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JOHNSON MATTHEY TECHNOLOGY REVIEW

Johnson Matthey’s international journal of research exploring science and technology in industrial applications

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Johnson Matthey’s international journal of research exploring science and technology in industrial applications

Contents Volume 61, Issue 3, July 2017

170 Guest Editorial: Industry and Sustainability By Deirdre Black 172 Methanol Production – A Technical History By Daniel Sheldon 183 One Hundred Years of Gauze Innovation By Hannah Frankland, Chris Brown, Helen Goddin, Oliver Kay and Torsten Bünnagel 190 Osmium vs. ‘Ptène’: The Naming of the Densest Metal By Rolf Haubrichs and Pierre-Léonard Zaffalon 196 The ‘Nano-to-Nano’ Effect Applied to Organic Synthesis in Water By Bruce H. Lipshutz 203 “Sustainability Calling: Underpinning Technologies” A book review by Niyati Shukla and Massimo Peruffo 207 Highlights of the Impacts of Green and Sustainable Chemistry on Industry, Academia and Society in the USA By Anne Marteel-Parrish and Karli M. Newcity 222 UK Energy Storage Conference A conference review by Jacqueline Edge 227 “Particle Technology and Engineering: An Engineer’s Guide to Particles and Powders: Fundamentals and Computational Approaches” A book review by Domenico Daraio, Giuseppe Raso and Michele Marigo 231 Organometallic Catalysis and Sustainability: From Origin to Date By Justin D. Smith, Fabrice Gallou and Sachin Handa 246 Industrial Low Pressure Hydroformylation: Forty-Five Years of Progress for the LP OxoSM Process By Richard Tudor and Atul Shah 257 T wo Hundred Proud Years – the Bicentenary of Johnson Matthey By W. P. Griffith 262 Johnson Matthey Highlights http://dx.doi.org/10.1595/205651317X695857 Johnson Matthey Technol. Rev., 2017, 61, (3), 170–171

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Guest Editorial Industry and Sustainability

This themed issue focuses on ‘Sustainable Industry’ opportunities to pursue sustainable options – and from the perspective of research advances and challenges in pursing them – all along a value chain. technological solutions. Starting with a high level policy The specifics depend on company size and business context, it is clear that the roles and responsibilities area, but many companies are including an explicit of industry are broader than technology and go way narrative about sustainability in their strategy and beyond what happens within industry. identity. People have been thinking about the issues and Companies are building thinking about sustainability options encompassed in the word ‘sustainability’ for into their business models and operations. Products decades. An important example is the “Limits to Growth” and components can be designed for reuse or report from the Club of Rome (1). This organisation recycling, to last longer or to be lighter. Companies are started as an informal group of “scientists, educators, committing to using energy from renewable sources, to economists, humanists, industrialists, and national and reducing the use of water in manufacturing, to working international civil servants” and the 1972 report was for together through industrial symbiosis and colocation its ‘Project on the Predicament of Mankind’. of raw material sourcing, component production, Today, the language and approach to sustainability manufacturing and waste management. focuses on solutions and opportunities as well as In terms of the science and technology innovation understanding “predicaments” and “problems”. In 2015 focus of this journal there are many promising research world leaders adopted the Sustainable Development advances: catalysis to increase energy efficiency, Goals which are at the core of the United Nations (UN) reduce dependence on platinum group metals, recycle 2030 agenda for sustainable development (2); that carbon dioxide or enable nitrogen fixation; green is “development that meets the needs of the present chemistry; reducing the use of solvents or improving without compromising the ability of future generations their recycling or disposal; and bio-based feedstocks to meet their own needs” (3). enabling reduction in energy use and environmental Sustainability has many facets, each with layers, impacts associated with raw material extraction or interactions and tensions. One dimension is trade-offs production. in terms of what is sustainable from environmental, public health, economic and societal perspectives. The Voice of Industry Another is balance between short-term options and long-term consequences. A third dimension is impacts The importance of industry in the sustainability and solutions on local, national and global scales. A agenda lies also in informing, influencing and fourth element is people, behaviour and accountability implementing policy. Many issues fit under the across individual citizens, organisations, companies ‘sustainability-related policy’ umbrella – from broad and policymakers. areas like energy, climate, air, food and water to specific topics like chemicals regulation and waste Sustainable Industry management. Industry can also influence research and innovation policy as an advocate for funding One lens for seeing the key role of industry in for research and development on sustainable sustainability looks within companies. There are technologies.

Leaders in industry are being proactive in making area can often have a positive impact on another. the business as well as the environmental case for An example is transport where reducing the number sustainability and at the same time policymakers of journeys, increasing engine efficiency, switching increasingly recognise the need to include a business to non-fossil fuels or using electric vehicles usually perspective and its value in identifying realistic options. reduces both carbon dioxide emission and air pollution. This is visible for climate change where Christiana To be truly sustainable, opportunities to develop and Figueres, the UN diplomat at the heart of the 2015 deploy environmentally sustainable solutions must 21st Conference of the Parties (COP-21) process and also be societally and economically sustainable. The the Paris Agreement, has been unequivocal about division of risk, responsibility and reward between the the importance of having industry at the table: “We’re public and private sectors will vary by issue, place and delighted that at every COP, we are able to open that time. What is clear is that industry is pivotal in achieving door more and more to the recognition of business” (4). sustainable development, because of what companies On the industry side there are perspectives from do and because of what leaders in industry say. groups like the World Business Council for Sustainable Development chaired by Paul Polman, Unilever CEO: DEIRDRE BLACK “The reality is, if we don’t tackle climate change we won’t Science Manager achieve economic growth” (5). Or the Risky Business Royal Society of Chemistry, Thomas Graham House, project quantifying the economic risks of climate Science Park, Milton Road, Cambridge, CB4 0WF, UK change, such as a likely US$35 billion increase in the Email: [email protected] annual average price tag associated with hurricanes and other coastal storms in the USA (6). References Another example of the industry-policy-sustainability 1. D. H. Meadows, D. L. Meadows, J. Randers and W. W. interplay is the May 2016 United Nations Environmental Behrens III, “The Limits to Growth”, Universe Books, Programme resolution on Sound Management of New York, USA, 1972 Chemicals and Waste (7), calling on the private sector 2. Resolution Adopted by the General Assembly on 25 to play a significant role in financing and capacity September 2015, ‘Transforming our World: The 2030 building and inviting industry to join other stakeholders Agenda for Sustainable Development’, A/RES/70/1, in supporting the Global Partnership on Waste United Nations, General Assembly, New York, USA, Management. 21st October, 2015 This is paralleled by the Responsible Care® initiative 3. ‘Our Common Future, Chapter 2: Towards Sustainable from the International Council of Chemical Associations Development’, from “Our Common Future: Report and by participation of industry in the development of the World Commission on Environment and of regulation like the European Regulation on Development”, A/42/427, UN Documents, United Registration, Evaluation, Authorisation and Restriction Nations, Secretary General, New York, USA, 4th of Chemicals (REACH) or the US Toxic Substances August, 1987 Control Act (TSCA) and in new areas like microplastics 4. J. Makower, ‘Christiana Figueres: Why business and persistent pharmaceutical pollutants. matters at COP’, GreenBiz Group Inc, Oakland, CA, Industry is critical in collecting and reporting data USA, 18th June, 2015 to enable development and implementation of 5. R. Harrabin, ‘Unilever Boss Urges World Leaders to environmental regulation. This is costly so there may Reduce Carbon Output’, BBC News, London, UK, need to be incentives or imperatives for companies to 18th May, 2015 invest in monitoring and reporting systems and to make 6. “Risky Business, The Economic Risks of Climate information available to policymakers and agencies. Change in the United States”, A Climate Risk Assessment for the United States, Risky Business, Sustainable Solutions New York, USA, June, 2014 7. ‘Sound Management of Chemicals and Waste’, Sustainability challenges like climate, water, energy UNEP/EA.2/Res.7, United Nations Environment and air are related in what is often called a nexus. Assembly of the United Nations Environment This gives cause for optimism in that solutions in one Programme, Nairobi, Kenya, 3rd August, 2016

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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

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). A second development at a similar time gave hydro- desulfurisation catalysts, which remove sulfur from the naphtha or natural gas feedstock and preserve the activity of the reforming catalyst. This gave a process Converter for supplying high purity syngas at increased pressure. Synthesis gas The cost of compressing syngas is much greater than the cost of compressing natural gas, so the opportunity to move compression duty upstream also provided an Circulator energy efficiency benefit to plant designs. By the 1960s, methanol was being made almost Purge gas solely from natural gas and naphtha using low pressure reforming and high pressure synthesis, with a broad Interchanger range of process licensors all offering a very similar Catchpot configuration. Substantial gains in process efficiency had been made since the very early plants, partly due to the larger scale of the later plants. One technology Methanol Crude cooler that the largest plants of the time could take advantage of was centrifugal compressors, offering much lower Fig. 2. Basic components of a pressurised methanol costs at high gas flow rates compared to the previous synthesis loop reciprocating machines (16). With these gains

174 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) increasing with equipment size, the drive for bigger and of ICI in August 1965 (18) to a catalyst containing bigger plants continued. the oxides of copper, zinc and another element from Groups II to IV of the periodic table, with aluminium The British Intervention being the preferred candidate. This was the catalyst that ICI installed in its own methanol plant constructed TM In the 1960s, arguably the biggest change to the at the time and forms the basis of the KATALCOJM industry was introduced by Imperial Chemical Industries 51-series of catalysts sold around the world by Johnson (ICI), UK. This began in 1963 when Phineas Davies Matthey today. and Frederick Snowdon filed a patent for a methanol ICI constructed and commissioned the first LPM plant production process operating at 30–120 atm (17). at its site in Billingham, UK, in 1966 (Figure 3) with a Using a copper, zinc and chromium catalyst, they had design capacity of 300 metric tonnes per day (MTPD) created a process capable of producing high quantities and an expected catalyst lifetime of six months. The of methanol without the need for very high pressures. synthesis section operated at only 50 atm (19). Two The lower pressures meant that fast reaction rates years later the catalyst was still operating and the plant could be achieved at lower temperatures of 200–300°C, could consistently produce 400 MTPD. This increased which reduced the formation of byproducts. This meant to 550 MTPD with the second catalyst charge and the catalyst was able to achieve a selectivity of greater some further plant upgrades. The converter had than 99.5%, based on organic impurities in the liquid 71 m3 of catalyst, with three cold shots of gas injected methanol. partway down the bed to cool the reacting gas. The At a similar time, ICI had developed its ‘high pressure’ plant operated until 1985. steam reformer, capable of transforming naphtha At the lower pressure of the new process, the or later, natural gas into syngas. The process was circulating gas volumes were greater and therefore therefore not just a method of synthesising methanol, centrifugal compressors were advantageous at lower but a complete process from natural gas to methanol: plant capacities (16). Much more efficient plants were the Low Pressure Methanol (LPM) process, which then available without needing to construct a large- remains the leading route to methanol to this day. scale facility. The catalyst was soon revised with a patent application ICI by this time had a long history of methanol by John Thomas Gallagher and John Mitchell Kidd production, stretching back to 1929 with its first high

Fig. 3. ICI (low pressure) methanol 1 plant at Billingham

175 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) pressure plant operated under licence from IG Farben (then owners of BASF). Following a few years of successful operation of the Billingham plant, ICI licensed the technology and in 1970 a 130 MTPD plant was commissioned for Chang Chun Petrochemical Co Ltd in Taiwan (20). In spite of a challenging two weeks of commissioning, with “torrential rain, a typhoon and an Equilibrium line earthquake”, this plant was to be the first of many and later that year a 1000 MTPD plant was commissioned

for Monsanto at Texas City, Texas, USA. Only a single Methanol, % high pressure synthesis plant was built after 1966 (21).

Methanol Converters Reaction path

The most distinguishing feature of most methanol plants (or licensors) is the type of converter used for Low High methanol synthesis. Broadly the converters can be Temperature divided into two categories based on how they remove Fig. 4. Reaction path in a quench converter the heat of reaction to maximise conversion: i. multiple adiabatic catalyst beds with external cooling of the gas the loop contribute to higher capital costs and series ii. internal cooling within one or more catalyst beds. adiabatic beds never really found favour in the industry. Externally cooled converters come in a variety of Internally cooled reactors began with Lurgi GmbH, configurations: quench converters inject cold, unreacted Germany, shortly after the first LPM plant from ICI. The gas after each adiabatic bed to reduce the temperature, Lurgi reactor was one that had already been used for whereas series adiabatic converters use heat many years in Fischer-Tropsch synthesis and consisted exchangers between the catalyst beds. Both externally of catalyst-filled vertical tubes surrounded by a shell of and internally cooled types were used in the early low boiling water, with the reaction heat transferred into the pressure plants, with the quench converters offered by shell to generate steam to be used elsewhere in the ICI benefitting from the simple vessel design minimising process. A steam drum local to the converter provides a cost. The early versions employed a single catalyst constant supply of water at boiling temperature through bed with gas injection points at multiple locations down natural circulation. This design achieved a more even the vessel. These designs were susceptible to large temperature distribution and lower peak temperature. temperature distributions developing and propagating Whilst the converter was more complicated than the down the vessel. A subsequent improvement on the ICI design, and therefore more expensive, the steam it design therefore collected the gas, mixed it with the generated at about 250ºC could be used elsewhere for incoming quench gas and distributed it across the next an efficiency benefit or even exported. The design also bed. This prevented temperature variations propagating required a lower catalyst volume. Figure 5 shows the from bed to bed. Many reactors of this design operate reaction pathway in such a converter, following more around the world today as ARC reactors, a joint ICI and closely the temperature for maximum reaction rate Casale SA, Switzerland, design from the early 1990s. compared to quench converters. Many variations exist Figure 4 shows the reaction pathway of a quench on this theme today, some with the catalyst and boiling converter, with successive additions of cold gas taking water reversed, such as in the Variobar of Linde AG, it back away from the equilibrium line to maximise Germany, which uses helical tubes in an axial catalyst conversion. bed to achieve pseudo-cross flow. Series adiabatic converters are more efficient users Other internally cooled converters use process gas on of catalyst as, without the need for quench gas that the cooling side, including ICI’s subsequent tube cooled bypasses the early beds, all the gas passes over all converter, in which cold gas rises inside empty vertical the catalyst and the temperature control for each bed tubes, absorbing heat from the surrounding catalyst is truly independent. Additional heat exchangers in bed before turning over at the top of the converter and

point of maximum reaction rate, a balance of the kinetic limitations of low temperature and the thermodynamic (equilibrium) limitations of high temperature.

Capacity Expansion Equilibrium line The basic formula was now set and so the plants could grow in size and scale. By the early 1970s the plants had gone from the 150 MTPD of the early low pressure

Methanol, % plants to 1500 MTPD. The second plant ICI built at Billingham in 1972 had a design capacity of 1100 MTPD and used 110 m3 of catalyst (22) operating at 100 atm. This second plant operated through to 2001 and struck Reaction path a better balance of operating pressure and equilibrium, with the vast majority of plants since having been Low High designed for 80–100 atm. This heralded the start of the Temperature first golden age of methanol expansion in the early part of the 1970s as people recognised the benefits of the Fig. 5. Reaction path in a water cooled converter new LPM process. Figure 6 shows the approximate capacity added each year using LPM technology, with a notable peak in the 1970s and further peaks in the flowing back down through the catalyst bed. The large 1980s and around 2010 that will be explored in the amount of heat generated by the synthesis reactions second half of this history. requires a high flow rate on the cooling side, which for By the early 1980s all new plants were being gas-based cooling is typically only available within the constructed using low-pressure technology and almost synthesis loop, with different designs utilising gas from all of the high-pressure plants had been converted to different parts of the loop. low pressure (23). Interestingly the pyrolysis of wood Most modern converters use internal cooling, either had not completely ceased as the use of ‘synthetic’ with circulating gas or by raising steam, which broadly methanol had not yet been accepted as an alcohol allows the temperature in the catalyst bed to track the denaturant in some countries. British Law to this day

3 50

10 Added capacity, tonnes per day × 10 Added capacity, 0 1960 1970 1980 1990 2000 2010 2020 Year

Fig. 6. Added global methanol capacity by year

(24) is based on the use of ‘wood naphtha’ to denature methanol was being considered as a way to move pure ethanol, a process whereby it is made unsuitable energy around in the face of global imbalance. To for human consumption and therefore exempt from produce sufficient quantities of methanol to achieve beverage sales taxes. Wood naphtha is the mixture this, production capacity would need to increase of substances derived from pyrolysis, primarily methyl rapidly with plants of up to 5000 MTPD, which would alcohol (methanol). have required 2000 tube steam reformers. The largest The 1980s saw the impact of the second oil crisis constructed at that time had only 600 (27). that followed the Iranian Revolution in 1979 and the The gap was ultimately filled with autothermal Iran-Iraq war that started soon after. The increased oil reforming; the controlled introduction of oxygen price meant that oil producing nations had significantly into (partially) reformed gas to combust some of the increased revenues and this allowed them to increase hydrogen, providing the heat for further reforming petrochemical production, including methanol. Thus reactions across another bed of catalyst. As the heat is began the second golden age of methanol expansion. produced and retained within the process, a lot of the But the oil crisis also prompted countries to start looking equipment associated with reformers is not needed, at how they could become less reliant on imported oil although a supply of oxygen is required, typically from and to start looking at production of synthetic fuels. an air separation unit. The technology is deployed in various configurations: Synthetic Fuels • parallel reforming – a steam reformer and autothermal reformer (ATR) are used in parallel The expansion of methanol is driven by demand for • combined reforming – the steam reformer is derivatives and a recurring theme throughout the partially bypassed and the bypass and reformed history is its potential use as an intermediate in the gas are combined and fed to the ATR to complete production of synthetic automobile fuel. Whilst interest the reforming process. has peaked on a number of occasions, typically when A further development by ICI in the 1980s was to a nation struggles with domestic supply, there have completely remove the traditional steam reformer in the been few plants actually constructed. One example Leading Concept Methanol (LCM) process. Rather than is the two methanol plants in Motunui, New Zealand, burning fuel gas to provide the heat for the reforming which were constructed for synthetic fuel production in reactions, the hot, autothermally reformed gas was 1985, using the Mobil licensed methanol to gasoline used to heat the catalyst tubes in a gas heated reformer (MTG) process (25). Both plants now solely produce (GHR). The feed gas first passes through the catalyst methanol and the MTG equipment has been removed. in the GHR, then the ATR and finally the heating side Whilst the production of a direct petrol replacement of the GHR to provide the heat for the initial reaction. has never found lasting favour, many plants today are It is possible to take these concepts even further and being constructed to feed methanol to olefins (MTO) some plants have only an ATR. Autothermal Reforming processes to produce olefins from coal instead of is susceptible to soot formation if significant quantities from naphtha or ethane, and an increasing amount of of higher hydrocarbons are present and so a simple methanol is blended into gasoline supplies around the adiabatic pre-reformer is required to de-rich the natural world to meet legislative requirements. gas. This arrangement produces a gas very rich in carbon oxides and is therefore most effective where a Autothermal Reforming and Alternative source of additional hydrogen is present to balance the Reforming stoichiometry of the gas. Typically, combined reforming gives a plant with a For a typical natural gas to methanol plant using steam reasonably sized steam reformer, a low level of methane reforming technology, roughly a half of the capital cost in the syngas and a stoichiometrically balanced syngas is in the steam reformer and it also accounts for a large for methanol formation. part of the footprint. Available technology limited the maximum economic size of a single reformer and a Modern Catalysts new technology was therefore required to allow plant capacities to expand beyond about 2500 MTPD (26). The speed of catalyst development had greatly This limit was first identified in the early 1970s when increased since the mid 1970s when testing equipment

178 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) began to be automated, greatly increasing the amount added back into the process before the reformer, to be of test work that could be conducted. This led to reformed and reused. a number of step changes in the performance of In, 2004 the long destined capacity of 5000 MTPD methanol synthesis catalysts, although the base recipe was achieved when the Atlas plant was commissioned of copper with a combination of zinc and aluminium or in Trinidad, only for it to be overtaken the following chromium oxides remained very similar. One such step year by M5000, also in Trinidad, producing up to change was in the early 1990s, with a new generation 5400 MTPD. This latter plant achieved its capacity with of catalysts being introduced, just as capacities were only a steam reformer containing less than 1000 tubes, ramping up and plant operators were looking to uprate showing the simultaneous improvements in reforming their original low pressure plants (28). ICI introduced catalyst and technology. Figure 8 shows the twin a, new more active catalyst using a four-component synthesis converters on M5000. system, adding magnesium to the existing copper, zinc and aluminium (Figure 7). China – The Coal Story Modern catalysts are expected to last at least three years and typically between four and six years is A lot of the growth in the methanol industry through the achieved, although six to eight years is not uncommon. early 21st century (the third golden age of methanol The catalysts are highly selective towards methanol expansion) came from China and its booming economy. synthesis and the effects of some of the early catalyst China’s petrochemical industry had been heavily candidates (iron and nickel) are better appreciated, dependent on imported crude oil, although China especially their role in the formation of paraffinic had plentiful supplies of cheap coal. China began to hydrocarbons, and these are now seen as catalyst embrace new technologies for converting their coal poisons. Despite the selectivity of modern catalysts into other chemicals and one key building block in that being in excess of 99.5%, there is still a need to process was methanol. Rapidly increasing demand remove various impurities from the condensed product for a wide range of methanol derivatives, particularly methanol to achieve either chemical or fuel sales olefins via the MTO process, has required a continuous grades. Generally, this is achieved at low pressure supply of new methanol plants using coal gasification with one, two or three distillation columns in series. to provide the syngas for methanol synthesis. Dissolved gases are removed first, along with low To take advantage of the economies of scale, and boiling point byproducts and then the difficult methanol- in some cases to fit in with the economic size of a ethanol separation must be conducted, along with downstream MTO plant, the demand for higher and water removal. The water can be reused in the steam higher capacity synthesis loops has grown. With the system, the light ends as fuel and the ethanol (actually methanol plants typically near to the coal in remote a mixture of many heavier organic compounds) can be locations, the main process equipment must be

