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50 | Chemistry World | May 2011 www.chemistryworld.org

0511CW - Fischer-tropsch.indd 50 19/04/2011 07:46:00 Liquid assets Nazi Germany and apartheid South Africa helped found the Fischer–Tropsch synthetic fuel industry. Andy Extance discovers how it is now adapting to polish its reputation

On 27 July 1914, the day before steam and to make In short Austria-Hungary invaded Serbia and and carbon dioxide. A 2:1 ignited the first world war, the Kaiser-  The Fischer–Tropsch hydrogen:carbon monoxide volume Wilhelm Institute for Research process was developed mixture they called synthesis gas, or opened in Mülheim, Germany. Franz to turn plentiful coal into , avoided contaminating their Fischer, its director, initially hoped oil and liquid fuels when catalysts with carbon. to perform basic research on coal – supplies were restricted These efforts didn’t pay off an abundant resource in Germany.  The catalytic process before peace broke out in 1919, but However, it soon became clear that turns syngas (CO and Fischer and Tropsch persevered, the country did not have enough of H2) into longer chain progressively replacing cerium, another resource – oil – essential to fuels cobalt or oxide catalysts power warfare in the 20th century.  New catalysts and previous processes had used. ‘It The programme at the institute microchannel reactors was a hit-and-miss process with the therefore shifted towards converting have taken the technology catalysts, but they finally settled on coal to petroleum, ultimately into new applications cobalt derivatives,’ Stranges tells leading to a process that has been  Moving from coal to Chemistry World. The pair also had exploited ever since. In that time the waste or even to manage what the historian calls Fischer–Tropsch process, as it has seawater as fuel sources the ‘tremendous amounts of heat’ become known, has been associated could help reduce overall generated by making with two of the 20th century’s most emissions in this way. ‘It was essential that they controversial political regimes. But had the temperature under control today its continuing use producing so they could carry out the reaction fuels from gas and renewable without worrying about apparatus feedstocks sees the process maturing deteriorating,’ he says. far beyond these links. By November 1935, less than ‘Fischer and Tropsch were three years after Germany’s Nazi primarily concerned with putting government came to power and Germany’s vast coal reserves to the initiated a push for petroleum best possible use,’ explains chemical independence, four commercial- historian Anthony Stranges from sized Fischer–Tropsch plants were Texas A&M University in Galveston, under construction. Soon, the first US. Stranges has collected records Franz Fischer (left) and four plants expanded to become nine, of the scientists’ work investigating Hans Tropsch were the whose production capacity peaked at a process that catalytically first to convert CO and H2 4.1 million barrels annually by 1944. hydrogenated carbon monoxide from coal into liquid fuels Fischer–Tropsch processes provided produced by coal to give hydrocarbons. Previous efforts to make chemicals from carbon monoxide had been hampered by its decomposition to carbon dioxide and solid carbon that deposited onto and deactivated catalysts.

Birth of a process Fischer first worked with Hans Tropsch on reducing carbon monoxide using excess hydrogen gas. Using high-temperature steam they could alter the proportions of the two gases in mixtures of volatile components baked out of coal. This ‘ shift’ reacts MAX PLANCK INSTITUTE OF COAL RESEARCH COAL OF INSTITUTE PLANCK MAX www.chemistryworld.org Chemistry World | May 2011 | 51

