Development of Process for Production of Highly Valuable Chemicals Derived from Dicyclopentadiene for Comprehensive Utilization of C5 Chemicals

Journal of the Japan Petroleum Institute, 62, (6), 245-254 (2019) 245

[Review Paper] Development of Process for Production of Highly Valuable Chemicals Derived from Dicyclopentadiene for Comprehensive Utilization of C5 Chemicals

Hideaki MIKI＊

Research and Development Center, Zeon Corp., 1-2-1 Yako, Kawasaki-ku, Kawasaki 210-9507, JAPAN

(Received March 29, 2019)

C5 chemicals (isoprene, dicyclopentadiene, piperylene) are co-produced by an extractive distillation process using C5 fraction, by-product of ethylene from naphtha cracker, as a raw material. The authors have developed a new process for producing cyclopentanone and a commercial process for manufacturing cyclopentyl methyl ether using dicyclopentadiene as a starting material for the comprehensive utilization of the C5 chemicals. In this report, we introduce the technical knowledge, especially about catalyst deactivation, obtained in the technical studies for the process development. In addition, we will review recent topics on the development of manufac- turing technology for C5 chemicals itself, which is essential to the growth of the C5 chemicals business.

Keywords C5 fraction, Dicyclopentadiene, Cyclopentanone, Cyclopentene, Catalyst deactivation, Cyclopentyl methyl ether

1. Introduction Production of IPM by extractive distillation is over- whelmingly cost competitive in terms of production The C5 chemicals is a generic name for compounds cost compared to other production processes3). But having 5 carbon atoms, and generally refers to three the concentration of IPM in the raw material (C5F) is compounds of isoprene (hereinafter IPM), dicyclopenta- relatively low, and the remaining components has been diene (hereinafter DCPD) and piperylene (hereinafter returned to ethylene center and has been treated as Pips). DCPD is classified as a C5 chemicals because alternative naphtha and/or fuel. Table 1 shows the it is produced by the dimerization of cyclopentadiene typical composition of C5F, and the boiling points of (hereinafter CPD). The first driver of C5 chemicals major components are shown in Table 24). was the development of isoprene rubber (IR). IR has a In order to solve this problem, derivatives of Pips and 5)～13) 1,4-cis structure similar to that of natural rubber, and is DCPD contained in C5F have been developed . mainly used as a tire rubber. 67 % (586,000 t/yr) of With the increase of demand for the derivatives devel- the global demand for isoprene in fiscal 2015 is the raw oped, the extractive distillation process for IPM produc- material for isoprene rubber. Global IPM demand is tion has been improved, and now Pips and DCPD are expected to steadily increase going forward, and IPM industrially co-produced from the same extractive dis- demand is said to reach 1,600,000 t/yr in fiscal 2030. tillation process. As an industrial production method of IPM, extractive The purity of Pips produced by the extractive distilla- distillation of C5 fraction (hereinafter C5F) obtained tion process is approximately 55-65 wt%. In order to from ethylene cracker, dehydrogenation of isopentane improve the purity of Pips, impurities such as amylenes and/or t-amylene, reaction of isobutylene with form- and C5 cyclic compounds such as cyclopentane (here- aldehyde (Prins reaction) are known. Among these, inafter CPA) and cyclopentene (hereinafter CPE) must the main industrial production process is extractive dis- be removed. However, due to the closeness in the tillation of C5 fraction, which accounts for 53 % of the boiling point of these impurities and Pips, distillation total production volume (478,000 t/yr in 2015) of IPM. purification requires a huge distillation column and The block flow diagram of typical extractive distillation enormous energy. So it is not economically feasible to process for IPM production, known as GPI (Geon purify the Pips by distillation. Therefore, the majority Process of Isoprene), is shown in Fig. 12). of Pips applications (90 % of the total application) are raw materials for petroleum resin. The fact that amyl- DOI: doi.org/10.1627/jpi.62.245 enes and cyclopentene, which are impurities, function ＊ E-mail: [email protected] as molecular weight modifiers at the time of petroleum

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Broken line stands for solvent circulation line.