Fig. 7. An example of the latest generation of methanol Fig. 8. 5000 MTPD of methanol synthesis capacity at TM synthesis catalysts; Johnson Matthey KATALCOJM 51-9S M5000, Trinidad

179 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695622 Johnson Matthey Technol. Rev., 2017, 61, (3) transported to the sites by rail, where bridges in particular syngas. Modern purification systems now allow the limit the maximum diameter and the infrastructure can syngas to be substantially cleaned of sulfur and other limit the maximum weight. Whilst vessels can be made impurities and a very pure gas is fed to the synthesis taller and taller, for catalyst beds this will soon result in loop, unlike the systems from the 1920s and 1930s. very high pressure drops. For synthesis loops above Typically, coal-fed plants give a much more carbon about 3000 MTPD the catalyst requirement is too great monoxide-rich syngas compared to steam reforming of to use a single vessel and multiple converters in a single natural gas, the more exothermic route to methanol and loop are required. Initially and at modest capacities, so the ability to remove heat is even more important. two identical parallel converters were sufficient. As capacities continued to increase, so did the complexity, Energy and Environmental Efficiency with multiple converters of different types used within single loops to reduce the capital cost of the loop Since the introduction of the low pressure process, equipment, as shown in Figure 9 with the Johnson the focus turned to energy efficiency, especially during Matthey Combi Loop. Other loops were designed using increasing energy prices in the 1970s and 1980s. the Johnson Matthey Series Loop where product is Table I shows the progression of efficiency over these recovered between converters to reset the equilibrium years by ICI through successive improvements to the and increase production. The largest plants in operation integration of the whole plant. by 2010 would typically have two or more converters With the ever increasing focus on environmental to make up to 5500 MTPD of methanol. To minimise performance, there are a number of designs and new pressure drop and therefore compression duty in large plants in recent years which aim to set new standards synthesis loops, larger water cooled reactors are now for efficiency or emissions. One particular plant is available in radial flow configurations. Carbon Recycling International’s (CRI) George Olah The second aspect of the growth in China is the coal Plant in Iceland, fully commissioned in 2012. Using to methanol story, which uses gasification technologies electricity from the fully renewable Icelandic grid, to convert coal and steam at very high temperature to it electrolyses water to provide hydrogen, which is

Axial steam- Steam raising converter

Boiler feed water Tube cooled converter Steam drum

Circulator

Purge Interchanger

Feed Condenser Separator Crude methanol

Fig. 9. Modern synthesis loop – Johnson Matthey Combi Loop

Table I Improvements in Feed and Fuel Consumption (29) Consumption, Flow sheet Year GJ MT–1 HP Pre-1966 42 LP – 50 atm 1966 36 LP – 100 atm 1972 36 BFW heating 1973 32.6 Optimisation 1975 32.2 Quench pre-heating 1977 31.4 Saturator 1978 30.1 Tube cooled converter 1983 29.3 LCM 1989 28.6

combined with carbon dioxide recovered from a local References geothermal power station (30). 1. M. Berggren, ‘Global Methanol: Demand Grows Other new plants are considering the emissions as Margins Atrophy’, 19th IMPCA Asian Methanol benefitsf o avoiding a steam reformer and using Conference, Singapore, 1st–3rd November, 2016 the GHR technology to set new standards for low 2. “Methanol Production and Use”, eds. W.-H. Cheng emission natural gas-based plants. The plans for and H. H. Kung, Marcel Dekker, Inc, New York, USA, Northwest Innovation Works (NWIW), USA, use the 1994, p. 2 technology and will be among the largest plants in the . 3. P Sabatier and J.-B. Senderens, Ann. Chim. Phys., world (31). 1905, 4, (8), 319 4. G. Patart, ‘Procédé de Production d’Alcools, The Future d’Aldéhydes et d’Acides à Partir de Mélanges Gazeux Maintenus sous Pression et Soumis à l’Action d’Agents With the imminent start-up of the 7000 MTPD plant of Catalytiques ou de l’Électricité’, French Patent Appl. Kaveh in Iran (32), the scale of plants continues to grow. 1922/540,543 Methanol demand has grown steadily for many years 5. J. B. C. Kershaw, ‘The World’s Future Supplies of fuelled by economic growth in major countries around Liquid Fuels’, The Engineer, 25th March, 1927, 316 the world, a trend which is likely to continue. Many of 6. A. Mittasch, M. Pier and K. Winkler, BASF AG, the current plant licensors and designers have flow ‘Ausführung Organischer Katalysen’, German Patent sheets capable of scaling up to 10,000 MTPD, but after 415,686; 1925 a number of purported projects, it remains to be seen if 7. ‘1902–1924: The Haber-Bosch Process and the the economy of scale is ready to be stretched that far Era of Fertilizers’, BASF, Ludwigshafen, Germany: or if the security of multiple trains once again wins out. https://www.basf.com/en/company/about-us/ At least for now, the production of methanol via the history/1902-1924.html (Accessed on 16th May 2017) LPM process remains dominant, despite research 8. A. Mittasch, M. Pier and C. Müller, IG Farbenindustrie interest into other themodynamically attractive routes. AG, ‘Manufacture of Oxygenated Organic Recent examples based on the partial oxidation of Compounds’, US Patent Appl. 1931/1,791,568 methane to methanol include the work of Zhijun Zuo 9. A. Mittasch and M. Pier, BASF AG, ‘Synthetic et al. (33) and Patrick Tomkins et al. (34). Whilst work Manufacture of Methanol’, US Patent Appl. such as this could open up a new, low temperature 1926/1,569,775 route to methanol, no such new routes have so far left 10. BASF AG, ‘Improvements in the Manufacture of Methyl the laboratory. Alcohol and Other Oxygenated Organic Compounds’, KATALCOTM is a trademark of the Johnson Matthey British Patent Appl. 1925/231,285 group of companies. 11. A. Mittasch and C. Schneider, BASF AG, ‘Producing

Compounds Containing Carbon and Hydrogen’, US Institute, California, USA, 1968, 146 pp Patent Appl. 1916/1,201,850 24. ‘The Denatured Alcohol Regulations 2005’, 2005 No. 12. F. C. Reed, ‘Process of Producing Compounds 1524, The Stationery Office Limited, London, UK, 8th Containing Carbon, Hydrogen, and Oxygen’, US June, 2005 Patent Appl. 1934/1,959,219 25. J. Ross, “Heterogeneous Catalysis: Fundamentals 13. “The Methanol Industry Past, Present and Working and Applications”, 1st Edn., Elsevier BV, Amsterdam, Towards a Sustainable Future”, Johnson Matthey The Netherlands, 2012, p. 188 GB Process Technologies, online video clip, YouTube , 26. K. Aasberg-Petersen, C. S. Nielsen, I. Dybkjær and J. 29th November, 2016 Perregaard, “Large Scale Methanol Production from 14. E. Błasiak, ‘Sposób Wytwarzania Wysokoaktywnego Natural Gas”, Haldor Topsøe, Lyngby, Denmark, 2008 Katalizatora do Syntezy Metanolu’, Polish Patent 27. B. M. Blythe and R. W. Sampson, Am. Chem. Soc., 34,000; 1947 Div. Fuel Chem., Prepr., 1973, 18, (3), 84 15. C. Murkin and J. Brightling, Johnson Matthey Technol. 28.. T J. Fitzpatrick, ‘New Developments in Methanol Rev., 2016, 60, (4), 263 Synthesis Catalysts and Technology’, International 16. G. E. Haddeland, “Synthetic Methanol”, Report No. Methanol Technology Operators Forum (IMTOF), 43, Process Economics Program, Stanford Research London, UK, 15th–16th June, 1993 Institute, California, USA, 1968, p. 4 29. K. Mansfield, ‘ICI Katalco and Methanol, Past, Present 17.. P Davies, F. F. Snowdon, G. W. Bridger, D. O. Hughes and Future’, International Methanol Technology and. P W Young, ICI Ltd, ‘Water-Gas Conversion Operators Forum (IMTOF), San Francisco, USA, and Catalysts Therefor’, British Patent Appl. 19th–22nd June, 1995 1965/1,010,871 30. ‘World’s Largest CO2 Methanol Plant’, Carbon 18. J. T. Gallagher and J. M. Kidd, ICI Ltd, ‘Methanol Recycling International, Kopavogur, Iceland, 14th Synthesis’, British Patent Appl. 1969/1,159,035 February, 2016 19. M. Appl, ‘Methanol-Born in 1923 and Still Going 31. ‘NWIW Adopts Pioneering Technology to Substantially Strong’, World Methanol Conference, Frankfurt, Reduce Facility Emissions’, Johnson Matthey Process Germany, 15th December, 1998 Technologies, Royston, UK, 6th August, 2015 20. ‘Stormy Start Up’, Process & Catalyst News, Number 32. ‘World’s Largest Methanol Plant to be Commissioned 1, ICI, Agricultural Division, 1st January, 1971 in Iran’, Chemicals Technology, News, London, UK, 21. K. Mansfield, Nitrogen, 1996, 221, 27 27th February, 2015 22. J. Brownless and E. Scott, ‘Experience of the No. 2 33. Z. Zuo, P. J. Ramírez, S. D. Senanayake, P. Liu and Methanol Plant Synthesis Converter at Billingham’, J. A. Rodriguez, J. Am. Chem. Soc., 2016, 138, (42), International Methanol Technology Operators Forum 13810 (IMTOF), London, UK, September, 1991 34. P. Tomkins, A. Mansouri, S. E. Bozbag, F. Krumeich, M. 23. G. E. Haddeland, “Synthetic Methanol”, Report No. B. Park, E. M. C. Alayon, M. Ranocchiari and J. A. van 43B, Process Economics Program, Stanford Research Bokhoven, Angew. Chem. Int. Ed., 2016, 55, (18), 5467

The Author

Daniel Sheldon is a Senior Process Engineer at Johnson Matthey, Chilton, UK. He obtained his MEng (Hons) in chemical engineering from the University of Manchester, UK. He joined Johnson Matthey on the graduate training scheme in 2011 and has spent time in catalyst manufacturing and technology development for the ammonia and methanol industries. Currently he provides technical support to Key Methanol Customers. He is a Chartered Member of the Institute of Chemical Engineers (IChemE).

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

One Hundred Years of Gauze Innovation Platinum gauzes for nitric acid manufacture celebrate a centenary

By Hannah Frankland*, Chris Brown, Helen Goddin, Oliver Kay and Torsten Bünnagel Johnson Matthey Plc, Orchard Road, Royston, Hertfordshire, SG8 5HE, UK

*Email: [email protected]

In the century since the first platinum gauze for nitric acid production was made by Johnson Matthey, the demand for nitric acid has increased considerably with its vast number of applications: from fertiliser production to mining explosives and gold extraction. Throughout Fig. 1. Johnson Matthey’s first woven gauze the significant changes in the industry over the past 100 years, there has been continual development in Johnson Matthey’s gauze technology to meet the In the 1930s small amounts of rhodium began to be changing needs of customers: improving efficiency, included in the gauzes to prevent losses of platinum increasing campaign length, reducing metal losses and while increasing the strength and conversion efficiency. reducing harmful nitrous oxide emissions. This article Palladium catchment gauzes were introduced in reviews the progress in gauze development over the the 1960s for platinum recovery, offering economic past century and looks at recent developments. benefits. These were initially palladium-gold, but as the price of gold increased it was replaced by nickel. Introduction 1996 saw the invention of knitted gauzes (Figures 2 to 4), which allowed a diverse range of structures and Johnson Matthey Plc recently celebrated a alloys to be used in the gauze packs, giving a better centenary since making its first platinum gauze metal distribution and contact area. This considerably pack (Figure 1), sold to the UK Munitions Invention improved conversion efficiency and overall plant Department in October 1916 for £25 to make nitric performance while also reducing manufacturing time acid for explosives during the First World War. The two compared to woven gauzes. This technology, pioneered 4″ × 6″ (approximately 101 × 152 mm) woven gauzes by Johnson Matthey, became the industry standard. were made with 0.065 mm diameter wire, woven in a A few years later gauze packs were developed with square mesh with 80 meshes per linear inch. Johnson Matthey’s proprietary Advanced Coating

(a) (b)

Fig. 2. (a) The structure of a knitted gauze; (b) a gauze knitting machine

Technology (ACTTM), reducing the time required to reach maximum production. Later in 2006 the company partnered with Yara International ASA, Norway, to supply its abatement catalyst to minimise harmful nitrous oxide emissions released during nitric acid production.

Gauze Development

In the same year, the catalyst and catchment were combined for the first time through Eco-CatTM systems. This combines platinum group metal (pgm) with complex ternary alloys and knit structures. Compared to conventional gauze alloys, it uses palladium in a controlled manner to replace some of the platinum, exploiting its metal recovery properties to catch platinum that is lost from the gauze during ammonia Fig. 3. HICON corrugated gauze oxidation. This system has shown an increased

Fig. 4. Installation of a gauze pack at a customer plant supplied by Paite, Johnson Matthey’s Chinese licensee

184 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695640 Johnson Matthey Technol. Rev., 2017, 61, (3) performance compared to standard catalyst packs, the relative gas flow variations in the burner, it was and (subject to plant operating parameters) offers found to be higher in certain areas. This was causing nitric acid manufacturers benefits including: extended faster depletion of the gauze in these regions and campaign lengths by 50–100%; maintained or therefore resulting in more platinum movement, while improved average conversion efficiency; a reduction also adversely affecting the ammonia conversion in installed pgm weight by 40–50%; a reduction in efficiency. installed platinum weight by 30–40%; reduced metal The solution drew upon a vast range of gauze structures losses by approximately 30–50%; and reduced nitrous and their mechanical properties, addressing the regional oxide emissions. flow issues in the burner while also considering one The improved performance of Eco-CatTM technology of the customer’s key requirements of reducing the compared to standard gauze packs is demonstrated in installed pgm content. As a result, the customer noticed Table I, showing the increase in campaign length and an improvement in the conversion efficiency. nitric acid production when using an Eco-CatTM system Analysis from previous campaigns along with the in a medium pressure plant. producer’s data allowed the design of the catalyst to be improved through tailored wire diameters and knit Case Study: Reducing the Cost of Nitric Acid structures. This optimised the reaction zone while also Production further reducing the installed pgm content. As shown in Figures 5–7, the customised Eco-CatTM Recently, Johnson Matthey worked with one customer system contributed to a substantial reduction in the to create a tailored Eco-CatTM system to solve its three producer’s costs per tonne of nitric acid. main requirements: increasing average conversion efficiency, reducing the installed pgm content of the Faster Light Off gauze packs and reducing metal losses. A progressive approach was taken to customising the gauze pack for A key goal for most nitric acid producers is to reduce the customer’s specific plant conditions using in-depth the time required to reach peak conversion efficiency. analytical data. In-house laboratory research into how peak efficiency Detailed examination of gauze samples from the first is reached has found that platinum is volatilised during installed Eco-CatTM system uncovered an operational normal operation and forms cauliflower-like structures issue related to the plant design that was impacting on the wire, which increases catalytic surface area. the gas flow over the catalyst. Upon measuring ACTTM allows a thin layer of platinum to be sprayed

Table I Nitric Acid Campaign Results using a Standard Johnson Matthey Gauze Pack and Two Developments of Eco-CatTM Technology

Eco-CatTM system Eco-CatTM system Standard gauze (Campaign 1) (Campaign 2)

Campaign length, days ~100 ~175 ~210

100% HNO produced, 3 ~85 ~135 ~160 kilotonnes equivalent

Total mass of installed ~50 ~40 ~40 platinum, kg

Total mass of installed ~3 ~2 ~2 rhodium, kg

Total mass of installed 0 ~10 ~15 palladium, kg

Eco-cat version 1 Eco-cat version 2 Eco-cat version 3 Fig. 5. The pgm content and value in Eco-cat version 4 Eco-cat version 5 developments of Eco-CatTM packs 250

200 216 198 205 182 174 150

100

50 67.8 59.2 61.2 54.4 48.8

0 Total pgm per annum, kg Installed metal value per annum, €100,000

Eco-cat version 1 Eco-cat version 2 Eco-cat version 3 Fig. 6. The pgm losses in developments Eco-cat version 4 Eco-cat version 5 TM 80 of Eco-Cat packs 70 75 70 70 72 60 65 60 61 50 52 40 45 30 33 20 10 6 5 6 5 4 0 Net loss Pt, mg tonne–1 Net loss Rh, mg tonne–1 Net loss Pd, mg tonne–1

Eco-cat version 1 Eco-cat version 2 Eco-cat version 3 Fig. 7. Overall costs and cost per 6 Eco-cat version 4 Eco-cat version 5 tonne of acid in various developments 5 of Eco-CatTM packs. (Overall cost = 4.92 manufacturing cost + metal handling 4 4.53 4.38 4.02 charge + refining assay + net metal loss) 3 3.72 2 1 1.4 1.35 1.3 1.19 1.11 0 Overall cost per annum, Cost per tonne acid, € €millions onto the surface of selected gauze layers to improve Using the company’s in-house ammonia oxidation the gauze pack’s activation, resulting in faster light-off facilities, data on light-off, selectivity and long-term (Figure 8). performance have been analysed to improve the design This technology has been shown to improve the early of the gauze pack. Initial trials of ACTTM coated gauzes performance of the gauze packs in several plants in two different knit structures (Nitro-LokTM gauze and when used in the top layers, but Johnson Matthey has Hi-LokTM gauze) both showed a 45% reduction in recently been investigating how ACTTM coatings can light-off temperature compared to the uncoated gauze further improve light-off and conversion efficiency. (Figure 9).

coating placement or weight has the potential to make a significant improvement on the time taken to reach peak conversion efficiency. This increased understanding of the mechanisms behind the coating and how this reduces the time to reach peak conversion efficiency has exciting implications for nitric acid plants, allowing the position and weight of the ACTTM coating to be tailored to minimise costs for producers.

Process Modelling

TM Fig. 8. ACT machine Along with catalyst, catchment and abatement solutions that Johnson Matthey supplies to the nitric acid industry, Fundamental to the design improvement is complex models of the reaction system can be provided understanding how the gauze changes with time. using its fundamental chemical and physical properties Scanning electron microscopy (SEM) has shown the alongside proprietary data. Through this knowledge ACTTM coating forming a series of discrete islands on and modelling of the burner, more information can the gauze, each of which locally increases the surface be found on the selectivity of ammonia conversion, in area and becomes a focus point for light-off (Figure 10). particular the extent and type of reaction. Inspection of the samples from the trials has also The complex model of the burner has been built shown the ACTTM coating restructuring (Figure 11) from extensive experience of gauze design along with much earlier than expected; a change to the ACTTM known process conditions using spent gauze analysis,

Fig. 9. Graph demonstrating a reduction in light-off temperature with ACTTM coatings Light-off temperature, ºC Light-off

Nitro-LokTM gauze ACTTM coated Hi-LokTM gauze ACTTM coated Nitro-LokTM gauze Hi-LokTM gauze

(a) (b)

76 mm 57.5 mm

Fig. 10. Scanning electron microscopy (SEM) images of the ACTTM coated gauze

(a) (b)

2 mm 2 mm

Fig. 11. SEM images of the ACTTM coating: (a) before and (b) after restructuring

test rig data and historical plant data. This provides an conversion efficiency and selectivity, where high gas in-depth understanding of how gauzes change over time temperatures and testing conditions of the sampling and how this impacts the overall conversion efficiency. point make it challenging to obtain a representative It can also help to identify where efficiency losses may gas sample over the gauzes. This makes it an be occurring; once this is found different sensitivities extremely useful tool in optimising the overall plant can be investigated to optimise the process, resulting operation. in maximum plant conversion efficiency. Compared to a process model that is theoretically derived, this Present Day model provides more accurate and valid data through the dynamic kinetic model of the burner. 100 years after making the first gauze catalyst, The detailed kinetic model allows predictions to Johnson Matthey now offers a full service package be made for the optimal knit structures and alloy for nitric acid manufacturers: catalyst, catchment, compositions for a campaign, for example looking at N2O abatement and containment engineering, the gauze restructuring which is closely linked to the technical analysis, plant cleaning to recover metal catalyst performance, where an increase in active through a partnership with R S Bruce Metals and surface area can improve the conversion efficiency. Machinery Ltd, UK, and process simulation through The model can also relate specific plant conditions to a partnership with ProSim SA, France. The latest metal losses, which can reduce costs for the producer additions to these services are absorption tower and again improve conversion efficiency of the burner. scanning through Tracerco and water treatment for Any findings from the model can then be compared to cooling and process water through MIOX®, both part experimental observations from gauze analysis. of the Johnson Matthey group. This robust gauze model overcomes difficulties ACTTM, Eco-CatTM, Nitro-LokTM, Hi-LokTM and MIOX® producers have historically faced in directly measuring are trademarks of Johnson Matthey Plc, UK.

