industrialized methanol synthesis in 1933 in Shimonoseki, Yamaguchi. Later, this catalyst was also sold to other Japanese companies and was used in the same form and composition up until 1989. 4 Celluloid compression In Daicel Corporation Himeji, Hyogo 1954 Dainippon Celluloid compression is a process tester storage Himeji Production Sector Celluloid Co., whereby cellulose nitrate and camphor Aboshi Plant Ltd. are mixed and then finished into blocks. While machines 1 and 2 were German-built and purchased in 1919, this is machine 3, the first domestically-produced machine.

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5 Fermentation ethanol In Japan Alcohol Izui, 1938 State-run Izumi A mash distillation column from the mash distillation storage Corporation Izumi Kagoshima Alcohol Plant second state-run alcohol plant to start column Factory operating in Japan. Despite being damaged in an air raid in August 1945, it was rebuilt and remained in use until 1997. 6 Fermentation ethanol In Japan Alcohol Iwata, 1939 State-run Iwata The Iwata Plant was the sixth of Japan’s distillation column storage Corporation Iwata Shizuoka Alcohol Plant 13 state-run alcohol plants to start plates Factory operating. These plates are part of a distillation column plate and a rectifying column or dehydrating column plate. 7 Fischer-Tropsch In Institute for Chemical Uji, Kyoto 1927-1938 Institute for Prof. Genitsu Kita’s laboratory at Kyoto artificial petroleum storage Research, Kyoto Chemical University started research on artificial synthesis catalyst and University Research, Kyoto petroleum synthesis from syngas in 1927, prototype University the year after the F-T process was discovered in Germany. Iron-based catalysts as a substitute for the existing cobalt-based catalysts were discovered in 1937. These items are a catalyst and a prototype. 8 Fischer-Tropsch In Takigawa Local Museum Takigawa, 1942-1945 Hokkaido Artificial petroleum product produced at artificial petroleum storage Hokkaido Artificial one of the large-scale F-T process product Petroleum Co., artificial petroleum factories established industrialization Ltd. through state policy. resource 9 Raw material feed In Mitsui Chemicals Iwakuni, 1958 Mitsui A raw material feed pump from the first pump from Japan’s storage Iwakuni Otake Factory Yamaguchi Petrochemical naphtha steam-cracking ethylene plant to first ethylene plant Industries Co., start operating in Japan. It operated from Ltd. 1958 to 1971. 10 Ethylene plant In Mitsui Chemicals Iwakuni, 1962 Mitsui A gas-driven compressor power piston, gas-driven compressor storage Iwakuni Otake Factory Yamaguchi Petrochemical arguably the central component, from the power piston Industries Co., second ethylene plant at the Iwakuni Ltd. Plant. Adopted as a state-of-the-art piece of technology at the time, it could handle a wide range of loads and fuel gas compositions.

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11 Japan’s first In Mitsui Chemicals Iwakuni, 1958 Mitsui Even on global standards, this is a very low-pressure HDPE storage Iwakuni Otake Factory Yamaguchi Petrochemical early polymerization machine for polymerization reactor Industries Co., producing low-pressure polyethylene, Ltd. invented by Prof. Ziegler of Germany in 1955. This operated from 1958 to 1989. 12 High-pressure LDPE In Institute for Chemical Uji, Kyoto 1951-1954 Institute for Diagrams, photographs, experiment notes pilot test data storage Research, Kyoto Chemical and internal reports from pilot tests for University Research, Kyoto producing high-pressure polyethylene University carried out after the war, based on small-scale wartime experiments. 13 Japan’s first On Sumitomo Chemical Niihama, 1958 Sumitomo Japan’s first full-scale industrial high-pressure LDPE display Company Ehime Factory Ehime Chemical Co., production of high-pressure polyethylene, product History Museum Ltd. using licenced technology from UK company ICI.