0511CW - Fischer-tropsch.indd 51 19/04/2011 09:46:38 Synthetic fuels

Into the 21st century At the same time, interest in fuel e fficiency was driving a shift from , which contains more unsaturated hydrocarbons and aromatic compounds, to diesel, which is a paraffinic, or saturated, fuel. Shortly after returning to Fischer– Tropsch, Shell realised that this was going on and that it meant rethinking the feedstock it used. ‘For a lower hydrogen content fuel like gasoline it makes more sense if you start from a hydrogen-poor synthesis gas, typically derived from a coal source,’ Mesters says. ‘If you start making synthesis gas from then it is hydrogen-rich. It makes sense to convert that into diesel, which has a higher hydrogen content.’ As a result, Shell worked through the 1980s to develop their gas-to-liquids (GTL) technology, which nonetheless retained many similarities to the German scientists’ original process, including a cobalt catalyst. In 1993 it an estimated 9 per cent of German CTL plants. These became all Rentech’s latest plants began operating its first commercial fuels during the second world war, the more important in the face of capture surplus heat GTL plant in Bintulu, Malaysia, and 25 per cent of its automotive fuel. economic sanctions over South from the process to which continues to produce around Africa’s racist apartheid policies, generate electricity 14 000 barrels of synthetic fuel a day. Forgotten technology Stranges notes. ‘They had no choice Shell has continued to develop The ability to fight on that this – they were cut off from other its process, Mesters explains, and provided Germany – despite limited supplies.’ is today in the process of starting oil supplies – initially attracted the Another company to take up up the first 140 000 barrel-per-day post-war US government’s attention, Fischer and Tropsch’s process at Fischer–Tropsch GTL plant. The and in turn significant investment. that time was Denver, Colorado’s plant in Ras Laffan Industrial City, But by the early-to-mid 1950s oil Rentech, which emerged from the Qatar, called ‘Pearl GTL’, is a joint production had expanded so much US National development by Qatar Petroleum that it made Fischer–Tropsch fuels Laboratory in 1981. ‘The original idea and Shell. Expected to cost $18-19 uncompetitive, and most major was to focus on coal-to-liquids using billion (£11-12 billion), it will be development work and commercial iron catalyst technology, reasonably the world’s largest source of GTL operations on the process ceased. similar to what is doing in products, providing around 10 times One exception was in South Africa, South Africa, because the US has the entire German Fischer–Tropsch whose large coal reserves were such vast coal reserves,’ recalls capacity of 1944. ‘To do something well suited to Fischer–Tropsch Robert Freerks, Rentech’s director of like the Pearl project, you’re trying to chemistry. State energy company product development. control a surface as small as square Sasol commissioned its first coal-to- Modern CTL processes typically nanometres, the actual catalyst site liquids (CTL) plant in 1955, which use iron catalysts, which are better where the reaction is going on,’ still operates today. suited to the low hydrogen content Mesters says. ‘You also have to control In the 1970s, oil crises originating synthesis gas coal produces. Rentech the project, simply in terms of its area, in the Middle East drove companies does just this, exploiting the iron Developing new, cheaper, on a square kilometre scale – 12 orders to consider the process once catalyst to raise the hydrogen more effective catalysts of magnitude difference. That is truly more. Carl Mesters, chief scientist content in the same way as when the is crucial for new Fischer– amazing to me.’ – chemistry and , at process was first invented, Freerks Tropsch applications multinational giant explains. ‘Our technology starts Turbocharged catalysts Shell, notes that this was when his closer to a 1:1 carbon monoxide: As GTL plants began to open in the company began to seriously look hydrogen ratio, utilising the water 1990s, Malcolm Green and Tiancun again at its brief post-war interest gas shift to make the hydrogen for Xiao at the University of Oxford, UK, in synthetic fuels. ‘In 1973, in line Fischer–Tropsch synthesis,’ he developed a Fischer–Tropsch catalyst with the realisation that we might says. While this process has some that would lead to the foundation of get a shortage on oil, Shell wondered environmental benefits, there is a company called Oxford Catalysts. what could be an alternative supply,’ less interest in CTL today, Freerks Green originally hoped to find says Mesters. ‘We got back to the admits. ‘We could produce fuel catalysts to couple methane to form same chemistry that Fischer and with lower carbon intensity than ethane, explains Roy Lipski, the Tropsch first published.’ crude oil,’ he points out. ‘But CTL company’s chief executive. ‘One of While a resurgence of interest plants, like new modern refineries the last catalysts, instead of doing followed, Sasol continued to be a producing clean fuels, are expensive what he hoped, did something dominant producer, and in 1979 it to build, and there is a reticence to quite different,’ he says. Green’s

OXFORD CATALYSTS OXFORD commissioned two further large use coal in the US.’ ruthenium catalyst was particularly 52 | Chemistry World | May 2011 www.chemistryworld.org