The Authors

Hannah Frankland joined Johnson Matthey as Marketing Specialist for the Noble Metals business unit in 2015 after previously working for the Royal Society of Chemistry, Cambridge, UK, where she was primarily involved in membership communications. With a Chemistry degree from the University of Bath, UK, she enjoys combining her technical knowledge with her passion for marketing.

Christopher Brown originally joined Johnson Matthey in 2001 as a Materials Scientist in the Noble Metals technology group after graduating from the University of Nottingham, UK. After moving into sales and marketing in 2004, Chris has worked in technical sales roles, primarily in the Nitro Technologies sector which has combined his passion for business, people and travel.

Helen Goddin is the Research Group Leader for Nitro Technologies, leading developments in ammonia oxidation products. Prior to joining Johnson Matthey two years ago, she worked at TWI, leading research projects on materials development and joining processes. She has a PhD in High Temperature Electronic Materials, from the University of Cambridge, UK.

Oliver Kay joined Johnson Matthey in 2015, from the University of Leeds, UK, where he read Chemical Engineering. Oliver is part of the Graduate Programme, originally based in Noble Metals, where he was involved in developing a service offering for the nitric acid business. Now Oliver is based in Maastricht, The Netherlands, working for Advanced Glass Technologies, where he has a varied role, ranging from New Business Development to Operational Excellence projects.

Dr Torsten W. Bünnagel began his career with Johnson Matthey in 2011 in the Technical Sales Team of Noble Metals, Royston, UK, advising nitric acid, caprolactam and hydrogen cyanide businesses around the globe on new developments in the areas of catalytic ammonia oxidation

and N2O abatement systems. In his current role as Sales Manager – Organometallics, Dr Bünnagel is commercialising novel materials utilised in various advanced chemical processes and technical applications. Prior to Johnson Matthey, he developed OLEDs for lighting applications and consumer electronics for Sumitomo Chemicals Company, Japan. He earned a Diploma Degree in Chemistry at the University of Wuppertal, Germany, and completed a PhD in Macromolecular Chemistry in the area of Organic Electronics in 2008.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

Osmium vs. ‘Ptène’: The Naming of the Densest Metal The early name ‘ptène’ is attributed to French chemists Fourcroy and Vauquelin

By Rolf Haubrichs and Pierre-Léonard (1755–1809), Nicolas-Louis Vauquelin (1763–1829) Zaffalon* and Hippolyte-Victor Collet-Descotils (1773–1815), as CristalTech Sàrl, Rue du Pré-Bouvier 7, 1217 Meyrin, they were all involved in the study of platinum ore in Switzerland the 1800s. In an earlier paper, the same author had concluded that Tennant was first inclined to call the *Email: [email protected] new element ‘ptène’ instead of osmium (4). In fact, we can confirm the later statement of Jaime Wisniak that the origin of ‘ptène’ was French (5). This paper reviews the use and relation of the word ‘ptène’ to osmium. While Smithson Tennant discovered A New Metal in Platinum Ore: ‘Ptène’ osmium in platinum ore in 1804, the French chemists Antoine-François Fourcroy and Nicolas-Louis The origin of the early research on platinoids was the Vauquelin simultaneously identified in a platinum partnership between Smithson Tennant (1761–1815) residue a metal they called ‘ptène’. This name was most and William Hyde Wollaston (1766–1828), two alumni probably attributed to a mixture of platinoids (excluding of Cambridge University, UK, to isolate any valuable platinum), mainly osmium and iridium. Nevertheless, substance from platinum ore. Wollaston was in charge Fourcroy later considered that ‘ptène’ was the name of the soluble part in aqua regia while Tennant took care they attributed to osmium. of the black residue. Wealthier than his friend, Tennant probably provided the money for the first purchase of Introduction nearly 6000 ounces of platinum ore and from 1800 they started their research separately (at Tennant’s death In a paper celebrating the bicentenary of the discovery in 1815, the amount of platinum they had purchased of osmium and iridium, the name ‘ptene’ or ‘ptène’ was totaled 47,000 ounces. A major supplier of Wollaston reported as an early synonym for osmium. No origin was John Johnson, a commercial assayer in London for this name could be found except the references and the father of Percival Johnson, co-founder of cited by the historians of science James Riddick Johnson Matthey Plc) (6–8). Partington (1886–1965) and John Albert Newton-Friend On 21st June, 1804, Tennant read a paper to the (1881–1966) (1–3). Both authors were contradictory Royal Society on the experiments he performed during on the origin of the word ‘ptène’ and it could not be the summer of 1803 on a platinum ore from New determined whether the author was Smithson Tennant Granada (now known as Colombia) (7). In his paper, he (1761–1815), the British discoverer of osmium, or one announced the discovery, isolation and naming of two of the French chemists Antoine-François Fourcroy new chemical elements: iridium and osmium, the latter

190 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695631 Johnson Matthey Technol. Rev., 2017, 61, (3) because of the “pungent and peculiar smell […] [of its] combined in metallic sulfides, copper, titanium, very volatile metallic oxide” (osmium tetroxide (OsO4)) chromium, gold, platinum and a new metal” (9). Across the Channel, an extract of Tennant’s paper (“le platine brut apporté en grains du Pérou, was translated in the Bibliothèque Britannique published contient au moins neuf substances différentes; in Geneva, Switzerland, and partially reprinted in the savoir, du sable quartzeux et ferrugineux, du fer, Annales de Chimie on 22nd October, 1804 (10). du soufre vraisemblablement combiné en sulfures Meanwhile, Fourcroy and Vauquelin were repeating métalliques, du cuivre, du titane, du chrôme, de experiments by the young Collet-Descotils who claimed l’or, du platine et un métal nouveau”) (18). to have isolated a new element from the black residue A second note was added in the next volume where of platinum after its treatment with aqua regia (11–14). different reactions on this new metal were reported Tennant himself was aware of these experiments and without naming it and the presence of osmium in the cited them in his 1804 paper (9). insoluble residue was noted by Fourcroy who reported The main interest of the French chemists was to isolate a “pungent, spicy astringent” smell (“âcre, piquante palladium. In April 1803 a strange notice circulated in comme styptique”) (an indication of OsO4) (19). the English gazettes that a new metal isolated from Although Collet-Descotils repeated Wollaston’s platinum ore was sold under the name of palladium experiments, no further paper was published by the by a merchant named Mr Foster in London. Wollaston French chemists in 1805 (20, 21). However, in the fourth resorted to this kind of subterfuge to establish his volume of the Encyclopédie Méthodique, Fourcroy priority on the first isolation of palladium while keeping compiled and defined chemical terms and under the his process secret until he had completed his research item ‘Docimasie’, we can read: on platinum melting (Wollaston was later involved “We did not speak about either the colombium in the preparation and sale of platinum hardware). discovered by Mr Hatchette nor tantalum Unfortunately the new metal was not recognised found recently by Mr Ekheberg nor ptene nor because a well-known analytical chemist, Richard cerium newly announced by Messrs Hisenger Chenevix (1774–1830), considered it as a mixture & Berzelius because their ores are still too of mercury and platinum (15, 16). This conclusion uncommon” intrigued the scientific community and several famous (“On n’a point parlé ici du colombium découvert chemists, including Vauquelin and Fourcroy, started par M. Hatchette, ni du tantale trouvé analysing platinum (11–14). dernièrement par M. Ekheberg, ni enfin du The first results of the three French chemists were read ptène, ni du cérium annoncé tout récemment at the Institut National (Class of sciences, mathematics par MM. Hisenger & Berzelius, parce que leurs and physics) on 26th September and 10th October, mines sont encore trop rares”) (22). 1803 (11–14). Collet-Descotils, a student of Fourcroy In the same volume, three ‘ptène’ derivatives were and Vauquelin, described a product with iridium-related presented as possible compounds: the “ptene malate” properties (11). (“malate de ptène”), “ptene gallate” (“gallate de ptène”) On 13th February, 1804, Fourcroy and Vauquelin and “ptene fluoride” (“fluate de ptène”) (22). However, presented their whole research in a second dissertation they were still unknown because nobody had isolated where they concluded on this newly discovered ‘ptène’ “in a state of purity and very abundantly” element: (“à l’état de pureté & assez abondamment”) (22). “we will not decide yet ... on the naming of this The only definition available in 1805 for ‘ptène’ was metallic body so different from those of the same settled as “metal combined with platinum” (“métal type” qui accompagne le platine”) (22). A more elaborated (“nous ne nous prononcerons encore … sur le definition was expected in the next volume but it never nom qu’il faudra imposer à ce corps métallique appeared (23). si différent de tous ceux du même genre”) (17). On 17th March, 1806, Fourcroy finally recognised the In a second set of publications on the same subject, presence of four new elements in platinum (in addition Fourcroy mentioned: to osmium and iridium, there were also palladium and “the platinum ore imported from Peru contains rhodium). He admitted that the metal they named ‘ptène’ at least nine different substances; namely was constituted of two distinct elements (although he quartz and iron-bearing sand, iron, sulfur likely also considered that the name ‘ptène’ was attributed

191 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695631 Johnson Matthey Technol. Rev., 2017, 61, (3) to osmium) (24). A note was added to remember the None of the references from the Encyclopédie contribution of Collet-Descotils (25). (This note contains Méthodique (in 1805 and 1808) refer to a possible a mistake: the paper of Collet-Descotils it refers to was paper on the naming of ‘ptène’ (22, 23). What should printed in the 7th issue. The 5th and the 6th issues were we understand? We believe that between 21st June, wrongly written in the title and the content of the note.) 1804, and 17th March, 1806, the French chemists “In a first report of my work on platinum [...] we were uncertain of the platinum chemistry and they announced [...] the existence of a new metal did not want to publish anything until their results firstly named ptene and later osmium and iridium were definitive. A possible source of delay to confirm in the black powder that resists the action of Tennant’s results was the difficulty in obtaining platinum nitro-muriatic acid [aqua regia] […] osmium is for their experiments (7). very volatile, very easily oxidised. We were the A first account of splitting ‘ptène’ into two distinct first to discover this singular and very different elements (osmium and iridium) had been suggested metal in summer 1803 [...] Mr Tennant found by Jean-André-Henri Lucas (1780–1825) in his book and distinguished it only a few months after “Tableau méthodique des espèces minérales” (1806) us because he mentioned in his dissertation whose acceptance for publication dated back to 13th the first Mémoire we had published in the November, 1805 (26). A similar observation was Annales de Chimie. We had proposed ptene done in Joseph Capuron’s work (27). The distinction as a name for this metal but we willingly accept between the platinoids was not clear to everyone: the denomination of osmium which seems a publication in the Journal de Physique (January preferable to us” 1806) presented rhodium and iridium as ‘ptène’ (28). (“Dans un premier extrait de mon travail sur le A possible explanation for this mistake may be due platine […] nous avons annoncé […] l’existence to a correction in the third edition of the Philosophie d’un métal nouveau nommé d’abord ptène et Chimique (1806) of Fourcroy where ‘ptène’ was depuis osmium et iridium dans la poudre noire mentioned with platinum (29). qui résiste à l’action de l’acide nitro-muriatique The story of ‘ptène’ was later revived by Jöns Jacob [aqua regia] […] L’osmium […] est très volatil, très Berzelius (1779–1848) during his research on osmium oxydable. Nous avons découvert, les premiers, in 1828. The history of the discovery of platinoids was dans l’été 1803, ce métal singulier et très- summarised as follows: différent […] M. Tennant ne l’a trouvé et distingué “The ancient chemists associated every metal que quelques mois après nous, parce qu’il cite contained in platiniferous sand, except gold, dans sa dissertation le premier Mémoire que with platinum until Collet-Descotils discovered nous avions publié dans les Annales de Chimie. two new substances; a blue sublimate … and a Nous avions proposé d’appeler ce métal ptène; red substance colouring the ammoniac muriate mais nous adoptons volontiers la dénomination of platinum which he attributed to an unknown d’osmium qui nous paraît préférable”) (24). metal. While Collet-Descotils was still involved in This naming history was summarised two years later his research, Fourcroy and Vauquelin, aware of in the Encyclopédie Méthodique where Fourcroy wrote it, started their own experiments and discovered an article on osmium: several properties of this new metal they named “From its last characteristic [the pungent smell ptene. Like Collet-Descotils they confounded

of OsO4] Mr Tennant proposed the name of under this name every metal associated with osmium from the Greek osmè, smell. We had platinum. Soon afterwards Wollaston discovered already discovered these features and we palladium and then rhodium … Tennant taking had proposed the name of ptene for which the care of the fraction of platinum insoluble in aqua name osmium, which we prefer, was substituted” regia found iridium and osmium at about the (“c’est de cette dernière propriété que M. Tennant same period” a tiré le nom d’osmium, du mot grec osmè, odeur. (“Les anciens chimistes prenaient tous les Nous avions déjà découvert ces caractères, & métaux contenus dans le sable platinifère, nous en avions tiré le nom de ptène, auquel celui excepté l’or, pour du platine, jusqu’au moment où d’osmium, que nous préférons, a été substitué”) Collet-Descotils fit connaître deux substances (23). nouvelles; un sublimé bleu … et la matière

colorant en rouge le muriate ammoniacal “I shall take, therefore, for the chemical sign, the de platine, qu’il attribua à la présence d’un initial letter of the Latin name of each elementary métal nouveau auquel il ne donna aucun nom substance: but as several have the same initial particulier. Pendant que Collet-Descotils était letter, I shall distinguish them in the following encore occupé à ses expériences, Fourcroy manner: 1. In the class which I call metalloids, et Vauquelin, instruits de ses expériences, I shall employ the initial letter only, even when commencèrent des recherches semblables, this letter is common to the metalloid and to et découvrirent plusieurs propriétés de ce some metal. 2. In the class of metals, I shall nouveau métal, qu’ils nommèrent ptène; mais distinguish those that have the same initials with ils confondirent, comme Collet-Descotils, another metal, or a metalloid, by writing the first sous ce nom tous les métaux inconnus qui two letters of the word. 3. If the first two letters accompagnent le platine. Wollaston découvrit be common to the two metals, I shall, in that peu de temps après le palladium, et plus tard case, add to the initial letter the first consonant le rhodium … Tennant, en s’occupant de la which they have not in common: for example, S partie de platine insoluble dans l’eau régale, = sulfur, Si = silicium, St = stibium (antimony), Sn trouva presqu’en même temps l’iridium et = stannum (tin), C = carbonicum, Co = Cobaltum l’osmium”) (30). (cobalt), Cu = cuprum (copper), O = oxygen, W. A. Smeaton adopted the same conclusions Os = osmium, &” (35). as Berzelius: in their 1803 and 1804 memoirs, the A general survey of the Berzelian symbolism can be French chemists reported the characteristics of found in the literature (36) and the influence of Thomson iridium ammonium salts and OsO4 (maybe rhodium on Berzelius has been reported (37). derivatives too) but failed to isolate a metal from the In the system of Berzelius, iridium and rhodium had residue of platinum ore (31). The precise description of respectively the symbols I and R because there were the pungent smell of OsO4 by Fourcroy and Vauquelin no other metals starting with the letter I or R (38). led them to consider that the name ‘ptène’ was mainly Things changed with the discoveries of iodine in 1811 attributed to osmium (23–25). (39) and ruthenium in 1844 (40). On the etymology of osmium or ‘ptène’, neither Since iodine was a metalloid according to Berzelius, it Tennant nor Fourcroy and Vauquelin were clear on a had the priority for the initial letter only. The modification Greek origin in their first publications (9, 24). Tennant could be read in his work ‘Essai sur la Théorie des only mentioned a connection with smell: Proportions Chimiques et sur l’Influence Chimique de “… as this smell is one of the most distinguishing l’Electricité’ of 1819. While the symbol for iridium is still I in character, I should on that account incline to call the main text, the table at the end of the book was correct: the metal osmium.” (9) I stands for iodicum (iodine in Latin) and Ir for iridium (41). In 1808, Fourcroy and Klaproth separately mentioned Concerning ruthenium and rhodium, Claus followed the Greek origin of osmium (osmè: smell) and of ‘ptène’ the rules of Berzelius when he correctly wrote the new (ptènos: winged) (23, 32). symbols Ru and Rh (40, 42).

History of the Element Symbols Conclusion

The story was not finished. None of the English, French To conclude, one may say that osmium and iridium were or Swedish scientists discovered the last element of definitely discovered by Smithson Tennant during the the platinum group, ruthenium (Ru). It was only in 1844 summer of 1803 (6–8). The team of French chemists that Carl Claus (1796–1864) isolated this metal and unfortunately did not achieve the separation of iridium the aging but world-respected Berzelius validated his and osmium although they described the properties discovery (33, 34). This discovery had an impact on of salts or oxides from both elements. Fourcroy and rhodium: it changed its chemical symbol from R to Rh. Vauquelin honestly attributed the discovery to Tennant In 1813, Berzelius, inspired by the “System of and no controversies occurred. The name ‘ptène’ was Chemistry” of Thomas Thomson (1773–1852), had attributed to a mixture of osmium and iridium which decided to give a chemical sign to each atom: joined the list of the “lost elements” recorded by Fontani

6. D. McDonald, Platinum Metals Rev., 1961, 5, (4), 146 7. D. McDonald and L. B. Hunt, “A History of Platinum and its Allied Metals”, Johnson Matthey, London, UK, 1982, 450 pp 8. M. C. Usselman, “Pure Intelligence: The Life of William Hyde Wollaston”, The University of Chicago Press, Chicago, USA, 2015, 424 pp 9. S. Tennant, Phil. Trans. R. Soc. Lond., 1804, 94, 411 10. S. Tennant, Ann. Chim., 1804, 52, 47 11. H. V. Collet-Descotils, Ann. Chim., 1803, 48, 153 12. A. F. Fourcroy and N. L. Vauquelin, Ann. Chim., 1803, 48, 177 13. A. F. Fourcroy and N. L. Vauquelin, Ann. Chim., 1804, 49, 188 14. A. F. Fourcroy and N. L. Vauquelin, Ann. Chim., 1804, 49, 219 Fig. 1. Blue-grey crystals of osmium (Courtesy of 15. M. C. Usselman, Ann. Sci., 1978, 35, (6), 551 CristalTech Sàrl, Switzerland) 16. N. L. Vauquelin, Ann. Chim., 1803, 46, 333 17. A. F. Fourcroy and N. L. Vauquelin, Ann. Chim., 1804, 50, 5 18. A. F. Fourcroy, Ann. Mus. Hist. Nat., 1804, 3, 149 et al. (43). See also the website of Peter van der Krogt 19. A. F. Fourcroy, Ann. Mus. Hist. Nat., 1804, 4, 77 on the periodic table (44). 20. H. V. Collet Descotils, J. des Mines, 1805, 18, Osmium still remains particular because of the strong (105), 185 smell of its volatile oxide but one often forgets its 21. J. L. Howe and H. C. Holz, “Bibliography of the Metals distinctive blue colour (Figure 1). In 1814, Vauquelin of the Platinum Group 1748-1917”, Bulletin 694, US wrote: Geological Survey, Washington, USA, 1919, 558 pp “As to its colour, if we can judge from certain 22. A. F. Fourcroy, “Encyclopédie Méthodique: Chimie et evidence, I believe that it is blue” Métallurgie”, Vol. 4, H. Agasse, Paris, France, 1805 (“Quant à la couleur, si l’on peut en juger sur 23. A. F. Fourcroy, “Encyclopédie Méthodique: Chimie et quelques apparences, je crois qu’elle est bleue”) Métallurgie”, Vol. 5, H. Agasse, Paris, France, 1808 (45). 24. A. F. Fourcroy and N. L. Vauquelin, Ann. Mus. Hist. Nat., 1806, 7, 401 Acknowledgments 25. A. F. Fourcroy and N. L. Vauquelin, Ann. Mus. Hist. Nat., 1806, 8, 248 The authors thank Jacques Falquet and Francine 26. J. A. H. Lucas, “Tableau Méthodique des Espèces Chopard for critical proofreading. Minérales: Première Partie”, D’Hautel, Paris, France, 1806 References 27. J. Capuron, “Nouveau Dictionnaire de Médecine, de Chirurgie, de Physique, de Chimie et d’Histoire 1. W. P. Griffith,Platinum Metals Rev., 2004, 48, (4), 182 Naturelle”, J. A. Brosson, Paris, France, 1806 2. J. R. Partington, “A History of Chemistry”, Vol. 3, 28. J. C. Delamétherie, J. Phys. Chim. Hist. Nat., 1806, Macmillan & Co Ltd, London, UK, 1962, p. 105 62, 32 3. J. N. Friend, “Man and the Chemical Elements: From 29. A. F. Fourcroy, “Philosophie Chimique ou Vérités Stone-Age Hearth to the Cyclotron”, Charles Griffin & Fondamentales de la Chimie Moderne”, 3rd Edn., Company Ltd, London, UK, 1951, p. 354 Tourneisen Fils, Paris, France, 1806 4. W. P. Griffith,Q. Rev. Chem. Soc., 1965, 19, (3), 254 30. J. A. C. Berzelius, Kongl. Vet. Acad. Handl., 1828, 16, 5. J. Wisniak, Indian J. Chem. Technol., 2005, 25; translated into French in Ann. Chim. Phys., 1829, 12, (5), 601 40, 52

