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Methanol Production – a Technical History a Review of the Last 100 Years of the Industrial History of Methanol Production and a Look Into the Future of the Industry

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Methanol Production – a Technical History a Review of the Last 100 Years of the Industrial History of Methanol Production and a Look Into the Future of the Industry http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3), 172–182 JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com Methanol Production – A Technical History A review of the last 100 years of the industrial history of methanol production and a look into the future of the industry By Daniel Sheldon Peligot. At a similar time, commercial operations using Johnson Matthey, PO Box 1, Belasis Avenue, destructive distillation were beginning to operate (2). Billingham, Cleveland TS23 1LB, UK There are many parallels between the industrial production of methanol and ammonia and it was the Email: [email protected] early development of the high pressure catalytic process for the production of ammonia that triggered investigations into organic compounds: hydrocarbons, Global methanol production in 2016 was around alcohols and so on. At high pressure and temperature, 85 million metric tonnes (1), enough to fill an Olympic- hydrogen and nitrogen will only form ammonia, however sized swimming pool every twelve minutes. And if all the the story is very different when combining hydrogen global production capacity were in full use, it would only and carbon oxides at high pressure and temperature, take eight minutes. The vast majority of the produced where the list of potential products is lengthy and almost methanol undergoes at least one further chemical all processes result in a mixture of products. Through transformation, more likely two or three before being variations in the process, the catalyst, the conditions, turned into a final product. Methanol is one of the first the equipment or the feedstock, a massive slate of building blocks in a wide variety of synthetic materials industrial ingredients suddenly became available and a that make up many modern products and is also used race to develop commercial processes ensued. as a fuel and a fuel additive. This paper looks at the last 100 years or so of the industrial history of methanol The First Drops production. Early research into methanol production quickly Introduction focused on copper as a prime contender for the basis of a catalytic process to methanol, with Paul Sabatier Methanol has been produced and used for millennia, and Jean-Baptiste Senderens (3) discovering in 1905 with the ancient Egyptians using it in the embalming that copper effectively catalysed the decomposition process – it was part of the mixture of substances of methanol and to a lesser extent its formation. A produced in the destructive distillation (pyrolysis) of lot of the early testing looked at what catalysts could wood. However, it was not until 1661 that Robert Boyle effectively destroy methanol, assuming they would produced pure methanol through further distillation, be equally as effective under alternative conditions at and only in 1834 was the elemental composition forming methanol. Following the start of large scale determined by Jean-Baptiste Dumas and Eugene ammonia production in Germany during 1913, the 172 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) pace of research picked up and in 1921 Georges Patart his work on the first industrial ammonia synthesis patented the basis of a high pressure catalytic process catalyst. The high pressures benefitted conversion that used a variety of materials including copper (along to methanol and to achieve sufficiently quick reaction with nickel, silver or iron) for methanol synthesis (4). rates, high temperatures also had to be used. Further A small experimental plant was later built using this increases in temperature would have drastic effects process in Patart’s native France, near Asnières (5). on the selectivity and equilibrium, so conditions were selected to be a compromise. Methanol production The German Effort began on 26th September 1923 at the Leuna site (7). The wood-based processes were always very limited Early Catalysts in scale and it was 1923 before production could be considered ‘industrial’ with a catalytic process The subsequent research into the catalyst was developed by Mathias Pier at Badische Anilin- & extensive, with the list of possible candidates covering Sodafabrik (BASF), Germany (Figure 1). large swathes of the periodic table, from antimony to The BASF process produced methanol from synthesis zirconium, bismuth to uranium (itself a popular catalyst gas (syngas), which at the time was a mixture of of the time) (5, 8). Given the extensive testing, it is hydrogen and carbon monoxide. The process works by perhaps unsurprising that in the list can be found many the following reactions: of the components that make up the modern catalysts used in methanol plants in the 21st century. CO + 2H D CH OH ΔH = –90.6 kJ (i) 2 3 Initially, iron was to be used for methanol