Fig. 1● Schematic Drawing of GPI Process

Table 1 Typical Composition of C5F from Ethylene Cracker The applications vary greatly depending on the grade. Components Content [wt%] Low-purity products and normal products are used as raw materials for unsaturated polyesters and petroleum C4 compounds 3.0 resins (including hydrogenated petroleum resins), and Pentanes 36.5 Pentenes 17.0 account for 69 % of DCPD applications (437,000 t/yr in Isoprene 15.0 FY 2015). High-purity products are used as raw mate- Pentadienes (Pips) 10.0 rials for ethylidene norbornene, as vulcanization accel- Cyclopenatdiene and dicyclopentadiene 15.0 erators for ethylene and propylene rubber (EPDM) and C6 compounds 3.0 as raw materials for special chemicals. These Acetylenes and alenes 0.5 applications account for 22 % of the overall applica- tions (139,000 t/yr in FY 2015). Table 2 Boiling Point of Main Components of C5F On the other hand, the use of high purity products is Components Boiling point [°C] only 9 % of the whole, and is used as a raw material of cycloolefin polymer (COP), cycloolefin copolymer 2-Methyl-butane 27.9 1-Pentene 30.0 (COC), poly-DCPD and reaction injection molding 2-Methyl-1-butene 31.2 (RIM). Isoprene 34.1 Looking at the applications of C5 chemicals, they are n-Pentane 36.1 overwhelmingly used as polymer raw materials. It trans-2-Pentene 36.4 seems that there is a history of preferential development cis-2-Pentene 37.0 2-Methyl-2-butene 38.6 of applications in which a certain amount of usage can Cyclopentadiene 41.0 be expected, since the production of IPM by extractive trans-1,3-Pentadiene 42.3 distillation results in co-production of DCPD and Pips cis-1,3-Pentadiene 44.1 at the same time in the amounts similar to IPM respec- tively. The exceptional ones are the fine chemical products from IPM developed by Kuraray Co., Ltd. resin production is also one of the factors that greatly They developed a wide range of fine chemical products, expanded the application of Pips to petroleum resins. including synthetic flavors linalool, ionone, citral, etc. On the other hand, DCPD is distributed in four Kuraray Co., Ltd. produces IPM by modifying the pro- grades: low purity (75 wt%), normal (85 wt%), high duction method by Prins reaction, which was originally purity (92 to 95 wt%), and ultrahigh purity (99 wt%). a two-step method, to a one-step method. Since this

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Fig. 2 Production Scheme of CPN and CPME from DCPD production method is a process of producing only IPM, 2. Development of the New Process for it is possible to adjust production according to the bal- Manufacturing CPN from DCPD ance of supply and demand. That seems to be the rea- son that the fine chemical business using IPM as a start- CPN is usually produced by a reaction of adipic acid ing material could be commercially realized. as shown in Scheme 117)～19). Raw materials of fine chemicals are generally required to have extremely high purity. When Pips is used as a raw material for fine chemicals, as described above, it is very difficult to improve the purity by distil- lation. Also, no practical application case of technology for producing Pips by a synthetic method has been found so far, and there is currently no method for eco- + + 2 t. 2 nomically obtaining high purity Pips. On the other hand, DCPD can produce a product with a purity of 90 % or more by distillation. DCPD Scheme 1 can be easily cracked by heat to generate CPD. CPE can be obtained by selective hydrogenation of CPD. In this production method, equimolar amounts of car- CPE is a very useful compound in introducing a cyclic C5 bon dioxide gas and water are generated. Since CPN unit in organic synthesis and can be easily converted to has an azeotropic composition with water, the unit energy an alcohol or ketone such as cyclopentanol (hereinafter consumption for purification is relatively large, and loss CPL) or cyclopentanone (hereinafter CPN). Also, the of CPN itself cannot be ignored. Particularly in the ether can be easily synthesized by addition of alcohol. case of electronic material applications, the specifica- CPN is produced worldwide at 26,000 Mt/yr tion of moisture is very strict, and the loss at the time of (FY 2015) and is widely used as a raw material for purification significantly increases. Moreover, this methyl dihydro jasmonate, which is the main compo- reaction is generally operated by a batch method. So nent of jasmine note, and as a solvent for electronic ma- in order to perform mass production, installation of a terials14). large-scale batch reactor is required, and there are many On the other hand, cyclopentyl methyl ether (herein- additional facilities which concern on processes other after CPME) is an entirely new type of ether developed than reaction. Furthermore, if the demand exceeds the mainly as a solvent for fine organic synthesis15),16). production capacity, it may be difficult to enhance the The production route of CPN and CPME starting from capacity. This is due to the need to install a large DCPD is shown in Fig. 2. number of equipment including ancillary equipment This is a production route for high value-added other than the reactor which is the main body. chemicals, which is completely different from conven- Furthermore, due to the problem of corrosion by adipic tional DCPD applications. Here, we will introduce acid, corrosion resistant materials must be used for the mainly the topics related to the catalyst obtained by the reactor body, which leads to increased investment in technical study for establishing this manufacturing equipment. route, and outline the future issues of the entire C5 In the view of these circumstances, the authors chemicals. focused on the fact that CPN has a 5-membered ring