31. W. A. Smeaton, Platinum Metals Rev., 1963, 7, 38. J. Berzelius, Ann. Philos., 1814, 3, 244 (3), 106 39. M. B. Courtois, Ann. Chim., 1813, 88, 304 32. M. H. Klaproth and F. Wolff, “Chemisches Wörterbuch”, 40. C. Claus, Bull. Cl. Phys.-Math., 1845, 3, (20), 311 Vol. 3, Voss, Berlin, Germany, 1808 41. J. J. Berzelius, “Essai sur la Théorie des Proportions 33. C. Claus, Gorn. Zh., 1845, (7), 157 Chimiques et sur l’Influence Chimique de l’Electricité”, Méquignon-Marvis, Paris, 1819 34. G. B. Kauffman, J. L. Marshall and V. R. Marshall, 42. C. Claus, Justus Liebigs Ann. Chem., 1846, 59, (2), 234 Chem. Educator, 2014, 19, 106 43. M. Fontani, M. Costa and M. V. Orna, “The Lost 35. J. Berzelius, Ann. Philos., 1814, 3, 51 Elements: The Periodic Table’s Shadow Side”, Oxford 36. M. P. Crosland, “Historical Studies in the Language University Press, New York, USA, 2015, 576 pp of Chemistry”, Dover Publications, New York, USA, 44. P. van der Krogt, “Names That Did Not Make 2004, 448 pp It”, Elementymology & Elements Multidict, The 37. J. R. Partington, J. Chem. Technol. Biotechnol., 1936, Netherlands, 2010 55, (40), 759 45. N. L. Vauquelin, Ann. Chim., 1814, 89, 225

The Authors

Rolf Haubrichs is a chemist and Pierre-Léonard Zaffalon received co-founder of CristalTech Sàrl, his PhD in bioorganic chemistry Switzerland, a young start-up from the University of Geneva, involved in the crystallisation of Switzerland, in 2012. In 2014, he platinum group metals. joined CristalTech Sàrl.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

The ‘Nano-to-Nano’ Effect Applied to Organic Synthesis in Water A remarkable opportunity to use not only water as the reaction medium but very little surfactant and catalyst containing only ppm levels of metal under mild conditions

Bruce H. Lipshutz The short answer is that times have changed and as Department of Chemistry & Biochemistry, University of environmental and human health issues continue to California, Santa Barbara, CA 93106, USA come into focus, so must our attention take note that the chemistry enterprise is creating huge amounts of Email: [email protected] organic waste, the most egregious component of which is organic solvents (9). Getting them out of organic chemistry should be a goal that chemists strive to The remarkable benefits associated with the attraction achieve, as the way this field is currently practiced is of polyethylene glycol (PEG)-containing nanomicelles just not sustainable. How can it be that there is not a to metal nanoparticles in water allows for varying types single key reaction parameter associated with the way of important catalysis to be done under very mild and catalysis is done today that overlaps with the manner green conditions. in which nature continues to practice organic chemistry (Figure 1)? Fortunately, there is already strong 1. Introduction evidence indicating that by redesigning surfactants for synthetic chemistry (5–8), these form nanomicelles Aqueous micellar catalysis is far from new (1, 2). that enable homogeneous catalysis to be efficiently Indeed, although a wealth of information on this topic applied to the very same reactions valued by synthetic has been accumulated over many decades (3, 4), an chemists, but with one major difference: they are done appreciation of the potential for this chemistry to replace under environmentally responsible conditions. organic solvents as the reaction medium in many of The two leading nonionic designer surfactants the most commonly used reactions in catalysis has forming micellar arrays in water that accommodate only recently been advanced (5–8). The explanations many differing reaction partners, catalysts and behind this surprising state of affairs may lie in the lack additives are DL-α-tocopherol methoxypolyethylene of training received in this area and the normal mindset glycol succinate (TPGS-750-M) (10) and β-sitosterol among synthetic organic chemists that the presence of methoxyethyleneglycol succinate (SPGS-550-M) also water in a reaction, in other than selected cases (for known as ‘Nok’ (11) (Figure 2). Both form nanomicelles example hydrolysis), is to be avoided. Hence, its use that, unlike the majority of surfactants typically found in as the entire reaction medium is rarely a consideration. catalogues frequented by the synthetic community, are Simply put, organic chemistry takes place in organic of the ‘right’ size or shape leading to bond formations solvents and so why ‘complicate’ an already challenging that are usually as good or better than those observed science? in organic media. But what had originally not been fully

Solvent/medium Reaction temperature Catalyst

Organic Organic Heating/ 1–5 mol% chemistry solvents cooling (10,000–50,000 ppm) Overlap: none! Nature Water Ambient Trace metals

Fig. 1. Extent of overlap as practiced by nature vs. modern organic chemistry: none

TPGS-750-M O O O Substrates O 17 housed inside O O

PEG portion Each forms Racemic vitamin E nanomicelles with (M)PEG portion O on outside O O O Nok H H 13 O H + H

(M)PEG portions on β-sitosterol outside of micelles deliver nanomicelles to catalyst NP catalyst

‘Nano-to-nano’ Fig. 2. Designer surfactants leading to nanomicelles that participate in ‘nano-to-nano’ effect

appreciated is that the methoxy polyethylene glycol to the catalyst. This ‘nano-to-nano’ effect offers a (MPEG) (or polyethylene glycol (PEG), in general) remarkable opportunity to use not only water as the present in these 40–60 nm spheres of TPGS-750-M reaction medium, but very little surfactant and catalyst or rods of Nok has a natural tendency to function as containing only ppm levels of metal, and to do such a stabilising ligand around metal nanoparticles (NPs) heterogeneous catalysis under atypically very mild (12, 13) that are also present as catalysts in the water. conditions (between 22ºC and 45ºC). In other words, generation of metal nanoparticles That this phenomenon is not only happening but also as catalysts attract the MPEG-containing micelles, likely to be responsible for the facile catalysis observed which is tantamount to an internal delivery system is clear from cryo-transmission electron microscopy of the reaction partners housed within the micelles (cryo-TEM) analyses. These data show an unequivocal

197 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695785 Johnson Matthey Technol. Rev., 2017, 61, (3) preponderance of nanomicelles aggregated around introduction of the same or an alternative educt, along metal NPs, whereas in the absence of such NPs with fresh reductant. The overall reliance on organic an otherwise even distribution of micelles in the solvents, therefore, was shown to be at least an order surrounding water is seen. While such an association of magnitude lower than amounts often required with does not prove that the observed catalysis is taking similar reactions in the literature (15). Moreover, these place as proposed, it does document the ‘nano-to- differences are to be realised prior to recycling of the nano’ effect that localises the high concentration of aqueous mixtures. substrate within the micelle directly at the catalyst A similar ‘nano-to-nano’ effect was seen with new surface, potentially accounting for the lack of energy NPs derived from the reduction of iron(III) chloride

(in the form of heat) needed to enhance interactions (FeCl3), where either the naturally occurring content of in these heterogeneous mixtures that otherwise might Pd within FeCl3 or by externally doping with Pd(OAc)2 be needed in organic solvents where no such formal at the ppm level sufficed to arrive at active catalysts delivery mechanism exists. useful for important cross-couplings (Figure 4) (16). That is, given the threshold presence of ca. 350 ppm 2. The ‘Nano-to-Nano’ Effect: Palladium, Nickel Pd, NP formation upon treatment of the mixture and Copper Nanoparticles (i.e., FeCl3 + 350 ppm Pd) with methylmagnesium chloride (MeMgCl) in tetrahydrofuran (THF) at ambient 2.1 Palladium temperatures affords the desired NP catalysts. When The first observation came unexpectedly when Pd NPs prepared in the presence of SPhos, the resulting were generated from the combination of palladium NPs mediate Suzuki-Miyaura couplings in aqueous acetate (Pd(OAc)2) and sodium borohydride (NaBH4) nanomicelles between room temperature and 45ºC. in aqueous TPGS-750-M at room temperature (14). Extensive analyses of this isolable powder, including The resulting heterogeneous aqueous mixture could a cryo-TEM experiment conducted on the reaction be used to great advantage, converting a variety medium (TPGS-750-M + water) again confirmed the of unsymmetrically disubstituted alkynes to the aggregation of nanomicelles together with the solid iron corresponding Z-alkenes, typically with >99:1 Z:E nanoparticles containing ppm levels of palladium (here selectivity (Figure 3). Part of the success observed in designated Fe/ppm Pd NPs). these net Lindlar-like reductions is the facility with which This newly developed NP platform, consisting of the reaction mixture could be recycled, including the mostly Mg, Cl and THF, with Fe accounting for only ca. water, the surfactant therein, and the Pd catalyst. Thus, 2.5% of the mix, can be altered as a function of the an ‘in-flask’ extraction with an ethereal solvent (for ligand added prior to their preparation. Changing the example methyl tert-butyl ether (MTBE)) afforded the recipe from inclusion of SPhos to XPhos now allows product, leaving behind all other ingredients ready for for efficient ‘nano-to-nano’ catalysis of Sonogashira

Lindlar-like reductions using Pd NPs: alkynes to Z-alkenes:

NH2 BnO OAc = NPs

90%, 95:5 Z:E 99%, >99:1 Z:E

Preparation: Pd(OAc)2 + NaBH4 OTHP TBSO in aqueous TPGS-750-M OH OBn OH 98%, >99:1 Z:E 91%, >99:1 Z:E Fig. 3. Representative Lindlar-like reductions of alkynes to Z-olefins (14)

Suzuki-Miyaura cross-couplings with Fe/ppm Pd NPs

Fe/ppm Pd NPs Ar-Br + Ar'-B(OH)2 Ar-Ar' Preparation: aq. TPGS-750-M K3PO4, RT–45ºC = NPs FeCl3 + 350 ppm Pd(OAc)2 + SPhos + MeMgCl in THF O Boc O H Me N N Cy N N N O F N N Me HN O O 26 h, 85% 16 h, 90% 20 h, RT, 94% 28 h, 86%

Fig. 4. Fe/ppm Pd NPs that enable Suzuki-Miyaura couplings in aqueous TPGS-750-M NPs based on the ‘nano-to-nano’ effect (16)

couplings in the same recyclable aqueous mixtures groups. Importantly, use of hydrogen gas in place of (Figure 5) (17). Recycling is smoothly orchestrated a borohydride is totally incompatible with this catalyst using very limited amounts of a single and recyclable, and in fact, is detrimental to the overall reduction. organic solvent for 'in flask' extraction. 2.2 Nickel These NPs derived from FeCl3 can also be prepared in the absence of any ligand, otherwise required for Notwithstanding the reported success of the catalyst (Fe/ – Pd-catalysed cross-couplings. In this case, the ‘nano- ppm Pd NPs + BH4 ) applied to nitro group reductions to-nano’ effect can be used to effect reductions of (above) (18, 19), doping of this NP platform with metals aromatic and heteroaromatic nitro groups in water other than Pd offers either additional benefits to existing at room temperature (18, 19). The stoichiometric processes, or potentially new opportunities to lower reductant is NaBH4, although as recently updated both base and precious metal usage to ppm levels. Part at Novartis in Basel, Switzerland, the addition of of the incentive to further investigate along these lines potassium chloride (KCl) or the use of fresh potassium is that the amount of residual metal(s) in the desired borohydride (KBH4) appears to be the hydride source products has been found to be below tolerance levels of choice (20). Only 80 ppm of palladium (as Pd(OAc)2) as established by the US Food and Drug Administration is required for these NP reductions, again implicating a (FDA). That is, going into these reactions with ppm palladium hydride species (Figure 6). The mild reaction amounts of transition metal catalysts, rather than the conditions account for the tolerance of many functional more typical 1–5 mol% range (10,000–50,000 ppm),

OTBS Ph TMS

F3C

CHO N

CF3 93% 98% 95% 89%

Fig. 5. Fe/ppm Pd NPs used for Sonogashira couplings in aqueous TPGS-750-M (17)

reagent, presumably benefiting from the same ‘nano-to- nano’ effect. Indeed, related NPs are formed using Cu(I)

R R admixed with the same FeCl3, followed by standard NO treatment with MeMgCl in THF (vide supra). Akin to 2 NH2 observations with other NPs in this series, the catalyst can be generated and used in situ or isolated for use NaBH4 at a later date. The first type of catalysis examined has been click chemistry between a terminal alkyne and an azide; when performed in aqueous TPGS-750-M at room temperature, cycloadditions to the anticipated triazoles take place quite readily (22). In addition to representative examples shown in Figure 8, products nano-Fe/ppm Pd formed upon recycling of the aqueous reaction mixture ‘nano-to-nano’ are suggestive that the catalyst does not lose its activity Fig. 6. Ligandless Fe/ppm Pd NPs applied to nitro group when handled under an inert atmosphere to prevent reductions (18–20) autoxidation to the otherwise inactive Cu(II) form. leads to acceptable ppm levels of metal impurities that 3. Summary obviate additional time and cost for their removal, a very common occurrence under traditional conditions Micellar catalysis has been made highly effective by in organic solvents. In work soon to appear (21), virtue of newly engineered nanoreactors in water, doping these Fe-based NPs with additional ppm levels offering the synthetic community an environmentally of a Ni(II) salt affords a reagent that has been found, responsible alternative to waste-generating organic likewise, to efficiently reduce nitro group-containing solvents as reaction media. The green attributes of aromatic or heteroaromatic compounds, but often at a this approach to synthesis, however, go well beyond far greater rate under otherwise identical conditions of this simple solvent switch. In fact, metal NP catalysts concentration, time and temperature. Figure 7 shows present in such aqueous solutions populated by a few comparison cases. MPEG-containing nonionic surfactants TPGS-750-M and Nok are active under very mild conditions due to 2.3 Copper this ‘nano-to-nano’ effect, a phenomenon not found Another metal used extensively in organic chemistry in traditional organic solvents. Applications of metal is copper and hence, doping the iron nanoparticles NPs that can be formed containing either base (for with ppm levels with a Cu salt, rather than Pd or Ni example Ni or Cu) or precious (for example Pd) metals (Fe/ppm Cu NPs) might form a potentially useful to important reaction types, such as reductions and

Fe/ppm Ni NPs Ar NO2 Ar–NH2 TPGS-750-M, H2O, RT O CF3 MeS Cl N

F3C N NO2 NO2 NO2

Original Fe/ppm Pd NPs 8 h, 90% 12 h, 72% 2 h, 94%

New Ni-doped NPs 8 h, 88% 2 h, 88% 30 min, 98%

Fig. 7. Faster reductions with new NPs doped with Ni (21)

N R Fe/ppm Cu nanoparticles R + R’-N3 N 2 wt% TPGS-750-M, H2O, RT N base R’

Ph N N N Cl H N N 9 N N N N

Bn Bn

90% 88% 93%

Fig. 8. Representative examples of Fe/ppm Cu NPs applied to click chemistry

cross-couplings, have been demonstrated. Future 10. B. H. Lipshutz, S. Ghorai, A. R. Abela, R. Moser, developments involving other precious metals, such T. Nishikata, C. Duplais, A. Krasovskiy, R. D. Gaston as rhodium and iridium, seem ripe for investigation, and R. C. Gadwood, J. Org. Chem., 2011, 76, furthering the appeal of this new green chemistry. (11), 4379 11. P. Klumphu and B. H. Lipshutz, J. Org. Chem., 2014, References 79, (3), 888 1. D. Myers, “Surfactant Science and Technology”, 3rd 12. Z. Hou, N. Theyssen, A. Brinkmann and W. Leitner, Edn., John Wiley & Sons, Inc, New Jersey, USA, Angew. Chem. Int. Ed., 2005, 44, (9), 1346 2006, 400 pp 13. B. Feng, Z. Hou, H. Yang, X. Wang, Y. Hu, H. Li, 2. M. N. Khan, “Micellar Catalysis”, Surfactant Science Y. Qiao, X. Zhao and Q. Huang, Langmuir, 2010, 26, Series, Vol. 133, Taylor & Francis Group LLC, Florida, (4), 2505 USA, 2007, 482 pp 14. E. D. Slack, C. M. Gabriel and B. H. Lipshutz, Angew. 3. T. Dwars, E. Paetzold and G. Oehme, Angew. Chem. Chem. Int. Ed., 2014, 53, (51), 14051 Int. Ed., 2005, 44, (44), 7174 15. R. A. Sheldon, Green Chem., 2017, 19, (1), 18 and 4. B. Lindman and H. Wennerström, ‘Amphiphile references therein Aggregation in Aqueous Solution’, in “Micelles”, Topics in Current Chemistry, Vol 87, Springer-Verlag, Berlin, 16. S. Handa, Y. Wang, F. Gallou and B. H. Lipshutz, Heidelberg, Germany, 1980, pp. 1–83 Science, 2015, 349, (6252), 1087 5. B. H. Lipshutz and S. Ghorai, Green Chem., 2014, 16, 17. S. Handa, Y. Wang, F. Gallou and B. H. Lipshutz, (8), 3660 manuscript in preparation 6. B. H. Lipshutz and S. Ghorai, Aldrichim. Acta, 2012, 18. J. Feng, S. Handa, F. Gallou and B. H. Lipshutz, 45, (1), 3 Angew. Chem., 2016, 128, (31), 9125 7. B. H. Lipshutz and S. Ghorai, Aldrichim. Acta, 2008, 19. M. Orlandi, D. Brenna, R. Harms, S. Jost and M. 41, (3), 59 Benaglia, Org. Process Res. Dev., 2016, just accepted 8. G. La Sorella, G. Strukul and A. Scarso, Green Chem., manuscript 2015, 17, (2), 644 20. C. M. Gabriel, M. Parmentier, C. Riegert, M. Lanz, S. 9. P. J. Dunn, R. K. Henderson, I. Mergelsberg and Handa, B. H. Lipshutz and F. Gallou, Org. Process A. S. Wells, ‘Moving Towards Greener Solvents Res. Dev., 2017, 21, (2), 247 for Pharmaceutical Manufacturing – An Industry Perspective’, 13th Annual Green Chemistry & 21. H. Pang and B. H. Lipshutz, manuscript in preparation Engineering Conference, Maryland, USA, 23rd–25th 22. A. Adenot, E. B. Landstrom, F. Gallou and B. H. June, 2009 Lipshutz, Green Chem., 2017, 19, (11), 2506

The Author

Bruce Lipshutz spent four years at Yale University, USA, (1973–1977) as a graduate student with Harry Wasserman. After a two-year postdoctoral stint with E. J. Corey at Harvard University, USA, as part of the team involved with the total synthesis of the antitumour agent maytansine, he began his academic career at the University of California, Santa Barbara, USA, in 1979, where today he continues as Professor of Chemistry. His programme in synthesis focuses on new reagents and methodologies, mainly in the area of organometallic chemistry. While these contributions tended to fall within the area of ‘traditional’ organic synthesis, more recently his group has shifted in large measure towards the development of new technologies in green chemistry, with the specific goal being to get organic solvents out of organic reactions. To accomplish this, the Lipshutz group has introduced the concept of ‘designer’ surfactants that enable key transition metal-catalysed cross-couplings, and many other reactions, to be carried out in water at room temperature. Most recently, his group has turned its attention to developing new catalysts for key Pd- and Au- catalysed reactions that involve bond formations requiring only parts per million levels of metal, each being conducted in water under very mild conditions. The potential for his group’s work in this field to significantly influence, and in time transform the way in which organic chemistry is practiced in the future, led to a Presidential Green Chemistry Challenge Award in 2011.