0511CW - Fischer-tropsch.indd 52 19/04/2011 07:46:44 active for partially oxidising methane in air, providing 97 per cent yield of hydrogen gas and 96 per cent of carbon monoxide, therefore being useful for producing syngas. Xiao replaced the expensive ruthenium catalyst with a cheaper cobalt analogue. But when BP tested this in the Fisher–Tropsch process, it soon became clear that it made the reaction proceed too quickly. ‘The rate of the reaction increases the higher the temperature,’ Lipski explains. ‘Unless you can effectively remove the extra heat that produces, you’re going to get a runaway reaction. The rate at which heat can be removed is limited in a conventional reactor, so they were too active.’ At a trade show in early 2007, Oxford Catalysts found the solution to that problem in microchannel reactors, produced by Velocys in Plain City, Ohio, US. ‘You’ve got more metal surface area – by which you put heat in or take heat out of the

reaction – to catalyst volume,’ Lipski CATALYSTS OXFORD says. ‘They enable much more active catalysts, but they need much more be used to generate electricity, Microchannel reactors high priority in terms of potentially active catalysts in order to realise Freerks explains. ‘You can capture improve heat transfer and making fuel wherever you need it, their benefits.’ After each company that energy, produce power to run open up new applications particularly as availability could discovered that they had what the the plant and, with the right designs, where size is a factor change,’ Willauer explains. ‘The other needed, Oxford Catalysts produce excess power to export,’ secretary of the Navy has also set bought Velocys in 2009. he says. In this way Rentech can goals of becoming green and carbon The microreactor format brings produce biomass-derived Fischer– neutral, and this fits right into Fischer–Tropsch chemistry to Tropsch fuels that actually decrease that.’ And while Willauer admits applications beyond those that overall emissions by that there is some way to go until are already well established, in displacing coal- and gas-generated turning seawater into fuel is a particular addressing the need for electricity from the grid, Freerks viable proposition, she underlines greener fuels. For example, small claims. that progress is being made. reactors allow GTL fuels to be made ‘We’ve scaled the electrochemical from waste methane extracted An ocean of energy apparatus to process half a gallon of alongside oil on drilling wells that Beyond carbon dioxide emissions, seawater a minute.’ would otherwise just be burnt off. oil price and fuel security concerns Technology may have advanced, ‘There’s enough gas flared every are mounting again. This has driven and the problems may be different year to supply 50 per cent of the a highly unusual Fischer-Tropsch compared to Franz Fischer’s original EU’s annual gas consumption,’ application: making from efforts. Yet today’s adaptations Lipski notes. ‘It’s a huge amount of seawater. The idea is to use carbon continue the spirit of that research, gas. It’s wasteful, and it’s painful, dioxide bound as bicarbonate in by providing fuel in the face of environmentally, commercially and seawater, explains Heather Willauer challenging restrictions, Willauer economically.’ Oxford Catalysts of the US Naval Research Laboratory notes. ‘That chemistry originated is also promoting its technology (NRL) in Washington, DC. out of a need for fuel and an for waste-to-liquid and biomass- ‘We’ve developed electrochemical abundant source of coal,’ she says. to-liquids (BTL) applications for technology to get carbon dioxide out ‘Now we’re looking at ways to move producing environmentally friendly of seawater, which also gives us the away from coal and petroleum and . That technology is already hydrogen that we need,’ she says. take other sources to end up with being tested in a 25 gallon per day ‘Then, a modified iron catalyst takes fuel – a similar need, but with more pilot plant at Güssing, Austria, to carbon dioxide and hydrogen and ‘We’ve constraints.’ produce from wood reduces carbon dioxide to carbon developed biomass. monoxide in the reverse water gas Andy Extance is a freelance science Rentech, which runs the largest shift, and polymerises it to ethylene electrochemical journalist based in Exeter, UK existing Fischer–Tropsch reactor and different olefins. We can then technology in the US, is also planning a BTL oligomerise those olefins to a jet fuel plant in Rialto, California, which type fraction.’ to get carbon Further reading turns the process’s heat output to its Like Oxford Catalysts, the dioxide and For more information on the history of Fischer– advantage. Gasifying wood biomass NRL is hopeful that it can exploit Tropsch chemistry, visit www.fischer-tropsch.org, hydrogen out of where Anthony Stranges’ collection has been also produces heat in large amounts, microchannel systems, particularly made available with support from US synthetic and consequently both stages can for use on a mobile platform. ‘It is a seawater’ fuel company Syntroleum www.chemistryworld.org Chemistry World | May 2011 | 53

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