J. Jpn. Petrol. Inst., Vol. 62, No. 6, 2019 248 structure, and devised a unique manufacturing route introduced in production facilities. In addition, a Ni- composed of 4 step reactions (Schemes 2 to 5)20). based catalyst is used to maintain a high raw material conversion rate. When the reaction is simply carried out with only the catalyst, hydrogenation proceeds more than necessary and a large amount of CPA is produced. Therefore, in order to achieve high selectivity to CPE, lopentene special additives are used in the liquid phase batch pro- P cess. On the other hand, in the gas phase continuous method, et 2 CPD obtained by the thermal clacking is introduced as it is in the form of gaseous into the selective hydroge- lopentene nation step without cooling and liquefying. This P means that the process of holding a large amount of Scheme 2 CPD in liquid can be fundamentally excluded from the process. Therefore, the commercialization of the gas

＋2 phase continuous method leads to avoid the Diels-Alder reaction above-mentioned, and has very important roenton tlst meaning also from the viewpoint of process safety. A lopentene large number of patents have been reported for metal P catalysts such as Ni-based and Pd-based hydrogenation catalysts for use in the gas phase continuous process, Scheme 3 but they have not been put to commercial use. This is due to the fact that a catalyst life is not enough to with- stand commercial operation. The authors investigated catalyst deactivation in gas phase selective hydrogena- ＋ 2 52),53) tlst tion to solve this problem . A bench scale reactor lopentnol was used to perform selective hydrogenation of CPD P using 0.5 wt% Pd/Al2O3 as a catalyst. When the oper- ation time reached 100 h, a decrease in catalyst activity Scheme 4 and an increase in CPE selectivity were observed at the same time as the point of maximum temperature in re- action tube (Hot Spot) disappeared in the temperature distribution in the reaction tube (Figs. 3 and 4)52). From the characterization of the spent and virgin cat- eroenton tlst alysts, model experiments with the spent catalyst after regeneration treatment, and the results of continuous operation using feedstocks of different purities, it is re- ＋2 vealed that the sulfur-containing impurities in the feed- stock are the main cause of the catalyst deactivation. lopentnone A conceptual diagram of the catalyst deactivation PN mechanism is shown in Fig. 553). By the way, in the production of CPN by the de- Scheme 5 hydrogenation reaction of CPL shown in Scheme 5, a fixed bed continuous reaction is adopted and a Cu/ZnO As for the production method of CPE by selective catalyst is used. When a Cu/ZnO catalyst is used for hydrogenation of CPD shown in Scheme 3, various the dehydrogenation reaction, activation treatment by methods such as liquid phase batch method and gas hydrogen reduction is generally performed before the phase continuous method have been studied21)～51), but start of the operation, but in the case of CPL dehydro- only the process by the liquid phase batch method has genation reaction, the hydrogen reduction significantly been applied to commercial production. This process reduces the selectivity. If CPL dehydrogenation is involves holding a large amount of liquid CPD. performed without hydrogen reduction, although some Liquid CPD is easy to start oligomerization (Diels- initial induction period exists, it has been confirmed Alder reaction) accompanied by heat, and is rapidly that stable operation can be performed for 300 h with progressed when it reaches a certain temperature, which high selectivity after the induction period20). may lead to a runaway reaction. Therefore, in order to Figure 6 shows the time course of catalyst activity ensure safety, a very complex interlock system has been and selectivity in continuous operation for 300 h.