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“Sustainability Calling: Underpinning Technologies” Pierre Massotte and Patrick Corsi, Innovation, Entrepreneurship and Management Series, ISTE Ltd, London, UK, and John Wiley & Sons, Inc, Hoboken, USA, 2015, 407 pages, ISBN: 978-1-84821-842-0, £104.00, US$130.00, €124.80

Reviewed by Niyati Shukla the Centre de Gestion Scientifique at Mines ParisTech Johnson Matthey, Orchard Road, Royston, in France. Previously, he had an extensive career Hertfordshire, SG8 5HE, UK with IBM Corporation and the European Commission as well as successful start-up experience in artificial Email: [email protected] intelligence. In this book are outlined a set of key concepts and Massimo Peruffo models to support a new notion of sustainability that Johnson Matthey, Lydiard Fields, Great Western Way, takes into account the ever increasing complexity Swindon, SN5 8AT, UK of today’s world. Sustainability has been primarily Email: [email protected] focused on environmental issues, however the authors expand the concept to society, economics, politics, welfare, innovation, competiveness and everyday life (Figure 1). A novel formalism is necessary to redefine Introduction this new concept of sustainability and the authors bring “Sustainability Calling” is focused on the definition the notion of transformative research to apply models of new paradigms to define a new concept of already used in different scientific fields to the concept sustainability. Pierre Massotte has worked for IBM in of sustainability. Quality Assurance and then Advanced Technologies. He spent several years in IBM’s research and Resilience and Sustainability development laboratories in the USA, then became Scientific Director in EMEA Manufacturing to improve In Part 1, resilience and sustainability are proposed the competitiveness of IBM’s European manufacturing as the main drivers for innovation at a global scale. In plants and Development Laboratories. He joined Chapter 1 the authors introduce the concepts of scale the École des Mines d’Alès, France, as Deputy and time in nature and the law of correspondence. Director. His research and development topics are Any system can be divided into levels or subsystems, related to complexity, self-organisation and issues of for example macromolecules, cells, tissues, organs, business competitiveness and sustainability in global organism, population, communities and finally companies. He is the co-author of several books in biosphere. Each of the subsystems can interact and production systems management. He is now involved, influence all the others, and the authors propose that as senior consultant, in various ‘inclusive society’ to take into account such complexity metamodelling projects. The second author Patrick Corsi is an is required. Examples of metamodels are: cross- international consultant based in Brussels, Belgium, cutting that focuses on the interactions between lower and an Associate Practitioner in intensive innovation at and upper levels; and the ‘one level method’ in which

Mathematics & Management statistics biology, life, Computer psychology & sciences social ecology

Cybernectics information Systems theory theory

AI Complexity Nonlinear Connexionism sciences dynamic systems cognitivism Clt and Meast theory (NLDS)

Self-organisation Agent Bsd & emergence cellular automata evolution

Fractal & chaos theory behaviour structure Artificial life Global networks collective thinking & & web sciences consciousness

Sustainable engineering convergence theory

Fig. 1. A global and advanced vision for gathering and linking together the different theories and technologies for solving production or sustainability problems (Copyright John Wiley & Sons, Inc)

generalisations must be applied to create models countries like China, Russia, India, Korea, Indonesia applicable to each subsystem. and South Africa. They say that such phenomena Chapter 2 asks whether globalisation is really new. are necessary for the evolution of humanity. As soon This chapter characterises globalisation and explains as a big disturbance occurs in a society, globalisation some of its features. It evaluates how big paradigm implies three main factors in the current context and changes, or disasters, impact human behaviour, biosphere: the impact of events on human beings; influencing our mind and thoughts, conscience and risk management under unpredictable conditions and modes of governance. The authors explain that uncertainties; and modes of governance. The example globalisation is similar to economic evolution and any is given of an earthquake hitting Haiti in January 2010 phenomenon in globalisation is always associated and how the country showed changes in governance with the emergence of spontaneous orders, whose and management levels and achieved extraordinary unexpected consequences are far beyond what could outcomes. The chapter also classifies the tools and be imagined by looking at historical events. They put methods used in industries: anticipation and prediction forward their argument from a geographical point of view and concludes that cooperation, emergence and self- and present a map of the trading posts in ancient Rome, organisation are three particularly important concepts as well as describing the economic rise of developing of the science of complexity.

Chapter 3 unveils the notion of disturbance in the disturbances which increase the survival likelihood of decision-making process and in nature in general. The a species by flexibility, however if the mutation rate authors introduce three notions: asymmetry, Coriolis increases over a threshold dictated by the birth rate and chirality that have previously been formalised the survival rate will be negatively affected. Similarly, only for physical systems but are applied here in the disturbances in a competitive world can increase the context of sustainability. Asymmetry is a strong driver survival of a business. In a global scale the aging, in the decision-making process. In a company all the death and survival of businesses finds correspondence interactions between different entities that bring a to a biological ecosystem, a quick interchange of disparity of information can lead to an asymmetry of individuals and species can increase the survival rate the parts and can lead to the wrong decision; however of the ecosystem, while in a business ecosystem it can most of the decisions taken are mostly determined by promote innovation. external pressure. For example political and emotional In Chapter 9 the authors explain people’s reactions pressures have a strong effect during the decision to new emerging technology and how its benefits and process and they are difficult to take into account in a weaknesses surface after varying lengths of time. The model. Similarly Coriolis forces influence the movement internet is used as an example: it is an unstable and of fluids on the earth’s surface, however to model the interactive system that makes communicating and effect of the Coriolis forces the model has to use an exchanging information very easy, even governments inertial frame of reference that is not needed when have favoured the emergence of this system although the system under investigation is of a smaller scale. they cannot control it. The chapter highlights that In this chapter the utilisation of fractal theory to model applications such as Snapchat (Snap Inc, USA) and complex systems is proposed, however a simplification Confide (Confide Inc, USA) can restrain the resilience similar to the ‘one level method’ has to be made. of information. The notion of temporary data is Chapter 4 studies aspects of issues raised by project interesting for the future because it avoids malicious managers related to information, information systems people using confidential or private data against and decision-making, linking the contexts of time, others. It also protects email or social communication quantum fluctuation and entropy. It first focuses on in the organisation. The authors conclude that using the concepts of time and space, and then moves to this concept of social networking on the internet the perception of space and impacts related to these, leads to scaling and organisation network problems different antagonisms, time reversibility and entropy whereas using the ‘transient web’ can lead to obtaining to better understand the future challenges humanity a sustainable system. will face. The authors explain that the perception of The next chapter is a reminder about the complexity situation involves sensorial organs, the mind, ideas, of systems and presents the basic principles required feelings and time. However perception of time is to understand system complexity. Examples are different for people and perception of event duration given of biomedical and metabolic pathways in a cell is different depending on context. It is also explained and the Krebs cycle is used to explain the complexity that perception of time and space changes as new of the system. The chapter also details some developments in technology arise. The chapter advances applicable to the evolution of networks concludes by saying that failures and crises are not which are relevant to so-called ‘network theory’. the result of lack of time or the presence of time- In the chapter, a network is considered a complex irreversible problems, but the result of either lack of system and the concept of sustainability is applied skills or societal evolution. to the growth of networks and how their capabilities change over time. The Notion of Competitiveness Chapter 11 looks at issues raised by the project managers at the Project Management Institute (PMI). Part 2 revisits the notion of competiveness that in According to the authors, the only current way to the industrial and financial system is often reduced measure the sustainability of a system is to measure to profitability. The authors point out that decisions the ‘entropy generation’ of the system. In the chapter, based only on profitability can compromise long-term issues related to information, information systems and planning. More examples of transformative research decision-making are linked to notions of time, quantum are presented: DNA mutations are presented as fluctuation and entropy. It is proposed that networking

205 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695758 Johnson Matthey Technol. Rev., 2017, 61, (3) and self-organisation are contributing factors for “Sustainability reducing entropy generation. Calling: Underpinning Technologies” The final chapter is about defining certain terms used throughout the book, like ‘consciousness’. The authors say that “Pre-cognition, self-recognition, reflection, understanding and planning some meanings and actions are fully linked with consciousness”. The chapter discusses the law of accelerating returns, telepathy and telesympathy and differentiates the concepts of telepathy and telesympathy. Two applications are detailed to understand their impact on system sustainability: how to implement sustainable communications; and metadesign of a collaborative development platform.

Conclusions

The book is an interesting source of new concepts to redefine sustainability and how to use it in the decision- making process. The authors give an overview of the References complexity of today’s world and provide new ideas and 1. M. Aupetit, P. Couturier and P. Massotte, ‘Function tools to help tackle this complexity. While the book Approximation with Continuous Self-Organizing can be of interest to a wide public, a wide range of Maps using Neighbouring Influence Interpolation’, notions are covered and further details to understand International ICSC Symposium on Neural the profound interconnections between all the different Computation (NC’2000), Berlin, Germany, 23rd– concepts are presented in previous publications by 26th May, 2000, “Proceedings of the Second ICSC Massotte (1–3). Symposium on Neural Computation”, eds. H. Bothe Overall, the book is likely to be interesting for and R. Rojas, ICSC Academic Press, Canada, professionals working within industry who wish to Switzerland, 2000, p. 247 maintain the sustainability of their organisations 2. P. Massotte and P. Corsi, “Operationalizing in a changing world. It explains complex systems Sustainability”, ISTE Ltd, London, UK, and John Wiley associated with sustainability and answers questions & Sons, Inc, New Jersey, USA, 2015, 438 pp raised by professionals. For people interested in the 3. P. Massotte, ‘How Social Innovation is Shaking subject, the book will provide in-depth knowledge of Business Foundations’, Paris Innovation Review, 13th sustainability on a global level. June, 2013

The Reviewers

Niyati Shukla is a Quality Control Massimo Peruffo joined Johnson Laboratory Technician at Johnson Matthey in 2015. He is currently a Matthey at Royston, UK. She joined Senior Scientist, Quality Control and Johnson Matthey in 2015 and her Characterisation Laboratory Manager work focuses on analysing samples in fuel cells. The main focus of his using a range of techniques and research is to define and develop new making sure that they meet the characterisation tools to support the customer’s specification. technology department.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

Highlights of the Impacts of Green and Sustainable Chemistry on Industry, Academia and Society in the USA Impacts of green and sustainable chemistry on US industries, analysis of green chemistry resources available in academia (higher education) within the USA, and a perspective on the role of green chemistry in US society over the past ten years

Anne Marteel-Parrish* chemistry practices. It also describes how researchers, Department of Chemistry, Washington College, policy makers, educators, investors and industries Chestertown, MD 21620, USA can work together to “build innovative solutions that transform and strengthen the chemical enterprise” (1) *Email: [email protected] while addressing environmental and social challenges. The goal of this article is to understand why green Karli M. Newcity** chemistry is still primarily viewed as Joel Tickner, Department of Chemistry, Washington College, Director of Green Chemistry and Commerce Council Chestertown, MD 21620, USA (GC3), University of Massachusetts, Lowell, USA, puts it: as “an environmental activity rather than one that, **Email: [email protected] as experience shows, yields economic benefit, and it has yet to be integrated into the fabric of the chemical enterprise, educational systems, or government Trends such as population growth, climate change, programs” (1). urbanisation, resource scarcity, conservation of energy and water, and reduction of waste and toxicity have 1. Historical Perspective: Paving the Way to led to the development of sustainable practices in Green Chemistry industry, education and society. The desire to improve ways of living, the need for performance materials, The practice of green chemistry began in 1990 when and the urgency to close the gap between developed the creation of the Pollution Prevention Act was seen and emerging nations have propelled creative and as the USA’s initiative to become directly involved in innovative solutions based on green and sustainable pollution prevention at the source (2). In 1995, former chemistry to the forefront. This article provides an President Bill Clinton introduced the Presidential Green overview of the main impacts of green chemistry Chemistry Challenge Awards based on five (later on industry, academia and society in the USA in the changed to six) award categories: Greener Synthetic past ten years, as well as a summary of the drivers Pathways, Greener Reaction Conditions, the Design and barriers associated with the adoption of green of Greener Chemicals, Small Business, Academic,

207 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) and a new category created in 2015 based on a Janeiro, Brazil. Its focus was for the world to commit to specific environmental benefit: Climate Change (for a more sustainable development. the reduction of greenhouse gas emissions). These In 2002 the World Summit on Sustainable awards are used as a marketing tool to communicate Development (WSSD) in Johannesburg, South Africa, how green chemistry’s contributions have impacted led to a commitment to reduce global greenhouse gas the world. emissions and to a suggestion that all governments In 1998, John Warner and Paul Anastas published the around the world become unified in taking action book “Green Chemistry: Theory and Practice” providing towards sustainable development (5). tools, resources and applications of the 12 Principles More recently it was devised by W. Cecil Steward, of Green Chemistry (3). In 2001, the Green Chemistry the President and CEO of the Joslyn Institute for Institute decided to join forces with the American Sustainable Communities, Lincoln, Nebraska, USA, Chemical Society (ACS) to become advocates of a to represent sustainable development using five more sustainable environment. In 2009, President domains of sustainability, which include the original Obama appointed Paul Anastas to the leadership of the three domains (environmental, economic and socio- US Environmental Protection Agency (EPA)’s Office of cultural) and the domains of technology and public Research and Development. Anastas resigned from policy (Figure 1) (6). this position and chose to pursue his career at the The first domain, environmental sustainability, is based Center for Green Chemistry at Yale University in 2012. on assuming that the present environmental processes Following the 12 Principles of Green Chemistry provide a way to keep society as stable as possible provides a way to approach environmental challenges. based on ideal-seeking behaviour. This domain relies The 12 Principles of Green Chemistry cover the topics on making the public aware of the limited amount of of: pollution prevention; atom economy; less hazardous natural resources. Knowledge of the existence of chemical synthesis; design of safer chemicals; the use renewable resources is another crucial tool that the of safer solvents and auxiliaries; design for energy human race must acquire to continue to thrive (6). efficiency; use of renewable feedstocks; reduction Properly harnessing and utilising the earth’s of derivatives; catalysis; design for degradation; natural resources is a key goal involving economic real-time analysis for pollution prevention; and inherently sustainability. The term ‘economic’ from a business safer chemistry for accident prevention, as mentioned in “Green Chemistry: Theory and Practice” (3). The philosophy of green chemistry is to produce substances in a way that does not harm the environment, health and society. A wise way to introduce green chemistry Environmental to future generations is to define it from a sustainable development point of view (4). The concept of sustainable development began during the 1970s when the post-war environmental movement Public Socio- policy cultural highlighted negative effects such as the direct impacts of pollution on the environment and health. In 1987, the Sustainable desire to address sustainable development at a global communities scale became important to the United Nations. Through the Brundtland Commission, sustainable development was defined in the commission’s report entitled ‘Our Common Future’ (5). This report encouraged Economic Technological individuals to become aware of the environmental and social issues. It was influential in discovering new approaches to protect future generations. In 1992, the United Nations Conference on Environment and Fig. 1. Five domains of sustainable development (6). Development, known as the ‘Earth Summit’ or the ‘Rio ECOStep: The Five Domains of Sustainability is a concept Convention’, was held by the United Nations in Rio de of W. Cecil Steward, FAIA, © 2017 Joslyn Institute for Sustainable Communities

208 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) standpoint takes into account the value of resources (7). was the establishment of the Toxics Release Inventory Ideally compatibility should emerge between improving (TRI), which: the utilisation of natural resources more efficiently and “tracks the management of certain toxic making a profit from the end products. These strategies chemicals that may pose a threat to human are defined as economic sustainability, which facilitates health and the environment. U.S. facilities in responsible usage of natural and manmade resources different industry sectors must report annually with no or minimal negative impact on the world. how much of each chemical is released to the Observing sustainability from an economic perspective environment and/or managed through recycling, allows businesses to capitalise on the positive effects energy recovery and treatment”. of change within society. (A “release” of a chemical means that it is emitted to the The socio-cultural domain pictures the necessity air or water, or placed in some type of land disposal). for a viable and sustainable future due to continued As mentioned in the 2015 TRI National Analysis, world population growth. Rising consumption levels 21,849 facilities reported to TRI that they managed undesirably impact environmental sustainability. In 27.2 billion pounds (12.2 million tonnes) of toxic order to improve the standard of living, implementing chemicals related to production-related wastes through strategies to educate society is vital to the foundation recycling, combustion for energy recovery, treatment of a more sustainable future. or disposal (10). As shown in Figure 2, quantities of Technological advances have a direct impact on toxic chemicals released decreased while quantities of policymaking. Governments use policies to regulate recycled toxic waste increased. As stated in the 2015 industries and ensure their practices are not detrimental TRI National Analysis, “87% of toxic chemical waste to the environment (6). As a society, implementing managed was not released into the environment due to fit-for-purpose policies is vital to becoming sustainable. the use of preferred waste management practices such When these five domains are considered in a as recycling, energy recovery, and treatment”. harmonious way, the development of a society, a The 2015 TRI National Analysis also highlights business or a nation willing to take steps towards a the total quantities of TRI chemicals disposed of or more sustainable future should be achieved. These otherwise released by industrial sector (Figure 3). domains provide an ideal platform as to how to About 3.4 billion pounds (1.5 million tonnes) of toxic structure a sustainable environment. Examples on how chemicals were released, mostly by three sectors: these domains have been exploited to impact industry, metal mining (37%), chemical manufacturing (15%) academia and society in the USA over the past ten and electrical companies (13%). Unfortunately the years are detailed in the next section. The limitations chemical manufacturing sector is among the leading on an article of this size mean that it focuses on the sectors in both production-related waste managed reduction or elimination of pollution and environmental (49%) as well as total releases (15%). toxics and on finding ways to reduce the consumption Throughout the development of the concept of green of nonrenewable resources, although this is only one of chemistry over the past 25 years, there have been many areas where green chemistry can have an impact. many considerations on how green chemistry can help Additionally, the geographical scope is also specific to minimise toxic waste production and therefore prevent the USA due to the limited length of this review. pollution. One way to manage and control toxic waste production is to continuously enforce a set of rules and 2. Overview of the Impacts of Green and regulations in order to keep our society and environment Sustainable Chemistry Initiatives safe. These rules require many businesses and corporations to follow strict guidelines in order to meet 2.1 In US Industries environmental safety requirements that include “waste Before green chemistry became “a framework to handling, treatment, control, and disposal processes” do chemistry” (8), the US Congress passed the (11). However, these approaches are a costly factor Emergency Planning and Community Right-to-Know for many businesses and corporations. Companies Act (EPCRA) in 1986, which aimed “to support and spend about $1.00 per pound (approximately 0.45 kg) promote emergency planning and to provide the public to manage waste (8), which is a direct cost to the with information about releases of toxic chemicals in business. The major challenge faced by both industries their community” (9). One of the outcomes of EPCRA and societies is to expand technological advances in

30000 30000 Recycled 25000 25000 Energy recovery

Number of facilities Treated 20000 20000 Disposed of or otherwise released 15000 15000 Reporting facilities

10000 10000 Millions of pounds 5000 5000

0 0 2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 Year

Fig. 2. Production-related waste managed by facilities reporting to TRI over 2005–2015 (10). US EPA’s 2015 TRI National Analysis

All others: 10%

Food: 4%

Paper: 5% Metal mining: 37% Hazardous waste management: 6%

Primary metals: 10%

Electric utilities: 13% Chemicals: 15%

Fig. 3. Total disposal or releases by industrial sector in the USA in 2015: 3.36 billion pounds (1.5 million tonnes) (10). US EPA’s 2015 TRI National Analysis order to achieve more sustainable ways to improve The adoption of green chemistry principles could the economy and the environment. As Paul Anastas be seen as a wise means to reduce costs. The defines it: businesses and corporations that have implemented “we wanted to begin a shift away from regulation green chemistry within their design and manufacturing and mandated reduction of industrial emissions, of chemical products and processes have seen major toward the active prevention of pollution through results on lowered environmental costs and increased the innovative design of production technologies sales and revenues. Examples of success stories themselves. And we placed an emphasis on on how some of the main chemical-based industries both the environmental and economic value, have benefited from the adoption of green chemistry because we knew the concept would not be principles are highlighted below. The examples viable otherwise.” (8) given here are based on selecting some of the most