production (as with ammonia production), but this along with nickel was CO2 + 3H2 D CH3OH + H2O ΔH = –49.5 kJ (ii) phased out in successive patent applications until the requirement for the process to be ‘completely excluding CO + H2O D CO2 + H2 ΔH = –41.2 kJ (iii) iron from the reaction’ was included in the mid 1920s (9). Methanol formation (Equations (i) and (ii)) is favoured During the early years there was a lot of effort looking by low temperatures and high pressures. All three at other combinations of carbon, hydrogen and oxygen. equilibrium reactions occur simultaneously, although it One major application was Fischer-Tropsch reactions: is common to only consider two of the three to simplify the creation of straight chain saturated hydrocarbons, any analysis, as it can be seen that Equations (ii) and for example for fuels. This is readily catalysed by (iii) combined are the same as Equation (i). iron at similar conditions to methanol synthesis. With The BASF process operated at above 300 atm and early iron-containing methanol synthesis catalysts, 300–400°C, using a zinc chromite (Cr2O3-ZnO) catalyst it was found that the iron would react with the carbon developed by Alwin Mittasch (6), about a decade after monoxide to form iron carbonyl, which decomposes at high temperatures to iron metal. It was therefore easy to transform the catalyst into one much more efficient at making hydrocarbons than methanol; reactions that are even more exothermic and not equilibrium limited, hence at risk of thermal runaway. The catalyst is not the only source of iron in such processes, with the obvious choice for construction of the early reactor vessels being steel, which itself contains iron. Many of the early plants were therefore either lined or made of non-ferrous metals, such as copper, silver or aluminium (10). Early Processes The equilibrium limitations of the methanol formation Fig. 1. First shipment of synthetic methanol from BASF reactions (Equations (i)–(iii)), especially under the Leuna, 1923 (Courtesy of BASF Corporate Archives, early operating conditions, were such that conversion Ludwigshafen/Rhine, Germany) to methanol in a single pass through a reactor was 173 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) very low. To overcome this, the gas had to be recycled year of methanol in new, catalysed, high-pressure over the catalyst a number of times. Each time, the gas processes (13). is cooled to condense any product methanol and the consumed reactants are replaced with fresh synthesis Catalyst Developments gas. The gas is rarely pure hydrogen and carbon monoxide, and any non-reacting species, such as Early on it was recognised that the most effective methane or nitrogen, introduced through the fresh gas catalysts used a combination of copper and another supply accumulate in such a loop, so a small fraction metal oxide, but the synthesis section and catalyst of the gas must be purged, also losing some reactants. remained very similar for about 25 years. Eugeniusz Figure 2 shows the basic components of a methanol Błasiak filed a patent in 1947 for a new catalyst synthesis loop, which are still used today. containing copper, zinc and aluminium, manufactured The interchanger is a more modern concept, reducing by co-precipitation (14). The patent claimed a method energy consumption by using the hot gas exiting the for producing a “highly active catalyst for methanol converter to heat the inlet gas. Early patents (11) show synthesis” and further laboratory testing over the a lot of the aspects of modern methanol production, following decades proved this. including the recycle loop and the use of a guard The biggest impediment to the use of copper catalyst bed of additional catalyst or absorbent to remove was the rate of poisoning by sulfur compared to the “traces of substances deleterious to the reaction”, zinc chromite catalysts typically used in those plants. early versions tending to be copper based. The loss The syngas generation process had moved on from of reactants through the purge was also considered coal and coke feeds to natural gas reforming, and in early processes, with Forrest Reed filing a patent it was accepted that sulfur in the feed would poison in 1932 (12) for recycling the purged gas through an the reforming catalyst and reduce the activity. The additional reactor in a loop with high concentrations of reformers were therefore run at close to atmospheric non-reacting components, complete with condensation pressure to prevent hydrocarbon cracking over the and separation. This approach is now used to revamp poisoned catalyst, which would cover the surface in a and add capacity to modern methanol plants. layer of carbon and remove all residual activity. Around The general concept spread rapidly and plants could this time, work was underway to create an alkalised be found around the world by the end of the 1920s reforming catalyst which was protected against carbon producing a total of around 42,000 metric tonnes per deposition and could therefore run at elevated pressure (initially 14 atm, but soon after up to 35 atm) (15).
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