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The results of catalyst characterization have revealed of the operation is caused by the decrease in aldol con- that the active components present in the form of CuO densation activity of CPN which is the main side reac- just after catalyst preparation are reduced to Cu by the tion. CPL dehydrogenation reaction itself. In addition, it is also clear that the reduction of the specific surface area 3. Development of the Process for Manufacturing is suppressed when the reaction is performed without CPME the hydrogen reduction, while the specific surface area of the catalyst is significantly reduced when the hydro- CPME is an entirely new type of ether, developed gen reduction is performed. Furthermore, as a result primarily as a solvent for fine organic synthesis. of examination by model experiments etc., it is clear Unlike tetrahydrofuran, CPME has excellent energy- that the gradual decrease in activity at the initial stage saving and safety characteristics; facile separation and recovery from water easy, a small latent heat of vapor- ization, and negligible generation of peroxide. Therefore, it is an environmentally friendly solvent and

(a) time on stream is 4 h, (b) time on stream is 59 h and (c) time on stream is 100 h. Fig. 4● Change of Relative Catalytic Activity (solid line) and Fig. 3● Change of Temperature Profiles of Reactor in the Selective Relative Selectivity (broken line) in the Selective Hydrogenation of CPD Using DCPD with 95 % Purity as Hydrogenation of CPD Using DCPD with 95 % Purity as Feedstock Feedstock

(a) virgin catalyst to Spt. Cat. (b) Spt. Cat. regenerated with alkali treatment. (c) Spt. Cat. regenerated by calcination. (d) Spt. Cat. regenerated with alkali treatment and calcination.

Fig. 5● Schematic Image of Deactivation and Regeneration Mechanisms of Pd/γ-Al2O3 Catalyst Based on the Examinations

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Table 3 Comparison of Physical Properties of CPME and Other Ethers

Ethers Cyclopentyl methyl ether (CPME) Tetrahydrofuran (THF) Diethyl ether e

Chemical structure

Density (20 °C) [g cm–3] 0.86 0.89 0.71 Vapor specific gravity (air＝1) [-] 3.45 2.49 2.56 Boiling point [°C] 106 65 34.6 Heat of vaporization (at boiling point) [kJ kg–1] 289.7 410.7 360.5 Solubility in water (23 °C) [g 100 g–1] 1.1 ∞ 6.5 Water solubility in ether (23 °C) [g 100 g–1] 0.3 ∞ 1.2 Flash point [°C] －1 －14.5 －45

NaI must be treated as waste. Also, additional equip- ment for this operation is required. Furthermore, since the raw material CPL is produced by hydrogenating CPN, the raw material is expensive. For these reasons, production of CPME by the reaction of Scheme 6 has not been economically feasible. Therefore, in order to develop a production method that can withstand mass production, the authors devised a production method by addition reaction of methanol (hereinafter MeOH) shown in Scheme 7 using CPE as a starting material16). Fig. 6● Change of Relative Catalytic Activity (solid circle) and Relative Selectivity (open circle) in the Life Test of Cu1.12Zn e Catalyst without Reduction tlst e its safety is suitable for university or college experi- mental curriculum from the viewpoint of ensuring stu- P P dent safety. The difference in physical properties be- tween CPME and other common ethers is shown in Scheme 7 Table 354). Being ethers having these properties, they are widely The authors examined the application of strongly used as reaction solvents for alkylation, silylation, acidic ion exchange resin to gas phase continuous reac- organometallic reactions, Grignard reactions, optically tion. As a result, it has been found that strongly acidic selective reactions, reduction reactions, polymeriza- ion exchange resins exhibit good catalytic performance tions, etc.55)～61). CPME was conventionally produced and are sufficiently applicable to gas phase continuous by a synthesis method using CPL as a starting material reactions62). However, in order to develop a process (Scheme 6). that can withstand commercial operation, it is necessary to confirm whether the catalyst life is economically suf- e ficient. Therefore, the authors examined the catalyst N, eI stability and deactivation factors in the CPME synthesis reaction by fixed bed gas phase continuous reaction cat- 63) 110 alyzed by ion exchange resin . From the results of 0. P experiments using an apparatus visualizing the inside of the reaction tube and the results of continuous operation Schem 6 using raw materials with different purities, it becomes clear that C5 diolefins contained in CPE as the raw Since this reaction is carried out in a batch process, it material are causal substances of the catalyst deactiva- is necessary to introduce a large-scale reaction kettle for tion. Figure 7 shows a schematic diagram of the ex- mass production. In addition, the reaction mixture perimental device that visualizes the inside of the reac- after reaction termination must be washed with water to tion tube, and Fig. 8 shows the change with time of the remove by-produced NaI, but since it is an equimolar length of the colored area of the catalyst layer measured reaction, CPME generated and equimolar amount of using the visualized experimental device. The change