210 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) recent winners of the Presidential Green Chemistry After finding out that microalgae have an inherent and Engineering Challenge Awards, selecting a ability to produce oils, they used genetic engineering variety of industrial sectors where a green chemistry to develop an unlimited variety of triglycerides. alternative was successful, and ensuring that most of Using Solazyme’s triglycerides results in lower the categories of awards are represented. The authors emissions of volatile organic compounds (VOCs), are not affiliated with any of the industries mentioned reduces the quantity of waste produced and lowers below, nor did they receive funding from any of these the environmental impact compared to traditional companies. petroleum-based oils. Solazyme won the 2014 Chemical giants and other large companies, such Presidential Green Chemistry Challenge Award in as The Dow Chemical Company, (now merged with the Greener Synthetic Pathways category (13). E. I. du Pont de Nemours and Company (DuPont)), SC • In the biodegradable plastics sector: Verdezyne Inc, Johnson & Son, Shaw Industries Group Inc, Merck & also based in Southern California, relies on “using Co Inc and Pfizer Inc have paved the way to define the power of biology to make a positive impact on best industrial practices in green chemistry. Smaller your products”. Verdezyne took advantage of the companies such as Patagonia Inc, the Warner Babcock well-known process of fermentation, using yeast to Institute for Green Chemistry LLC, Solazyme Inc produce everyday products at a lower cost. Their (now TerraVia Holdings, Inc) and Verdezyne Inc have yeast fermentation process works with renewable also engaged in the application of green chemistry feedstocks such as low cost plant-based oils, principles. which act as substitutes for petroleum-based According to the EPA and based on the winning products. Their products, such as adipic acid, are technologies developed by the Presidential Green intermediates used in the production of nylons and Chemistry Challenge Awardees (12): plastics. Verdezyne won one of the Presidential “Through 2016, our 109 winning technologies Green Chemistry Challenge Awards in 2016 in the have made billions of pounds of progress, Small Business Award category (14). They recently including: diversified their ‘green’ products by partnering with • 826 million pounds [375,000 tonnes] of Aceto Corporation to design FerroshieldTM HC, hazardous chemicals and solvents eliminated which is a nitrate-free mixture with anti-corrosion each year – enough to fill almost 3800 railroad properties useful in several applications such as tank cars or a train nearly 47 miles [75 km] metal cleaners, engine coolants and aqueous long hydraulic fluids. • 21 billion gallons [95 billion litres] of water • In 2016, the winner of the new Presidential Green saved each year – the amount used by Chemistry Challenge Award in the Specific 820,000 people annually Environmental Benefit: Climate Change category • 7.8 billion pounds [3.5 million tonnes] of was Newlight Technologies who developed a carbon dioxide equivalents released to low-cost thermoplastic named AirCarbonTM from air eliminated each year – equal to taking methane, a potent greenhouse gas. Several 810,000 automobiles off the road.” well-known companies such as Hewlett-Packard The main industrial sectors where green chemistry has Company, IKEA and Sprint have already adopted made an impact over the past ten years include but are AirCarbonTM in the production of their packaging not limited to: bulk and commodity chemicals, plastics, bags, furniture and cell phone cases (15). paints, coatings, pesticides, fuels and pharmaceuticals. • Representing the paint industry: one of the issues Several companies exemplify what green chemistry at in the paint and coatings industry is the emission work is about. Taking some of the Presidential Green of large amounts of VOCs when oil-based ‘alkyd’ Chemistry and Engineering Challenge Awards winners paints dry and cure. The well-known paint company as examples: Sherwin-Williams developed water-based acrylic • Representing the bulk and commodity chemicals alkyd paints with low VOCs that can be made sector: Solazyme Inc (now TerraVia Holdings, Inc) from recycled soda bottle plastic (polyethylene based in South California developed the production terephthalate (PET)), acrylics and soybean oil. of vegetable oils via the fermentation of microalgae. These paints exhibit the same properties as alkyd

and acrylic paints but with low VOC content, low the 2012 Presidential Green Chemistry Challenge odour, and non-yellowing properties. In 2010, Award in the Greener Synthetic Pathways Sherwin-Williams claimed that the manufacture category. of this high-performance paint helped to eliminate Communicating these success stories to the next over 800,000 pounds (360 tonnes) of VOCs (16). generation of scientists, the students of today, and Sherwin-Williams won the 2011 Presidential Green incorporating these real-world case scenarios in the Chemistry Challenge Award in the Designing K-12 curriculum and beyond is the key to generate a Greener Chemicals Award category. systemic interest in the field of green and sustainable • Dow AgroSciences LLC participated in the chemistry (20, 21). improvement of many pesticides over almost two decades. In the 1990s they developed a 2.2 In Academia biopesticide called spinosad to repel insect pests As mentioned by Haack and Hutchison in a review on vegetables. However, spinosad was not article titled ‘Green Chemistry Education: 25 Years effective for insect-pest control in tree fruits and of Progress and 25 Years Ahead’ published in 2016, tree nuts. In 2008 they received the Presidential green chemistry was first depicted as a possible Green Chemistry Challenge Award in the Designing solution to improve laboratory safety, to address issues Greener Chemicals Award category for the design of of inappropriate ventilation in laboratories and obsolete spinoteram which is a high-performance insecticide laboratory space, and to modernise the chemistry efficient when applied to tree fruits, tree nuts, small curriculum (22). Nowadays it seems essential for future fruits and vegetables. Spinetoram exhibits the citizens and leaders of the 21st century to be educated same environmental benefits as spinosad while about the concepts of green and sustainable chemistry being less persistent in the environment compared to participate in the creation of sustainable societies. to traditional organophosphate insecticides. Supporters of green chemistry in academia have Furthermore the toxicity to non-target species is low followed in the footsteps of leading societies such as well as its use rate (17). as the ACS, the US EPA and the Royal Society of • Two companies, Albemarle Corporation and CB&I Chemistry in the UK, to create reliable educational Corporation, have developed a greener solid acid materials and programmes based on the application catalyst for the production of alkylate, which is of green chemistry (2). Some of the educational a blending component for motor gasoline. The green chemistry resources available for educators AlkylClean® technology replaces liquid acid, typically are textbooks, laboratory experiments, summer hydrofluoric acid or sulfuric acid, with an optimised programmes, workshops, and more recently, the zeolite-based catalyst. This catalyst eliminates the opportunity to continue training and research in green production of acid-soluble oils and spent acids and chemistry by enrolling into specialised Masters and bypasses the need for product post-treatment. PhD programmes. These two companies were the recipient of the 2016 The goal of this section is not to present an exhaustive Presidential Green Chemistry Challenge Award in list of all initiatives pursued in the academic world but the Greener Synthetic Pathways category (18). to highlight the main current resources and to share • Several collaborators developed a greener some of the newest initiatives in academia in the past synthesis of drugs for the treatment of high ten years in the USA. Literature and online resources cholesterol. The latest to date was a collaboration dedicated to green chemistry have grown during this between Codexis Inc and Professor Yi Tang of the period, especially targeting undergraduate students. University of California, Los Angeles, who used Ten years ago, to discover how much content an engineered enzyme and a natural product to related to green chemistry was inserted in chemistry manufacture simvastatin, originally sold by Merck textbooks, two surveys were completed as a baseline under the trade name Zocor® (19). Their efficient by publishers’ representatives (23). The first survey biocatalytic process avoids the use of several took place in 2006 at the ACS National Meeting hazardous chemicals while eliminating waste and Exposition, and the second survey was in 2007 and, most importantly, meeting the needs of the at the University of Scranton. For the first survey, customers. Codexis and Professor Tang received nine publishers whose focus is the publication

212 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) of undergraduate textbooks were chosen. These laboratory manuals are being used to ‘green’ the publishers were Benjamin Cummings, Prentice Hall, curriculum at many US undergraduate and graduate Houghton Mifflin Company, McGraw-Hill Publishing institutions (32–34). Company, W. W. Norton & Company, Thomson Articles describing the implementation of green Corporation, W. H. Freeman and Company, John chemistry tools and strategies in the classroom or Wiley and Sons, and Jones & Bartlett Learning. A list of laboratory have seen exponential growth. Some these publishers’ undergraduate chemistry textbooks journals publishing this type of content include the for both chemistry majors and non-chemistry majors Journal of Chemical Education, Science and Education was compiled. For the second survey, they gathered and Chemistry Education Research and Practice as information from the same publishers above except well as ACS Sustainable Chemistry and Engineering. for W. W. Norton & Company and Jones & Bartlett The number of articles devoted to examples on how to Learning. After analysing the data from the two implement green chemistry in education has doubled surveys, it was determined that only 33 out of 141 since 2007 (22). textbooks examined from all of the publishers There are many online teaching resources that have contained a mention of green chemistry. emerged based on collaborations between advocates Ten years later, textbooks dedicated to green chemistry for green chemistry. The following resources do not occupy shelves at most college and university libraries represent an exhaustive list of tools and only a few (24–27). While these textbooks target science majors, examples are mentioned here. Some examples include: several textbooks incorporating chemistry in the a database called Greener Educational Materials context of sustainability suitable for non-majors were for Chemists (GEMs) which contains laboratory recently published (28, 29). The wide dissemination of exercises, course syllabi and multimedia content and textbooks facilitated the development of single green was created by the University of Oregon (35). The chemistry-based courses as well as the infusion of University of Oregon also created the Green Chemistry green chemistry into typical major courses such as Education Network, allowing educators to continue general, organic, inorganic, biochemistry, analytical their professional development through collaborating and physical chemistry (30). Courses may be modified and fostering the integration of green chemistry by choosing greener alternatives as replacements in education. The non-profit organisation Beyond to traditional examples. For instance, in an organic Benign, based in Wilmington, Massachusetts, USA, is chemistry laboratory, procedures can use renewable “dedicated to providing future and current scientists, reagents, apply the metrics of atom economy instead of educators and citizens with the tools to teach and learn percent yield, limit the amount of organic solvents and about green chemistry in order to create a sustainable use alternative energy sources such as a microwave. future”. It is focused on K-12 curriculum development For inorganic chemistry, these alternatives can and educator training, community outreach and consist in highlighting reusable catalysts and reagents workforce development (36). Another example is the anchored on inorganic solid supports, decreasing the iSUSTAIN™ Green Chemistry Index which is an online use of heavy metals and of solid acids and bases. tool used to assess the sustainability of products and For biochemistry, these alternatives can focus on processes (37). biocatalysis, biosynthesis and the use of raw materials Mentoring and the creation of a green and sustainable from renewable resources. For analytical chemistry, chemistry community of practice is also taking place at reducing the use of column chromatography or high- conferences and workshops. National and international energy distillations is a step in the direction of green conferences on sustainability are bringing researchers chemistry principles. For physical chemistry, a lesson together from all over the world. Examples of on the thermochemistry of biodiesel, the use of kinetics well-known conferences involving presentations and catalysis, and the benefits to using computational of green chemistry educational materials are the studies can be introduced. national and regional ACS meetings, the Annual However the most prominent place for green Green Chemistry and Engineering Conference and chemistry to be taught is still in a laboratory setting. the Biennial Conference on Chemical Education in the The design of green chemistry laboratory exercises, USA, as well as international conferences such as the mostly in organic chemistry, created a successful draw International IUPAC Conference on Green Chemistry, to this ‘metadiscipline’ (31). Several organic chemistry the International Symposium on Green Chemistry and

213 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) the International Conference on Green and Sustainable Although progress has been made, it is important to Chemistry. keep in mind that the implementation of green chemistry To foster critical thinking skills and engage students in the curriculum needs to be tailored to the specific and faculty, workshops and awards are available. mission and type of institutions involved (four-year Each year the Green Chemistry Institute at the ACS undergraduate institutions, community colleges, large offers workshops designed for students at the Annual research universities). One approach does not fit all. Green Chemistry and Engineering Conference; It is also essential that all stakeholders from academia Beyond Benign designed workshops for K-12 teachers’ and industry are involved in addressing emerging training as well as online courses for educators; needs for new content related to toxicology as well as the University of Oregon was one of the pioneers for metrics and best educational practices. To attempt to in offering weeklong Green Chemistry Education fill in the gaps, a Green Chemistry Education Roadmap workshops for educators. Besides the Presidential Visioning Workshop took place in September 2015 to Green Chemistry and Engineering Challenge Awards delineate “the Roadmap Vision and the set of green for professional chemists, students can also be actively chemistry core competencies that every student with a challenged and participate in design competitions bachelor’s degree in chemistry, chemical engineering such as the People, Prosperity and the Planet (P3) and allied sciences should attain by graduation” (40). Student Design Competition launched by the EPA in While the roadmap vision is well established as follows: “Chemistry education that equips and inspires chemists 2002 (38). The goal of this competition is to expand the to solve the grand challenges of sustainability”, the breadth of participation by involving interdisciplinary “transformative potential of green chemistry” on society teams of students interested in not only chemistry but has not been explored yet since the societal impacts also engineering, architecture, art and business. The are often not taken into account when assessing the University of Berkeley’s Greener Solutions programme entire life cycle of newly designed green chemicals gathers both undergraduate and graduate students and processes (40). The next section attempts to give with local businesses and governmental agencies examples of how green chemistry is expected to play to come up with greener chemistry solutions in a a role in addressing environmental and human health real-world context (39). issues in a social justice context. Students have the opportunity to earn awards such as the Ciba Travel Awards in Green Chemistry, which 2.3 In Society are used for a student to travel to an ACS conference Even if the field of green chemistry inspires scientists focused on green chemistry; the Joseph Breen to tackle sustainability-related issues on a global Memorial Fellowship, which is for a student to present scale, the limited knowledge about the global research on green chemistry at an international green risk associated with exposure of the human body chemistry conference; and the Kenneth G. Hancock to chemical pollution is leading to “an emerging Memorial Award, which recognises “outstanding perspective that addresses the confluence of social student contributions to furthering the goals of green and environmental injustice, oppression for humans chemistry through research and/or studies”. and nature, and ecological degradation” (31). Since Finally, it is possible for undergraduate and graduate the development of chemistry has left unintended students to specialise in the study of green chemistry marks on humans, especially in non-white and and earn a degree in this discipline. While most low-income communities, it is essential to consider the institutions endorse some type of green chemistry social consequences of high levels of environmental programming (courses, laboratory curricula focused on pollution by hazardous chemicals. green chemistry, workshops), some universities such The US EPA defines ‘environmental justice’ as: as the University of Toledo, Ohio, are offering a BS “the fair treatment and meaningful involvement or an MS degree with a minor in green chemistry and of all people regardless of race, color, engineering, and Chatham University offers an MS in national origin, or income, with respect to the green chemistry focused on entrepreneurial skills. The development, implementation, and enforcement University of Massachusetts at both Boston and Lowell of environmental laws, regulations, and offer a PhD in Green Chemistry. policies. EPA has this goal for all communities

and persons across this nation. It will be achieved environmental justice online map across the USA when everyone enjoys: called EJSCREEN which: • The same degree of protection from “highlights low-income, minority communities environmental and health hazards, and across the country that face the greatest health • Equal access to the decision-making process risks from pollution. The analysis combines to have a healthy environment in which to live, demographic and environmental data to identify learn, and work.” (41) where vulnerable populations face heavy The EPA recently decided to implement plan EJ burdens from air pollution, traffic congestion, 2020 which accounts for “improving the health and lead paint, hazardous waste sites and other environment of overburdened communities”. By 2020, hazards.” (46) they will: Applying the 12 principles of Green Chemistry to • “Improve on-the-ground results for overburdened address social disparities affecting underprivileged communities through reduced impacts and populations can lead to many benefits such as the enhanced benefits delineation of methodologies to provide: • Institutionalize environmental justice integration in i. cleaner air through decreasing the emission EPA decision-making of hazardous chemicals during use (such as • Build robust partnerships with states, tribes, and pesticides) or the unintentional release (during local governments manufacturing or disposal) of toxic chemicals • Strengthen our ability to take action on environmental leading to health issues but also global warming, justice and cumulative impacts ozone depletion and smog formation • Better address complex national environmental ii. cleaner water by preventing the contamination of justice issues.” (42) drinking water with hazardous chemical wastes Environmental justice and social justice are mutually iii. increased safety for workers using chemicals as inclusive as demonstrated in the following definitions of part of their profession so that the use of toxic social justice as: materials is minimised and the need for personal “A state or doctrine of egalitarianism protective equipment is lessened (Egalitarianism defined as 1: a belief in human iv. safer consumer products such as the production equality especially with respect to social, political, of pharmaceutical drugs with less waste and the and economic affairs; 2: a social philosophy replacement of cleaning products and pesticides advocating the removal of inequalities among with safer alternatives people)” v. safer food based on the reduction of the amount of according to the Merriam-Webster Dictionary (43). persistent toxic chemicals present in pesticides or The National Association of Social Workers states as endocrine disruptors (47). that “Social justice is the view that everyone deserves Aligned with the leadership approach of the EPA, equal economic, political and social rights and scientists are motivated to determine that chemical opportunities” (44). exposures fluctuate with social disparities. The It has been stated that green chemistry “is one of following section highlights examples where social the tools for improving the quality of human life and injustices stemming from chemical exposure have been welfare”. Consequently it seems appropriate to refer the subject of peer-reviewed research. An attempt to to the green chemistry philosophy as the spring board demonstrate how green chemistry principles can help to change the negative perception associated with the address these social disparities is also presented. chemical enterprise and to “reduce the level of social burden on the personnel and people living nearby” 2.3.1 Pesticides Exposure and Farmworkers (45). The population of farmworkers in the USA is severely The successful implementation of green chemistry affected by pesticides exposure. It is estimated that of in industry, the role of green chemistry in increasing the 2.5 million farmworkers in the USA, 60% of them public well-being and sustainability leadership across and their dependents live in poverty (48). About 88% disciplines, sectors, and cultures are essential to of all farmworkers are Hispanic and more than 78% of promote environmental and social justice. To help them are foreign-born without legal documentation and achieve this goal, the EPA created an interactive no higher education (49).

Issues associated with the language barrier and the so that at the end of their function they break down into lack of health insurance coverage were brought up in a innocuous degradation products and do not persist report titled ‘Exposed and Ignored. How Pesticides are in the environment” (3). The challenge to remove Endangering our Nation’s Farmworkers’ in 2013 (48). A pesticide residues in the soil, water and air has led study conducted by Washington State Department of scientists at Carnegie Mellon University to develop Health showed that only 29% of pesticide handlers were specific TAML® catalysts targeting the degradation able to read in English and to some extent in Spanish. of pollutants from water without presenting endocrine Analysis of the blood work of pesticide handlers who disrupting activity (52). could not read English showed significantly greater Another example based on the control of pests pesticide exposure compared to those who could read affecting vineyards, the goal of research conducted English to some degree. by Jocelyn Millar at the University of California at Pesticide poisoning or exposure causes farmworkers Riverside was to “identify less-toxic pesticides that may to suffer more chemical-related injuries and illnesses be effective alternatives to organophosphates”. Instead than any other workforce in the USA (48). Worldwide, of using heavy loads of pesticides, the group developed 25 million agricultural workers experience pesticide a pheromone to control the vine mealybug population poisonings each year (50). Protective clothing does based on mating disruption. Their pheromone was not not provide adequate protection against pesticide only successful in trapping the vine mealybugs but was exposure, especially when handling organophosphate also beneficial to attract the vine mealybugs’ predators, and N-methyl carbamate pesticides. Since pesticide which was an unexpected benefit to the preservation residues are often invisible and odourless, only a blood of the ecological balance and of the natural predator test would be useful to monitor exposure to these toxic populations (51). chemicals. In a thorough report titled ‘Green Chemistry and 2.3.2 Exposure to Endocrine Disruptor Sustainable Agriculture: The Role of Biopesticides’ Bisphenol A and Children by Peabody O’Brien et al. in 2009, the role of Bisphenol A (BPA), a synthetic organic compound green chemistry applied to the agricultural world used to make plastics and epoxy resins for a variety and biopesticides in particular was validated (51). of common consumer goods, has been under scrutiny Biopesticides are derived from plants or from microbial since 2008 when several governmental agencies pesticides. They are less toxic, more pest specific, investigated its safety, especially with respect to its use they biodegrade more quickly and do not affect the in baby bottles and ‘sippy’ cups. BPA and polyfluoroalkyl ecological balance. chemicals (PFCs) are oestrogen-like chemicals found Another approach is outlined in the Green Chemistry to “disrupt reproductive development, body weight Principle #7: “Chemists should, whenever possible, and metabolic homeostasis, and neurodevelopment, use raw materials and feedstocks that are renewable”. and to cause mammary and prostate cancer.” Many Green chemists are currently using agricultural waste comprehensive reviews regarding the impacts of BPA products as renewable feedstocks and are synthesising on health have been published (53–55). biocatalysts to increase the “conversion of agricultural While concerns about the potential hazards of materials into high value products, including novel endocrine-disrupting chemicals such as BPA are still carbohydrates, polysaccharides, enzymes, fuels and debated, and after several countries have banned chemicals” (3). As explicitly mentioned in the Peabody its use, a study published by Nelson et al. in 2012 O’Brien report: addressed the population disparities in exposure to “Green Chemistry and sustainable agriculture these chemicals. Their findings demonstrated that: are inherently intertwined; farmers need green “people with lower incomes, who may be more chemists to make safe agricultural chemical likely to suffer from other disparities in health and inputs. Green chemists need farmers practicing exposures, have a greater burden of exposure sustainable agriculture to provide truly “green” to BPA. The results for children are especially bio-based raw materials to process into new troubling. Children overall had higher urinary products.” (51) BPA concentrations than teenagers or adults, Additionally, as defined in the Green Chemistry but children whose food security was very low Principle #10: “Chemical products should be designed or who received emergency food assistance - in

other words, the most vulnerable children - had about the strange taste and colour of the water but the highest levels of any demographic group. no further investigation was conducted. Thousands of Their urinary BPA levels were twice as high children among the majority of the African American as adults who did not receive emergency food population of Flint were exposed to lead without being assistance. Concerns about health effects from properly informed since this information was not made BPA exposure are strongest for young children public. It was not until January 2016 that a federal state and neonates because they are still undergoing of emergency was declared (60). In March 2017, the development. Results for BPA by race/ethnicity, EPA awarded US$100 million to the State of Michigan adjusting for income, revealed that Non-Hispanic to upgrade Flint water infrastructure, especially lead Whites and Blacks had similar urinary levels, and service lines (61). being Mexican American appeared to be highly While the cause of the increased level of lead in Flint’s protective.” (56) potable water was due to corrosion in the lead and It is thought that: iron pipes that distribute water to city residents, green “eating more fresh fruits and vegetables is likely chemistry has been at work to provide environmentally to be associated with eating less canned foods, friendly alternatives to chemical water treatment such which may explain the lower urinary BPA levels as the use of nanomaterials (62), the use of ‘green seen in Mexican Americans compared to other additives’ (63) or the use of photocatalysts (64). groups.” (57) Some green chemistry advocates are concentrating Several companies are now selling BPA-free products their efforts to address the social and environmental but do not always inform what substitute is being (in)justice of chemical exposure using the concept of used. It is even considered that some of the BPA- sustainable chemistry as framework in their academic free alternatives may actually not be safer than their research and outreach efforts. This has become a BPA-containing counterparts. Karen Peabody O’Brien, priority at academic institutions such as Bridgewater former Executive Director of the scientific foundation State University where Professor Ed Brush is starting a Advancing Green Chemistry, and John Peterson Myers, Participatory Action Research programme (65). In this CEO and Chief Scientist at Environmental Health programme the community will be involved in research Sciences, both located in Charlottesville, Virginia, have projects targeting social injustice. His research suggested using green chemistry tools to create: students are interested in assessing the impacts of “a new generation of non-petroleum-based diesel particulate matter emissions on populations materials from scratch, simultaneously protecting with a high risk of developing asthma such as females, public and environmental health while reducing children, people of colour and people of mixed race as dependence on foreign oil” (58). well as those living in poverty or with low incomes. The In 2014, Richard Wool and his research group at the plan is for students to collect data using air collectors University of Delaware achieved that by converting and then report their findings related to diesel exhaust lignin fragments, a waste product of the papermaking pollutants’ impact on health. The ultimate goal is to and other wood-pulping processes, to a compound delineate how green chemistry principles can be put to called bisguaiacol-F (BGF). BGF has the same shape work to decrease the exposure of minorities to diesel as BPA, but does not interfere with hormones and exhaust pollution. It is expected that studies related to retains the desirable thermal and mechanical properties biofuels will inspire their green chemistry proposal to of BPA (59). reduce social disparities due to exposure to emissions exhaust (66–68). 2.3.3 Contaminated Drinking Water and Air in Poor Communities 3. Conclusions The most recent example of social injustice was the water crisis in Flint, Michigan. When the town of Flint Advances in chemical knowledge and research have switched the source of water for its residents in 2014, brought great progress to the field of green and corrosion inhibitors were forgotten to be added to the sustainable chemistry. As mentioned earlier this article new water source, which caused lead levels to raise was written in the context of attracting attention to to 25 ppb (above the maximum level of 15 ppb set problems related to chemical pollution and resource by the EPA). Residents complained numerous times depletion and it also proposes some alternatives related