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A list of abbreviations for the product names used in this document Abbreviation Name Details 2,4-D 2,4-Dichlorophenoxyacetic acid Herbicide (agricultural chemical)

ABS resin Acrylonitrile-butadiene-styrene resin Semi-general-purpose plastic

ACH Acetone cyanohydrin Organic intermediate AE Alkylethoxylate, alcohol ethoxylate Nonionic surfactant AES Alkyl ether sulfate Anionic surfactant

AOS α-Olefin sulfonate Anionic surfactant AS Alkyl sulfonates Anionic surfactant AS resin Acrylonitrile-styrene resin Semi-general-purpose plastic

BHC Benzene hexachloride Insecticide (pesticide) BPA Bisphenol A Monomer

BR Butadiene rubber General-purpose synthetic rubber

CMC Carboxymethyl cellulose Dispersion stabilizer for food, binder, emulsifier COP Cyclic olefin polymer Excellent plastic for optic use

CPP Cast polypropylene film Transparent packaging film Film CR Chloroprene rubber Synthetic rubber outstanding in weather resistance DBP Dibutyl phthalate Plasticizer DDT Didchlorodiphenyl-trichloroethane Insecticide (pesticide, drug for public heath) DMF N,N-dimethylformamide Polar solvent DMSO Dimethyl sulfoxide Polar solvent DMT Dimethyl terephthalate Monomer DOP Dioctyl phthalate Plasticizer EDC Ethylene dichloride Organic intermediate EDTA Ethylenediaminetetraacetic acid Chelating agent EG Ethylene glycol Monomer, antifreeze

EPDM Ethylene propylene diene monomer Synthetic rubber rubber EPR Ethylene-propylene rubber Synthetic rubber EVA Ethylene-vinyl acetate copolymer Plastic, adhesive

HDPE High-density polyethylene General-purpose plastic

HIPS High impact polystyrene General-purpose plastic

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Abbreviation Name Details HNBR Hydrogenated nitrile rubber Special synthetic rubber IIR Isobutylene isoprene rubber (butyl Special synthetic rubber rubber) IPA Isopropyl alcohol Solvent IR Isoprene rubber General-purpose synthetic rubber LAS Linear alkylbenzenesulfonate Anionic surfactant

LDPE Low-density polyethylene General-purpose plastic

L-LDPE Linear low-density polyethylene General-purpose plastic MAO Methylalumoxane Component of polymerization catalysts MDI Methylene diphenyl diisocyanate Monomer

MEK Methyl ethyl ketone Solvent MMA Methyl methacrylate Monomer MTBE Methyl tertiary butyl ether Gasoline additive

MVA Monovinylacetylene Organic intermediate NBR Nitrile rubber, acrylonitrile butadiene Special synthetic rubber rubber OPP Oriented polypropylene film Transparent packaging film film PBT Polybutylene terephthalate General-purpose engineering plastic PCB Polychlorinated biphenyl Heat transfer medium, solvent, insulating oil

PCP Pentachlorophenol Herbicide, disinfectant

PEEK Polyether ether ketone Super engineering plastic PES Polyether sulfone Super engineering plastic PET Polyethylene terephthalate Plastic, synthetic fiber

PP Polypropylene General-purpose plastic PPE Modified polyphenylene ether General-purpose engineering plastic PPO Polyphenylene oxide General-purpose engineering plastic PPS Polyphenylene sulfide Super engineering plastic PTA High-purity terephthalic acid Monomer PTFE Polytetrafluoroethylene (Teflon) Plastic PTMG Polytetramethylene ether glycol Monomer

SAN Styrene acrylonitrile (same as AS General-purpose plastic resin) SBR Styrene-butadiene rubber General-purpose synthetic rubber

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Abbreviation Name Details SBS Styrene-butadiene-styrene block Thermoplastic elastomer copolymer SIS Styrene-isoprene-styrene block Thermoplastic elastomer copolymer TDI Toluene diisocyanate Monomer THF Tetrahydrofuran Solvent, monomer ULDPE Ultralow-density polyethylene Plastic VLDPE Very low-density polyethylene Plastic Note: The above names are not based on the IUPAC Nomenclature, but are usually used in the chemical industry.

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