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Fig. 7● Schematic Drawing of the Lab. Scale Reactor for the Accelerated Life Test

Fig. 10● Schematic Drawing of the Catalyst Deactivation Mechanism with C5 Diolefins Polymerization

the tar covering the catalyst surface is formed by the polymerization of C5 diolefins. Figure 10 shows a schematic of the assumed catalyst deactivation mecha- nism. Based on the findings obtained through these studies, we established a process for removing impurities in the raw material and conducted a final demonstration test of the catalyst life. As a result, the target 1000 h of Fig. 8● Change in the Length of Colored Catalyst Bed in the Accelerated Life Test stable operation was achieved.

4. Future Challenges for the Development of the C5 Chemicals Business

The authors commercialized the CPN manufacturing process, using DCPD as a starting material, in 2003, and the CPME manufacturing process in 2005 respec- tively. The two processes are still running well and product demand is also showing strong growth. On the other hand, DCPD, which is a raw material, is produced by the extractive distillation process described in Chap. 1., and the production amount is determined in consideration of the supply and demand balance includ- Fig. 9● Change in Relative Yield (solid line) and C5 Diolefins ing IPM and Pips. This is because the production Leakage (broken line) in the Accelerated Life Test amounts of the three types of C5 chemicals are limited by the concentration in C5F, the raw material, and can with time of the specific yield of CPME and the C5 di- be said to be the fate of the distillation process. olefins leakage are shown in Fig. 9. The length of the Therefore, the current situation is that the production colored area of the catalyst bed increased linearly with volume of C5 chemicals does not always match the de- time on stream (Fig. 8). On the other hand, the rela- mand volume. tive yield slowly decreased with time on stream, whereas Recently, some efforts are under way to overcome the diolefin leakage increased (Fig. 9), until the opera- this situation. For example, a process of actively con- tion time reached 21 h, when 86 % of the catalyst bed trolling the balance between supply and demand of was colored. These observations suggest that polym- three types of C5 chemicals by utilizing the C5 raf- erization of C5 diolefins proceeded rapidly on the ion finates which has not been utilized conventionally, and exchange resin because of its strong acid cites. utilizing by-produced hydrogen has been studied64). Furthermore, from the fact that the tar deposited on Also, studies on individual unit operations of the pro- the catalyst is soluble in CPA and the results obtained cess are being conducted65)～68). On the other hand, by pyrolysis gas chromatography, it is concluded that studies are also underway to convert linear and/or

J. Jpn. Petrol. Inst., Vol. 62, No. 6, 2019 252 branched C5 hydrocarbons into DCPD69). chemical by the present extractive distillation may Petrochemical complexes in Japan are mainly com- become difficult in terms of securing raw materials. posed of ethylene cracker, and use ethylene and other As mentioned in Chap. 1., C5 chemicals produce a wide by-products (propylene, aromatic compounds, etc.) to variety of unique products. Future technological inno- produce various petrochemical products. In ethylene vation is also expected for the C5 chemicals manufac- crackers in Japan, almost all the raw materials for pro- turing process that supports the basis of variable and ducing ethylene are naphtha (some of them are de- attracting C5 derivatives. signed to use ethane, propane and butane), and their cost competitiveness largely depends on naphtha price. 5. Conclusion On the other hand, in the West, there are many crackers that use raw materials other than naphtha. Figure 11 As part of the comprehensive utilization of C5 chem- shows the composition of the petrified material in icals, the authors have been working on the develop- Japan, the US and Europe70). ment of methods for producing high value-added prod- The product distribution of the ethylene crackers is ucts, using DCPD as a starting material. As a result, highly dependent on the source. The relationship we commercialized a new production method of CPN between raw materials for ethylene production and and a production method of CPME. As we proceeded product distribution is shown in Table 471). with technological development, we were able to obtain When ethylene is produced using ethane as a raw various findings on catalyst life in particular. Progress material, the amount of C5F generated is reduced to in developing unique products and their manufacturing about 1/10 as compared to the case where ethylene is methods is expected in the future. On the other hand, produced using naphtha as a raw material. On the other since DCPD, which is a raw material, is co-produced by hand, when ethylene is produced using ethane as the IPM and Pips in an extractive distillation process, it is raw material, its breakeven point is said to be over- difficult to perfectly match supply and demand. In whelmingly better than when ethylene is produced addition to downstream development of DCPD, there is using naphtha as the raw material72). In the future, as also a need to strengthen competitiveness through tech- ethane cracker becomes mainstream, production of C5 nological innovation in the C5 chemical manufacturing