217 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695776 Johnson Matthey Technol. Rev., 2017, 61, (3) to the application of green chemistry. The overall goal empowerment on how to solve existing challenges was to demonstrate that the significant development using green and sustainable chemistry principles. of green and sustainable chemistry has opened up Although many educational materials are available, a new way of performing and teaching chemistry, challenges remain for academia, such as (22): demonstrating that green chemistry is applicable to all • The slow implementation of green chemistry in the fields of research and that it should not be a tradeoff undergraduate and graduate curriculum based on a between cost and environmental impact. In industry, “lack of uniform demand”, which can be perceived while the implementation of green chemistry is driven as curricular conservatism from academic and by government regulations, consumer awareness industrial stakeholders and higher demand for more environmentally benign • “The resistance to infuse green chemistry into the products, the rate of adoption is slow. In 2015, T. main general and organic chemistry textbooks or Fennelly & Associates, Inc identified some possible the ACS standardized exams” which does not accelerators of green chemistry adoption such as (69): motivate departments to make changes in their • Collaborative efforts relying on establishing price curriculum and performance trade-offs where transparency • The lack of expertise and confidence from is addressed and where “open innovation” is inexperienced educators to help students learn welcome. The word “coopetition” has been used about green and sustainable chemistry, and “as a model to drive competition and innovation” • Finally, the presence of key gaps in terms of content while simultaneously enabling the growth of green such as the introduction of toxicology and metrics chemistry as well as well-defined curricular objectives and • Compromise is a step in the right direction. assessments. When companies shift away from regulations Through the applications of green chemistry in industry and mandated reduction of industrial emissions and academia, it has been shown how green chemistry towards active pollution prevention, continuous can make a difference in the sustainable development improvement of a product will be justified for its of human civilisation. While this article described some economic and environmental value of the efforts undertaken in the USA, the scope of • Finally, continued and enhanced education in green this article could be expanded by highlighting efforts and sustainable chemistry is crucial among the outside the USA such as the commitment of the United work force. Nations to develop 17 sustainable development goals Even if the implementation of green chemistry to transform our world (70). Additionally chemical practices in industry face adversity, strategies have been companies around the world such as Dow Chemical identified to accelerate the adoption of green chemistry Company designed their own set of sustainability goals such as: continued research and communication to help “redefine the role of business in society” (71). among all stakeholders; support for ‘smart’ policies that Recognised as a means to aid society to live longer enhance green chemistry innovation and adoption; and better, green chemistry’s focus on the humanistic fostering collaboration; dissemination of information level will drive modern society in the direction of global to the marketplace; and tracking of progress using sustainability. metrics (1). With educators passionate about the green and sustainable chemistry field, not only are institutions References taking an interest in promoting the ‘green’ concept 1. “An Agenda to Mainstream Green Chemistry”, Green to their students, there are also plenty of resources Chemistry & Commerce Council, Massachusetts, available to encourage them to make a difference. The USA, 2015, 28 pp incorporation of green chemistry-based courses and 2. ‘Basics of Green Chemistry’, US Environmental the design of academic degrees in green chemistry Protection Agency, Washington, DC, USA: is vital to establishing awareness and knowledge of https://www.epa.gov/greenchemistry/basics-green- environmentally benign chemistry. Students, who gain chemistry (Accessed on 5th May 2017) insight about how green chemistry can positively impact 3. P. T. Anastas and J. C. Warner, “Green Chemistry: local communities as well as the entire world, enter Theory and Practice”, Oxford University Press, New the work force with a head start and a sense of ethical York, USA, 1998, 135 pp

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The Authors Anne Marteel-Parrish grew up in the North of France and got her Engineering degree in Materials Science from the Ecole Polytechnique de Lille, France, in 1999. She received a PhD in Chemistry with concentration in Materials Science from the University of Toledo, Ohio, USA, in May 2003. Shortly after, she was hired as Assistant Professor in Chemistry at Washington College in Chestertown, Maryland, USA. Anne received tenure and was promoted to the rank of Associate Professor in 2009. She achieved full professorship in 2016. She was the Chair of the Chemistry Department at Washington College from 2010 to 2016. In 2011 she was invested as the Inaugural Holder of the Frank J. Creegan Chair

Credit: Shane Brill, Washington College Credit: Shane Brill, Washington in Green Chemistry.

Karli Newcity received her BS in Chemistry at Washington College, Maryland, in 2013. Before completing her studies, she took an internship with the Domestic Nuclear Detection Office at the US Department of Homeland Security where she trained in Radiochemistry and Nuclear Forensics. Currently, she is a Chemist supporting the Detection Branch of the Engineering Directorate of the Edgewood Chemical Biological Center, Edgewood, MD, USA, where she performs a wide variety of laboratory operations in a test and evaluation laboratory.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

UK Energy Storage Conference Research progress, economics and policy considerations in the field of energy storage

Reviewed by Jacqueline Edge Delegates were enthusiastic and highly engaged Energy Storage Research Network, Energy Futures in the programme, which involved long sessions Lab, Electrical Engineering, Imperial College London, running until late afternoon. During the breaks, Exhibition Road, London SW7 2AZ, UK discussion groups formed, either around the highly topical posters or to discuss possible future Email: [email protected] collaborations. The presentations reviewed below consist of a selection of those who volunteered their slides for public access. The three winning posters are also Introduction reviewed in this article. For a full listing of the talks presented at UKES2016, please go to the conference The third UK Energy Storage Conference (UKES2016) website. Where permission has been granted, the was held at the Edgbaston campus of the University slides are available to download. The top three of Birmingham, UK, from midday on Wednesday 30th posters were selected by a panel of judges. Digital November to midday on Friday 2nd December 2016. copies of these and a few others, all volunteered The aim of the conference, organised by the Energy by the presenters, are available on the conference Storage Research Network on behalf of the UK website. Research Council funded Energy SuperStore Hub and The conference presentations were arranged within chaired by Professor Nigel Brandon (Imperial College the following themes: London), is to provide an inclusive platform for the UK • Demonstration Projects energy storage community to come together and share • Policy and Economics of Storage in Energy their work and views. Systems The conference was well attended, with a total of 280 • Storage for Transport delegates, 61 from industry and six from government. • Integration of Storage into Energy Networks The rest were from academia, including 89 students. • Hydrogen for Energy Storage Most of the delegates were from the UK, but 28 were • Flow Batteries international. A total of 73 posters were on display • Thermal, Mechanical and Thermochemical throughout the conference, stimulating discussions Storage during refreshment breaks. • Electrochemical Energy Storage Judging by the positive feedback received, the • Advanced Tools and Diagnostics conference appears to have been a success. • Power Management and Control.

Batteries and Control session. Battery management systems improve safety, balance the performance of multiple Dan Rogers (University of Oxford, UK) gave an cells and monitor cell degradation to predict failure engineering perspective of grid-scale energy storage early on. Embedding this into cells at the time of in his plenary talk on the second day, explaining manufacture can reduce costs, extend lifetimes his work on power electronics. This field involves and validate warranties. Jorn Reniers (University using semiconductor devices to control and convert of Oxford) won a prize for his poster in this theme, electrical energy. This allows large arrays of cells to entitled ‘Offering Multiple Grid Services in Parallel be monitored and managed electronically, through while Minimising Battery Degradation’. The results of carefully constructed algorithms. For large arrays, it is a battery pack simulation are presented, showing that more probable that at least one cell will be significantly the cost benefits of extending the lifetime of the battery weaker than the rest and therefore the construction through active management outweigh the revenue loss of simple large arrays becomes challenging. Power from occasionally missing grid revenue opportunities. electronics can be inserted into the pack to mitigate The session on demonstration projects aimed to the influence of the weaker cells and improve overall showcase a range of automotive and grid scale performance (capacity utilisation and system reliability). projects currently being developed. Colin Arnold (AGM Using Markov chain reliability modelling, Rogers Batteries Ltd, UK) introduced two new automotive was able to show that the reliability of high voltage projects that AGM Batteries Ltd are heavily involved grid-scale batteries (comprising very large numbers of in, ‘UK Automotive Battery Supply Chain’, funded by cells connected in series) can be greatly improved by the Advanced Propulsion Centre (APC), UK, and adding power electronics within the pack (Figure 1), ‘Sodium-Ion Batteries for Electric Vehicles’, funded by even if the power electronics devices themselves are Innovate UK. The first requires the development of highly significantly less reliable than the cells. innovative embedded electronics whilst establishing These themes were discussed further in a keynote the foundations of a world class UK lithium battery delivered by Joel Sylvester, the Chief Technical supply chain involving industrialists and academics Officer for Dukosi Ltd, UK, in the Power Management working together to share insights and expertise. The second project aims to take advantage of exciting sodium-ion chemistry to develop safer and lower cost batteries for electric vehicles and other sectors. Power electronics During the evening of the first day, the APC hosted a panel session focused on energy storage applications in the automotive industry. Chris May (APC) opened the session with a talk on how the APC is working to identify strategic opportunities for the UK automotive supply chain (Figure 2). Mike Woodcock (APC) and Professor David Greenwood (University of Warwick, UK) then went on to explain how the APC is bringing together the academic and industrial communities to capitalise upon these opportunities. Xiaohong Li (University of Exeter, UK) delivered one of the keynote addresses in the flow batteries session

M cells per module on a redox flow battery (RFB) system which does not use membranes. In most commercially available RFBs, the ion exchange membrane comprises about a third of the production cost, so removing the need N modules in a pack for this membrane will offer opportunities to make RFB technology economically viable for grid-scale Fig. 1. The cells in a battery pack can be divided up into N applications (Figure 3). Her technique is to develop modules, with each module of M cells controlled by power electronics (Reproduced with permission) a zinc-nickel RFB which uses a single electrolyte, eliminating the need to separate two electrolytes with

Fig. 2. The ‘hub and Funding Road-mapping spoke’ model of the APC’s accelerated low carbon strategy for helping the development technology UK automotive industry of low carbon Internal trends technologies combustion capitalise on low carbon engines technologies (Reproduced Energy with permission) Electric storage machines Strategic and energy and power technologies management electronics for the UK automotive Supporting industry Identifying and low carbon Lightweight technology- developing Intelligent vehicle and led supply SMEs and powertrain mobility supply chain chain structures opportunities Developing and linking industrial and academic communities

Ion-exchange membrane Fig. 3. A conventional RFB has two electrolytes, Electrolyte Electrolyte separated by an ion-exchange tank tank membrane and requiring

Electrode duplicate storage and flow mechanisms. A membrane- Electrolyte Electrolyte free system uses a single electrolyte for reactions at Electrode both electrodes, eliminating a large proportion of the components (indicated by the faded out sections) (Reproduced with permission)

Pump Power/load Pump

a membrane. This will also improve performance and to explore the link between microstructure and greatly simplify device manufacture and operation. performance. One of her PhD students, Pelin Yilmaz, In the session on electrochemistry, Professor won a prize for her poster, ‘Biomass-Derived Low Cost Maria-Magda Titirici presented her work on anodes Negative Electrodes in Na-Ion Batteries’. for sodium-ion batteries at Queen Mary University of London, UK. Sodium is cheaper and more abundant Energy Storage than lithium and is therefore an attractive option for making large scale batteries. The research challenge The policy session included a joint talk from Catherine is to find a suitable anode material and Professor Bale (University of Leeds, UK) and Andrew Pimm Titirici is researching carbon derived from biomaterials (University of Edinburgh, UK), describing the objectives

224 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695839 Johnson Matthey Technol. Rev., 2017, 61, (3) and progress of the Consortium for Modelling and powered by excess renewable energy. The talk Analysis of Decentralised Energy Storage (C-MADEnS). discusses the options for similar installations to be Two case studies were presented, one examining the established around the world, mainly in China and the public perception of domestic energy storage and the USA. He concluded that renewable energy generation other exploring the potential for peak demand reduction integrated with underground hydrogen storage is the using Tesla Powerwall installed in 100 homes in the least expensive way to supply 100% of the world’s city of Leeds. The first study is still underway, but the electrical energy demands. second study found that it was possible to reduce peak Pau Farres-Antunez (University of Cambridge, UK) demand by more than 50%. gave a talk on pumped thermal energy storage (PTES), Graham Oakes, the Founder and CEO of Upside a high energy density thermomechanical form of energy Energy Ltd, UK, gave a keynote address in the storage storage having no dependence on nearby geographical integration session, entitled ‘Stimulating Storage features. If liquid reservoirs are used instead of solid, Research through Open Innovation’. Upside Energy then each tank of liquid can be stored at low pressure considers the many uninterrupted power supply and maintain a single temperature, rather than the batteries around the UK as a distributed storage gradient necessary for solid thermal reservoirs. The asset and has developed online control systems design of these enables a greater separation between to enable these devices to connect to the grid, the hot and cold stores, limiting the opportunities for providing automated demand side flexibility services thermal transfer after the charge has been completed, (Figure 4). Upside Energy was funded by the Innovate which is a source of loss in thermal storage systems. UK programme and is an excellent showcase for the The research at Cambridge is exploring ways to improve benefits of innovation-level funding, demonstrating the efficiency of these systems. Haobai Xue, a PhD one way in which the deployment of storage can be student working in the same research group as Pau, encouraged. presented a winning poster in this theme, comparing A keynote address on the role of storing hydrogen compressed air energy storage (CAES) systems with underground was delivered by Professor Bent PTES and showing that while the system efficiency for Sørensen (Roskilde University, Denmark). There CAES systems tend to be higher than for PTES, PTES are two facilities in operation in Denmark which use achieves a much higher energy density. underground storage of natural gas: one using a salt Professor Phil Taylor, Director of the new Centre for cavern and the other using an aquifer store. They could Energy Systems Integration at Newcastle University, both be converted to hydrogen stores at a low cost and UK, closed the conference on 2nd December with do not require high pressures or low temperatures to a plenary talk on the broader perspective of how store hydrogen in a condensed form. In both cases, energy storage fits into future energy systems. His talk hydrogen would be produced using electrolysis, examined how the apparently disjointed aspects of

Open innovation community

Develop advanced algorithms

Delivers Device Sells devices Offers device balancing Energy capacity suppliers manufac- and services Device Upside services turer and owner platform System and reseller DNOs

Increases value proposition Gives device owners an Builds and operates Pays for to their customers income for shifting demand Upside Cloud platform service

Upside operating company

Fig. 4. Schematic showing the Upside operation platform and all stakeholders (Reproduced with permission)

225 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695839 Johnson Matthey Technol. Rev., 2017, 61, (3) energy storage addressed during the conference could Conclusions be joined up through integration of the technology into an advanced test bed (Figure 5). The new facilities at The conference succeeded in its aim to bring the UK Newcastle University are part of the Engineering and research community together to discuss a wide range Physical Sciences Research Council (EPSRC) £30 of topics in the field of energy storage, spanning million programme funding research equipment at economics and policy considerations, through to several universities around the UK and enable energy advanced diagnostics materials and devices. The storage devices to be integrated into a reconfigurable presentations, both oral and poster, were of a high grid. This will allow testing of many aspects, such as the standard and served to report research progress in performance of the devices, ways in which they could these diverse fields, stimulating discussion between be combined to provide multiple grid services or new people with expertise in diverse research areas, to system operating paradigms to extract the maximum identify and address the key research challenges for value from the integrated assets. the further deployment of energy storage.

Fig. 5. The Newcastle University energy storage testbed (Reproduced with permission)

The Reviewer

Jacqueline Edge holds two BSc degrees from the University of Cape Town, South Africa, in Zoology and Computer Science. After a career in online banking development, she returned to academia to study Nanotechnology at University College London (UCL), UK, followed by a PhD in Hydrogen Storage. She now manages the Energy Storage Research Network at Imperial College London, facilitating research collaborations through the running of conferences such as the UK Energy Storage Conference.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

“Particle Technology and Engineering: An Engineer’s Guide to Particles and Powders: Fundamentals and Computational Approaches” By Jonathan Seville and Chuan-Yu Wu (University of Surrey, UK), Butterworth-Heinemann, an imprint of Elsevier, Oxford, UK, 2016, 294 pages, ISBN: 978-0-08-098337-0, £51.10, US$84.00, €60.16

Reviewed by Domenico Daraio*, Giuseppe introducing the basic knowledge required for two Raso and Michele Marigo computational approaches (DEM and FEM). It gives Johnson Matthey Technology Centre, PO Box 1, a wide ranging introduction to the fundamentals of Belasis Avenue, Billingham, Cleveland, TS23 1LB, UK particle mechanics and computational aspects for particulate systems. For more in-depth discussion, *Email: [email protected] the authors refer the readers to other, more extensive, works. The book is divided into three main sections: • Part one: provides an overview of fundamental Introduction characteristics of particles and powders in bulk form and how they can be determined (Chapters The authors of this book, Professor Jonathan Seville 2 and 3) and Professor Chuan-Yu Wu, are globally recognised • Part two: consists of three chapters and comprises experts in the field of particle technology. Professor the bulk of the book. This section describes the Seville has a degree in Chemical Engineering from complexity of a surrounding phase: firstly, as single the Universities of Surrey and Cambridge, UK, with a particle interactions (Chapter 4), then considering strong background in the design and manufacturing of multiple particles in the gas phase (Chapter 5) products for the pharmaceutical, home care and fast- and finally considering multiple particles in liquid moving consumer goods industries. Professor Wu has (Chapter 6) a degree in Chemical Engineering and a PhD from • Part three: Chapters 7 and 8 describe the Aston University, UK, in finite element method (FEM) fundamental mechanics of particle systems both at of particle impact problems from which he later moved the bulk level and particle level. This provides the to discrete element methods (DEM). basics for an understanding of the last two chapters The book is intended to provide an initial overview of the book (Chapters 9 and 10) which introduce two of the field of particle technology by summarising computational methods – DEM and FEM applied to the essential scientific fundamentals of particles and particle technology.

Particle Characterisation diagram. Then pneumatic conveying, a few rules of thumb and the most important variables to be Chapters 2 and 3 examine the fundamental properties considered when designing pneumatic conveying of bulk solids such as powder density, flowability, systems are presented. particle size and shape, surface area, compressibility The last part of Chapter 5 focuses on gas-solid and compactibility and the related experimental separations and illustrates the operating principles techniques which can be used to characterise these for cyclones and filters. An example of cyclone scale- properties. The book underlines the importance for up (Figure 1) and a brief discussion of multi-cyclone particle properties related to final product quality systems are included. control and process monitoring purposes. Importantly, A description of the rheology of suspensions is particle characterisation allows a better understanding examined in the first part of Chapter 6. Different of the correlations between bulk behaviour, product rheological behaviours can be exhibited by solid quality and process performance. Furthermore, suspensions: this section summarises typical the authors consider particle size measurements rheological responses and their fitting to models such as and the importance of their physical and statistical power-law types (for example shear thinning and shear representation. Finally, an often overlooked issue thickening). Then a brief touch on pastes is presented in industry is how representative a sample is of a by giving useful examples of paste characterisation larger quantity. General rules to design and prepare a and a list of common problems associated with paste representative sample to obtain reliable measurements extrusion. The last part of the chapter gives an outline are presented. The general principles in this section of the agglomeration process and provides a schematic should be useful for a new practitioner in the area of mechanism for wet agglomeration. This description particle technology but should be considered golden aids understanding of the influence of several process rules for working in the particle technology field.