Fig. 11 Comparison of Feedstocks for Ethylene among Japan, United States and Europe in 2011

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Table 4 Comparison of Products Distribution among the Various Feedstocks for Ethylene Production

Feedstock Ethane Propane n-Butane Full range naphtha Sevierity of operation - - - High Middle Low Yield [wt%]

H2 4.1 1.5 1.2 0.9 0.9 0.8 CH4 2.9 25.0 19.6 16.5 14.6 12.5 C2H2 0.4 0.5 0.8 1.1 0.7 0.4 C2H4 54.1 37.4 39.8 32.8 30.0 26.7 C2H6 35.0 4.1 4.0 3.3 3.9 4.0 C3H4 0.1 0.5 1.1 1.1 0.9 0.6 C3H6 0.8 12.5 15.5 13.8 16.7 17.2 C3H8 0.2 6.3 0.2 0.3 0.4 0.5 C4H6 1.1 4.0 4.0 4.6 4.7 4.5 C4H8 0.2 0.9 1.8 3.5 5.0 6.5 C4H10 0.2 0.1 5.0 0.2 0.4 0.8 C5 fraction (C5F) 0.3 1.7 1.4 2.6 3.7 5.2 C6-C8 non aroma 0.4 0.3 1.1 0.6 2.2 5.8 Benzene 0.3 2.7 1.9 7.1 5.3 4.1 Toluene 0.1 0.6 0.5 2.4 4.4 4.3 C8 aromatics - 0.6 0.4 0.7 1.7 2.0 C9～ heavy (b.p. 200 °C) - 0.9 0.9 0.7 1.6 1.9 Cracked fuel 0.1 0.5 0.9 4.4 3.1 2.2 Total 100.0 100.0 100.0 96.4 100.0 100.0 process as the upstream. Through these efforts, I 9) Toho Sekiyu Jushi, Jpn. Kokai Tokkyo Koho JP1981-106912 (1981). would like to greatly expect further development of the 10) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2015-19547 (2015). more attractive C5 chemical business. 11) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2001-48924 (2001). 12) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2001-213944 (2001). Acknowledgment 13) Hitachi Chemical Co., Ltd., Yuki Gosei Kagaku Kyokaishi, 28, H. M. would like to express heartfelt thanks to Dr. N. (12), 1280 (1970). 14) QYR Chemical & Material Research Center, “Global Kogoshi for his dedication to a lot of experiments to Cyclopentanone Industry 2016 Market Reserarch Report,” make clear the mechanism of the catalyst deactivation (2016), pp. 1-22. described in Chap. 3. He also would like to gratitude 15) The Society of Synthetic Organic Chemistry, The Japanese so much to Ms. Misako Asada, team leader of analytical Society for Process Chemistry (ed.), “Kigyoukennkyuusyatachi team, basic technology laboratory of Zeon no Kandou no Syunkan̶Monozukuri ni Kakeru Yume to ” ’ Jounetsu, Kagaku-Dojin Publishing Co., Inc., Tokyo (2017), Corporation s Research & Development Center, who p. 189. gave me dedicated assistance in various analysis to 16) Miki, H., PETROTECH, 41, (9), 701 (2018). advance the series of research described on this review. 17) Rhone-Poulenc Chimie, Jpn. Kokai Tokkyo Koho, JP1995- H. M. would also like to thank Prof. Y. Sakata of 25809 (1995). Yamaguchi University for his advice on consolidating 18) Rhone-Poulenc Chimie, Jpn. Kokai Tokkyo Koho, JP1995- 33703 (1995). this review. 19) Zeon Corp., Jpn. Kokai Tokkyo Koho, JP2007-191445 (2007). 20) Miki, H., J. Jpn. Petrol. Inst., 62, (6), 282 (2019). References 21) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2006-206536 (2006). 22) BASF, U.S. Pat. 6153804 (2000). 1) IHS Chemical Special Reports, “C5 Value Chain Study: From 23) Lassau, C., Dang V. Q., Hellin, M., Hydrocarbon Processing, Cracker to Key C5 Derivative Applications for Isoprene, 52, (8), 105 (1979). DCPD and Piperylene,” (2015). 24) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2000-053597 (2000). 2) The Japan Petroleum Institute (ed.), “Petrochemical 25) Zeon Corp., Jpn. Kokai Tokkyo Koho JP2004-175685 (2004). Processes,” Kodansha Scientific Ltd., Tokyo (2001), p. 81. 26) Bayer, Jpn. Kokoku Tokkyo Koho JP1981-81001292 (1981). 3) Elkin, M. L., “A Private Economics Program No. 28 A-1, 27) Kaneka Corp., Jpn. Kokoku Tokkyo Koho JP1977-33627 Isoprene,” Stanford Research Institute, (1971), pp. 4-5. (1977). 4) Takao, S., “Process Handbook Vol. 1,” B, 73/12, The Japan 28) Tonen Corp., Jpn. Kokoku Tokkyo Koho JP1993-13703 (1993). Petroleum Institute, Tokyo (1973). 29) Shell, U.S. Pat. 2360555 (1944). 5) Zeon Corp., Jpn. Kokai Tokkyo Koho JP1975-21088 (1975). 30) Du Pont, U.S. Pat. 2584531 (1952). 6) Zeon Corp., Jpn. Kokai Tokkyo Koho JP1999-171913 (1999). 31) Esso Research and Engineering Co., U.S. Pat. 2793238 (1957). 7) Kolon Industry, Jpn. Kouhyou Tokkyo Koho JP2018-526482 32) Ruhrchemie, U.S. Pat. 2887517 (1959). (2018). 33) Uniroyal Inc., U.S. Pat. 3408415 (1968). 8) Hitachi Chemical Co., Ltd., Jpn. Kokai Tokkyo Koho JP1979- 34) BP p.l.c., G.B. Pat. 919702 (1959). 19440 (1979). 35) Song, Y., Lin, X., Guan, Y., Wu, G., Speciality Petrochemicals,

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26, (2), 18 (2009). 53) Miki, H., J. Jpn. Petrol. Inst., 61, (4), 227 (2018). 36) Wang, W.-J., Li, H.-X., Deng, J.-F., Appl. Catal. A: Gen., 203, 54) Zeon Corp., “Technical Data Book of Cyclopentyl Methyl (2), 293 (2000). Ether,” (2018), p. 2. 37) Liu, C., Xu, Y., Liao, S., Yu, D., J. Molecular Catal. A: Chem., 55) Kimmer, K. L., Robak, M. T., Ellman, J. A., J. Am. Chem. 157, 253 (2000). Soc., 131, (25), 8754 (2009). 38) Wang, W.-J., Li, H.-X., Deng, J.-F., J. Chem. Tech. Biotech., 56) Saito, N., Yamazaki, T., Sato, Y., Chem. Lett., 38, (6), 594 75, (2), 147 (2000). (2009). 39) Wang, W.-J., Li, H.-X., Xie, S.-H., Li, Y.-J., Deng, J.-F., Appl. 57) Fei, Z., Wu, Q., Zhang, F., Cao, Y., Liu, C., Shieh, W., Xue, S., Catal. A: Gen., 184, (10), 33 (1999). McKenna, J., Prasad, K., Prasha, M., Baeschlin, D., Namoto, 40) Wang, W.-J., Qiao, M.-H., Li, H.-X., Deng, J.-F., J. Chem. K., J. Org. Chem., 73, 9016 (2010). Tech. Biotech., 72, (3), 280 (1998). 58) Hayashi, M., Nakamura, S., Angew. Chem. Int. Ed., 50, 2249 41) Wang, W.-J., Qiao, M.-H., Li, H.-X., Dai, W.-L., Deng, J.-F., (2011). Appl. Catal. A: Gen., 168, (1), 151 (1998). 59) Shimada, T., Suda, M., Nagano, T., Kakiuchi, K., J. Org. 42) Wang, W.-J., Qiao, M.-H., Li, H., Deng, J.-F., Appl. Catal. A: Chem., 70, 10178 (2005). Gen., 166, (2), L243 (1998). 60) Tanaka, Y., Mino, T., Akita, K., Sakamoto, M., Fujita, T., J. 43) Wang, W.-J., Qiao, M.-H., Yang, J., Xie, S.-H., Deng, J.-F., Org. Chem., 69, 6679 (2004). Appl. Catal. A: Gen., 163, 101 (1997). 61) Yamamoto, T., Abe, M., Takahashi, Y., Kawata, K., Kubota, K., 44) Fígoli, N. S., Barberis, J. P., L’Argentière, P. C., J. Chem. Tech. Polymer J., 35, (7), 603 (2003). Biotech., 67, (1), 72 (1996). 62) Kogoshi, N., Miki, H., 61st Annual Meeting of Jpn. Petrol. 45) Hirai, H., Komatsuzaki, S., Toshima, N., Bull. Chem. Soc. Jpn., Inst., Tokyo, 2018, A01. 57, (2), 488 (1984). 63) Miki, H., J. Jpn. Petrol. Inst., 62, (4), 173 (2019). 46) Černeny, L., Vopatová, J., Ruzička, V., Reaction Kinetics 64) Zeon Corp., WO2018/163828 (2018). Catal. Lett., 19, 223 (1982). 65) Zeon Corp., WO2016/121377 (2016). 47) Gagarin, S. G., Makar’yev, S. S., Krichko, A. A., Petroleum 66) Zeon Corp., WO2017/169195 (2017). Chemistry U.S.S.R., 22, (4), 189 (1982). 67) Zeon Corp., WO2018/181349 (2018). 48) Gryaznov, V. M., Ermilova, M. M., Gogua, L. D., Orekhova, N. 68) Zeon Corp., WO2018/180210 (2018). V., Morozova, L. S., Bull. Academy Sci. USSR Div. Chem. Sci., 69) Exxon Mobile Patents Inc., Jpn. Kohyou Tokkyo Koho, 30, (4), 672 (1981). JP2018-532794 (2018). 49) Makar’evc, S. S., Zhuzhikova, G. A., Solid Fuel Chem., 13, (1), 70) Japan Petrochemical Industry Assoc., “Shalegas ga Wagakuni 88 (1979). ni Oyobosu Eikyou ni Kansuru Chousakennkyuukekka ni 50) Ermilova, M. M., Basov, N. L., Smirnov, V. S., Rumyantsev, A. tsuite,” Tokyo (2013), p. 4. N., Gryaznov, V. M., Bull. Academy Sci. USSR Div. Chem. Sci., 71) The Japan Petroleum Institute (ed.), “Petrochemical 28, (8), 1633 (1980). Processes,” Kodansha Scientific Ltd., Tokyo (2001), p. 29. 51) Weng, H. S., Engenberger, G., Butt, J. B., Chem. Eng. Sci., 30, 72) Fuji Chimera Research Inst. Inc., “Shalegas Kakumei ni yoru 1341 (1975). Kagakusangyou no Shoraizou,” Tokyo (2014), p. 17. 52) Miki, H., J. Jpn. Petrol. Inst., 61, (1), 37 (2018).

要 旨

C5ケミカルの総合利用を指向したジシクロペンタジエンを出発原料とする高付加価値製品の生産技術開発

三木 英了

日本ゼオン（株）総合開発センター，210-9507 川崎市川崎区夜光1-2-1

C5 ケミカル（イソプレン，ジシクロペンタジエン，ピペリ シクロペンテンの製造用触媒の活性低下要因に関する研究，シ レン）は，ナフサクラッカーで副生する C5留分を原料として， クロペンテンを出発原料としたシクロペンチルメチルエーテル 抽出蒸留プロセスにより同時生産される。著者らは，これら 合成用触媒の劣化要因に関する研究，シクロペンタノールを出 C5 ケミカルの総合利用を目的として，ジシクロペンタジエン 発原料としたシクロペンタノン合成用触媒の活性変動要因に関 を出発原料とするシクロペンタノンの新製造法とシクロペンチ する研究について述べる。また，C5 ケミカル事業の発展に不 ルエーテルの製造法を開発した。本報では，技術開発の中で得 可欠な C5 ケミカル自体の製造技術開発について，最近のト られた触媒劣化に関する技術的な知見を紹介する。具体的に ピックスを概観する。 は，シクロペンタジエンを出発原料とした気相水素化法による

J. Jpn. Petrol. Inst., Vol. 62, No. 6, 2019