Interaction with a Surrounding Phase

The second part of the book focuses on multiphase flow of solids in fluids. Chapter 4 examines the Eddy interaction of a single solid particle immersed in a fluid. Dusty air inlet The analysis of the forces exerted on a single particle by the surrounding fluid and the estimation of the drag Vortex finder force coefficient are presented as a starting point for the calculation of the terminal velocity in either steady- Outer vortex state or under unsteady motion. The value of terminal velocity is one of the key parameters for the design of unit operations such as fluidised beds and solid Inner vortex of cleaned air separation systems. Systems with multiple solid particles in contact with a continuous gas phase are considered in Chapter 5. Beginning with the gas-solid contact regimes and a list of application examples, the chapter continues Disengagement with a well-presented description of the equations hopper for pressure drop in packed beds and minimum fluidisation velocity. An entire section is dedicated to fluidisation and fluidisation regimes, with particular Dust discharge via flap focus on bubbling beds and models for the prediction valve or rotary valve of bubble size and velocity (very important elements in mass and heat transport phenomena involving Fig. 1. An illustration of cyclone scale-up (Reprinted with multiphase flow). Typical fluidisation behaviours are permission from Elsevier/Butterworth-Heinemann, summarised by the established Geldart classification Copyright © 2016)

228 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695848 Johnson Matthey Technol. Rev., 2017, 61, (3) variables such as mixing intensity, liquid flow rate and initially developed for other purposes but has more droplet size. recently found wider application in different engineering Chapter 7 introduces powder bulk behaviour. disciplines including structural dynamics, heat transfer, Differences between bulk solid and fluid mechanics fluid dynamics and aerodynamics. The potential and are illustrated and the concepts of powder failure, efficacy of the FEM is shown in two representative internal friction and wall friction are presented. One of cases: the analysis of a normal impact between a the classic problems in bulk solid mechanics is stress sphere particle and a substrate and the continuum analysis in storage vessels and the counterintuitive modelling of powder compaction. For both applications, stress distribution in bulk solid containers is well if high stress levels and deformation are present DEM presented. This analysis together with the Coulomb cannot be used to describe the problem since most of model for friction are the key elements for silo design. the energy will be dissipated in plastic deformation. The discharge of storage hoppers is considered in the last part of the chapter. A comparison between Conclusions flow patterns is provided together with the equations for calculating mass flow under different conditions. The book gives the reader a full but fairly approachable Further, transmission of stresses in powders during overview of the fundamentals of particle technology, powder compaction is described with reference to reporting the current state of this field and providing tablet quality density. perspectives on future challenges. A good overview of particle characterisation, the link between the Computational Approaches microscopic and macroscopic properties and the future role of computational methods (DEM and FEM) in Chapter 8 illustrates the mathematics required to particle technology is provided in this book. describe the particle-particle interactions influencing Particle technology is a broad subject and this text the mechanical behaviour for bulk solids. Both may be sufficient for the interests of a beginner and elastic and elastoplastic particles are considered for might awaken a sense of curiosity that will drive the normal impacts, tangential loading, adhesive forces reader to more exhaustive texts such as the Handbook and capillary forces. This subject is not presented in of Powder Technology of which the latest volume was complete mathematical detail, with full derivations of published in 2007 (1). all the equations. The reader is given a good overview of the complexity of the impact analysis in the case “Particle Technology of simple perfectly elastic impacts. In Chapter 9 the and Engineering: numerical DEM (that was originally developed in An Engineer’s Guide to Particles the field of soil mechanics and further developed for and Powders: other disciplines) is introduced. The authors give an Fundamentals and exhaustive description of the calculation cycle utilised Computational by typical DEM algorithms and they conclude the Approaches” chapter with a data analysis section. The DEM data post-processing analysis is a key step in the use of this numerical technique where the ultimate goal is to relate the microscopic interparticle phenomena to the macroscopic bulk behaviour of the material. The application of DEM is limited by the amount of plastic deformation that can be reliably represented. In situations where the plastic deformation of the particle is not negligible or for impact problems including contact of irregular shape particles, FEM Reference has been used to model the state of stress inside the 1. “Particle Breakage”, eds. A. D. Salman, M. Ghadiri and particle body. This different computational method is M. J. Hounslow, Handbook of Powder Technology, Vol. introduced in Chapter 10. Like DEM, this method was 12, Elsevier BV, Amsterdam, The Netherlands, 2007

The Reviewers

Domenico Daraio is an EngD Student in Formulation Engineering at the University of Birmingham, UK, and he has a degree in Chemical Engineering from the University of Pisa, Italy. He is currently working on DEM modelling of milling systems to better understand how the energy input into the system is transferred at different scales.

Giuseppe Raso is a Marie Curie Early Stage Researcher at the University of Twente, The Netherlands, and the University of Edinburgh, UK. He graduated from the University of Calabria, Italy, in Chemical Engineering. His project involves the rheological study of wet powders and the application of DEM for the simulation of wet granular systems in industrial processes.

Michele Marigo is a Principal Scientist at Johnson Matthey Technology Centre, Chilton, UK. He obtained an undergraduate degree with a master’s in Mechanical Engineering from the University of Padua, Italy, and a doctorate in Chemical Engineering (EngD) from the University of Birmingham. Michele’s expertise includes materials science, particle engineering, discrete element modelling and finite element modelling.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

Organometallic Catalysis and Sustainability: From Origin to Date Rapid progress towards more sustainable processes for industry

Justin D. Smith Introduction Department of Chemistry, University of Louisville, Louisville, Kentucky 40292, USA Nature is the best-developed and largest biochemical reactor, synthesising countless chemical entities Fabrice Gallou in high purity and yield without exhausting itself. Novartis Pharma AG, CH-4057 Basel, Switzerland Beautifully, its processes exhibit quantitative reaction yield, low E factor, excellent atom economy, Sachin Handa* absence of toxic metals and solvents, ultra-purity of Department of Chemistry, University of Louisville, products, excellent chemoselectivity and outstanding Louisville, Kentucky 40292, USA reaction reproducibility throughout billions of years – all accomplished at ambient temperature in *Email: [email protected] water (Figure 1(a)). Conversely, synthetic processes prevail with breadth of substrate scope and reaction kinetics, but only due to availability of powerful Organometallic catalysis has its origins in the 18th and organometallic catalysts, which, in combination with 19th centuries. Then, the emphasis was on achieving other discoveries in chemistry, materials and other remarkable chemical transformations, but today the disciplines, have enabled synthetic organic chemists focus is increasingly on sustainability. This article to construct almost any desired molecule. Astonishing summarises the current promising approaches with catalytic transformations have been developed with special regard to those that have commercial potential, modified enzymes (1), nanomaterials (2), photoredox including non-aqueous and water immiscible solvents, chemistry (3) and organocatalysts (4). Asymmetric modified enzymes, micellar catalysis, catalysis with catalysis has led to independence from chiral auxiliaries low loading, metal-free catalysis and catalyst recycling. and nonracemic starting materials (5). The 18th and Environmental metrics, a key evaluation tool for any 19th century progenitors of organometallic chemistry, industrial chemical process, are used in micellar Cadet (6), Frankland (7) and Zeise (8), could not catalysis to demonstrate their usefulness, especially have imagined this boom in organometallic catalysis, to achieve streamlined protocols, reduce losses and which continues into the 21st century with milestones eliminate toxic materials. including the birth of nanocatalysis (9), the renaissance

(a) (b) Toxic Toxic solvents Toxic solvents gases

O2 100% chemoselectivity

CO2 Practical but sustainable

E factor catalysis N2 Man-made Dry reactor organic solvent

Ultra purity Nature

Fig. 1. (a) Nature versus (b) man-made catalytic processes

of photoredox catalysis (10) and the harnessing of goal presently seems unrealistic. Due to older beliefs, micellar conditions to perform air-sensitive chemistry in even gold was considered catalytically inactive (14), water at room temperature (11). leaving Sir Geoffrey C. Bond to remark: “We are at a However, in the big picture, in spite of major advances loss to understand why these catalytic properties of in the development of novel transformations, ligands, gold have not been reported before, especially since catalysts and technologies, the majority of today’s the preparative methods we have used are in no way catalytic transformations suffer from many drawbacks remarkable”. Today, even gold-assisted photoredox in terms of sustainability, as evinced by very high E chemistry is possible (15), and for the matter at hand, factors (12), poor atom economy (13), use of hazardous Frances Arnold’s inspired work on mimicking natural material and toxic organic solvents (12) and the catalytic processes already provides a guiding light involvement of energy intensive routes (Figure 1(b)). (1). Developments helping to save our reserves of A very simple question must strike any organic threatened metals through the merger of photoredox chemist’s mind: when has Nature run any reaction chemistry with enzymatic, micellar and nanocatalysis in dry tetrahydrofuran (THF) at –78ºC or in any other are also noteworthy (1–4). Accordingly, endeavours to organic solvent under very harsh conditions? While discover sustainable new catalysts, transformations following Nature and enjoying the wealth of chemical and technologies that will preserve our beautiful blue properties of transition metals, one must marvel at planet should be undertaken with careful attention to how amazingly our processes differ. Are they not all aspects of how Nature performs chemistry. Such responsible for huge chemical waste generation? This attention will yield solutions to many current and even issue is somewhat truer with chemistry laboratories untouched problems. in academia where we put much focus on current trends while ignoring sustainability issues, deferring Historical Origins the topic to process chemists. Our preset perceptions sometimes blind us from important innovations, which Organometallic catalysis has a rich history. In 1731, may be particularly true for sustainability in chemical Stahl published a report on the synthesis of Prussian catalysis. If Nature can perform biochemical catalysis blue, Fe4[Fe(CN)6]3 (16). However, the traditional so ideally, why is it not generally possible to perform classification of metalloid complexes as organometallics chemical catalysis in the same fashion? Perhaps this would date the first synthesis of an organometallic

232 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695866 Johnson Matthey Technol. Rev., 2017, 61, (3) compound to 1757, when Cadet encountered the (23). Subsequently, Sabatier clearly distinguished foul smell of cacodyl oxide and tetramethyldiarsine, homogeneous and heterogeneous catalysis through generated from arsenic-containing cobalt salts while his method development for hydrogenation of organic trying to develop new invisible inks (6). The true compounds in the presence of finely divided metals genesis of organometallic chemistry happened in (24), an achievement that led to a Nobel Prize in 1827 when the first p-complex, trichloro(ethene) Chemistry shared with Grignard in 1912. Important platinate(II), now known as Zeise’s salt, was reported milestones during the next 50 years include the (Scheme I(a)) (17). Further noteworthy metal alkyl Fischer-Tropsch synthesis of linear hydrocarbons from complexes were reported between 1849 and 1863, syngas (25–27), vanadium oxide catalysed oxidation of including diethyl zinc, tetraethyl tin, diethyl mercury benzene (28), silver-catalysed epoxidation of ethylene and trimethylboron (18, 19). The first metal carbonyl (29), cobalt-catalysed hydroformylation of olefins, the complex, dichlorodicarbonyl platinum, was synthesised oxo process (30), the Pd-Cu-mediated Wacker process in 1868, followed by syntheses of binary metal carbonyl for acetaldehyde formation (31) and the Ziegler-Natta complexes, including tetracarbonyl nickel in 1890 catalysts for olefin polymerisation, which earned their and pentacarbonyl iron in 1891. At the time, catalytic developers the 1963 Nobel Prize in Chemistry. The utility was unknown, and the bonding and structure Wacker process in particular was a bellwether of future of organometallic complexes was a mystery. Early directions, being the first useful transformation to assumptions held that ligands were aligned in a chain employ homogeneous organopalladium catalysis. with metal at the terminus. The coordination theory The golden period of homogeneous catalysis proposed by Werner in 1893 based on his experimental started in 1962 when Vaska reported a 16-electron data was the first of many models to more correctly iridium complex, now known as Vaska’s complex explain the nature of bonding in organometallic (Scheme I(b)), having the unusual property of complexes (20). reversible bonding with oxygen; this complex is the basis The seminal application of organomagnesium for the modern iridium complexes used in photoredox compounds to organic synthesis by Barbier, Grignard chemistry (32). In 1963 Fischer isolated the first metal- and Sabatier occurred in 1900 (21, 22), and the birth of carbene complex (33), a tungsten-based complex organometallic catalysis was soon to follow. Although that later provided a simple and fascinating means of concurrent discoveries of organometallic reactions olefin metathesis (34). Another important achievement facilitated by unconsumed chemical mediators were was the development of the first homogeneous rationalised into conceptual unity by Berzelius with his hydrogenation in 1965, independently reported by articulation of the concept of catalysis in 1835, the fusion Wilkinson and Coffey (35, 36). Control on chirality of these two domains into organometallic catalysis did was first accomplished in 1966 by Nazoki and Noyori not begin until Ostwald’s work on chemical equilibria and who reported synthesis of cis- and trans-cyclopropane catalysis in 1902. This work initialised homogeneous carboxylate (10% and 6% ee, respectively) from styrene catalysis and organometallic chemistry with its reports and ethyldiazoacetate using 1 mol% of a chiral Cu(II) on the first alkyl metal and metal hydride catalysts complex (Scheme II(a)) (37). This work marked the

– (a) + Me Co Cl K I Me H CO Pt Pt Fe Cl Cl H CO Me CO Zeise salt Alkyl metal complex Metal hydride complex (1827) (Pope, 1909) (Hieber, 1931)

(b) O O H H Ph P O 2 Ph P Cl 2 Ph P H 3 Ir 3 Ir 3 Ir OC PPh3 OC PPh3 OC PPh3 Cl Cl Scheme I Discovery of metal complexes important from catalysis perspective. (a) Early reported examples of metal complexes; (b) unusual properties of the Vaska complex

(a) N2CHCO2Et Ph CO Et H CO Et + 1 mol% catalyst 2 + 2

Ph Ph H H Ph H 10% ee 6% ee N O Cu O N

Catalyst Ph

(b) MeO CO2H (i) Rh catalyst, H2 MeO CO2H

NHAc + H NHAc AcO (ii) H3O AcO

Scheme II Asymmetric catalysis at a very early stage. (a) The first reported asymmetric catalysis; (b) Knowles application of asymmetric catalysis in the synthesis of L-DOPA advent of asymmetric organometallic catalysis. At about and Materials (SusChEM) programme is likewise a key the same time, Kagan reported an asymmetric rhodium- initiative to attract more chemists in order to attain long- catalysed hydrogenation to obtain chiral amino acids term sustainability goals. using a C-2 symmetric chiral 2,3-O-isopropylidene-2,3- dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) Advances in General Sustainability ligand (38), a discovery that soon led to the synthesis of enantiomerically pure L-3,4-dihydroxyphenylalanine Many advancements in organometallic catalysis and (L-DOPA) by Knowles (Scheme II(b)) (39). Thereafter, synthesis have been achieved and a few of them are asymmetric epoxidation of allylic alcohols was reported summarised here. by Sharpless (40). Noyori and coworkers finally accomplished the synthesis of the very important Aqueous Reaction Media 2,2’-bis(diphenylphosphino)-1,1’-binaphthyl (BINAP) ligand in 1976 after two years of method development, When has Nature ever run a reaction in organic solvent? paving the way for many similar ligands that are widely The answer is ‘never’. So if Nature can do chemistry in an used today (41). These many discoveries in asymmetric aqueous environment, why then do chemists not do the catalysis by Knowles, Sharpless and Noyori earned same? Partly, we are not able to perfectly mimic Nature them a Nobel Prize in 2001. in every aspect, but conducting catalysis in water, even The intense scientific interest in organometallic at room temperature, is certainly possible. However, catalysis has not abated in the new millennium with performing chemistry in water and then introducing Nobel Prizes being awarded for work in the area in that water into the waste stream would still adversely 2005 and 2010. At present, however, it is shocking impact our environment and be a topic of criticism. The to observe that we seemingly have yet to fully realise cost of such contaminated water treatment may even the challenges that will be faced for decades into the be greater than the disposal of organic solvents, and of foreseeable future. Awareness has begun to take course, the impact may be more detrimental. root, thanks to the emergence of the green chemistry Is it possible to recycle the water if contaminated from concept beginning in 1990 and its promotion of a catalytic reactions that are conducted in water? Very more sustainable and environmentally responsible recently, a micellar technology has been introduced by practice of chemistry (42). More recently, in the USA, Lipshutz and co-workers where dissolution of 2% (w/v) establishment of the ACS Green Chemistry Institute of amphiphile named tocopherol methoxypolyethylene has provided better direction for the community, the glycol succinate (TPGS-750-M) in water forms US Presidential Green Chemistry Challenge Award nanomicelles (43). The hydrophobic interior of is encouraging chemists to focus on innovative nanomicelles has been harnessed for chemical sustainable methods and the National Science catalysis. Coupling reactions including Suzuki-Miyaura, Foundation (NSF) Sustainable Chemistry, Engineering, Buchwald-Hartwig amination, Sonogashira, Hiyama,

Heck and C–H activation are well reported under micellar to conventional, oftentimes toxic, organic reaction conditions. In addition, asymmetric gold catalysis, media. Financial concerns also prompt this renewed aerobic oxidation, ring-closing metathesis (RCM), consideration, since with conventional reaction media Cu-H reductions, nitro reductions, trifluoromethylation we first pay upfront for toxic solvents and then pay and many more have been explored (Figure 2) (44). again in the end for their disposal. While a temporary Interestingly, the authors are able to recycle the catalyst answer is to focus on the use of greener solvents, such and reaction medium many times. Amphiphile TPGS as using 2-methyltetrahydrofuran in place of water- and its components are environmentally benign and soluble THF, alternative reaction media are currently do not yield any toxic fragments. Recycling has been needed that are not only green but also do not lead to performed without any energy intensive procedure. the same waste streams. Products of resulting reactions have been extracted by One class of alternative reaction medium, ionic liquids, a minimal amount of organic solvent and the aqueous has been put forward as a safer choice than organic layer is reused for the next catalytic reaction. solvents (45), but despite the limited volatility, inert nature and relative stability of ionic liquids, risk of their post- Greener Reaction Media reaction release into the environment is a significant concern. As Jordan and Gathergood noted: “The Reaction medium is an important parameter to the parameters of biodegradability, toxicity – and recently success of any catalytic process and the isolation of its mutagenicity – are becoming more significant” (46). resulting product. Large amounts of organic solvents Supercritical carbon dioxide presents a nontoxic, are annually consumed in chemical transformations. nonflammable alternative, but high pressure and

Dissolution of all components of a reaction including temperatures are required to maintain CO2 in its liquefied the resulting product is traditionally considered as state. It has been explored as a reaction medium in beneficial, especially for reaction yield and determining many valued reactions such as Pd-catalysed Heck reaction kinetics and mechanism. With the emergence reactions and Rh-catalysed hydroformylation (47). of green chemistry, this parameter has received fresh Traditionally, fluorinated solvents have also been attention as chemists have begun to seek alternatives considered to be safer and greener media (48). This class includes perfluorinated hydrocarbons, fluorous amines and ethers. The characteristic supporting their greenness is their immiscibility with water, and thus, TPGS-750-M inability to contaminate water. However, their miscibility with water is temperature-dependent. Heating the fluorous-bound catalyst in a non-fluorous solvent leads to homogeneity, resulting in catalysis. After reaction completion, cooling provides the separation of phases Suzuki- and ease of product separation from the organic solvent C–H Water activation Miyaura layer. New fluorous solvents, catalysts and reagents couplings are now available that drop the costs associated with bond constructions (49). Gold Reactions take Buchwald- catalysis place here Hartwig ‘Switchable solvent’ is another technology assisting amination organic chemists to move away from using traditional Vitamin E core organic solvents (50). Generally, switchable solvents Aerobic Sonogashira reversibly change their physical properties in response oxidation couplings to external stimulus such as a change in external Ring temperature and addition or removal of gases. The closing Nitro ‘switchable’ solvent is also widely recognised for metathesis reductions its practical applications to wastewater treatment, Cu–H Many reduction more CO2 capture and solvent recovery. For example, dimethyl sulfoxide (DMSO) is a high boiling solvent

Fig. 2. Versatility of micellar approach for catalysis in water and this property makes product isolation very difficult. Piperylene sulfone (51), a switchable solvent,

235 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695866 Johnson Matthey Technol. Rev., 2017, 61, (3) has been used to replace DMSO for nucleophilic mimicry of Nature in catalysis and a move away from substitution reactions. It is synthesised by reaction of scarce metal catalysed processes. trans‑1,3‑pentadiene and sulfur dioxide in the presence of a radical inhibitor. Heating the piperylene sulfone ‘In Water’ and ‘On Water’ Catalysis above 110ºC causes thermal decomposition back to the low-boiling starting materials (Scheme III). Thus, it Notwithstanding, these milestones in exploring is more convenient to recover the solvent and reaction enzyme-mediated transformations in water are not the product. only simpler alternatives to traditional non-sustainable organometallic catalysis and organic solvents. Much Modified Enzymes as Biocatalysts better catalytic activities (ee’s, functional group tolerance and yields) have been observed while An aqueous environment is also ideal for enzymatic conducting the reactions with modified enzymes in processes, and many known transformations of water. Although reactions ‘on water’ are very well synthetic utility can be effectively conducted (52). explored (59, 60), further advances are still needed Extension of the repertoire to other valued but regarding the interactions involved between substrates, unknown organic transformations catalysed by catalysts and water (61), this knowledge gap remains naturally occurring enzymes is the area of directed atypical within the synthetic community. Nonetheless, evolution (Scheme IV) (53). With the aid of protein recent studies by Kobayashi and co-workers further engineering, enzymatic properties can be fine-tuned demonstrate the synthetic potential of water in catalysis through iterative mutagenesis, and then can be utilised (62). In their report, a new nonracemic Cu(II) catalyst as biocatalysts to perform target-oriented synthetic leads to asymmetric conjugate additions of the Fleming organic chemistry and enantioselective biocatalysis. dimethylphenylsilane (PhMe2Si) residue in enones and In a Perspective titled ‘The Nature of Chemical enoates as well as unsaturated nitriles and nitro olefins, Innovation: New Enzymes by Evolution’, Arnold with ee’s ≥90%. Interestingly, neither the reaction elaborated on several ‘non-natural’ reactions that can partners nor the copper catalyst is soluble in water. Use be carried out by modifications of cytochrome P450- of organic solvents including dichloromethane, THF, derived enzymes (54). Representative transformations DMSO, methanol and ethanol provided lesser reaction using this approach include cyclopropanations (55), yields and ee’s. The superior results with water may be aziridinations (56) and regio-divergent aminations (57). due the formation of higher order aggregated states of Very recently, directed evolution of cytochrome c for the catalyst. carbon–silicon bond formation has been reported (58). Enzymes had not previously been known to catalyse Low Catalyst Loadings C–Si bond formation. This conjuncture between living systems and synthetic organic chemistry is a stepping Annually, about a billion tonnes of bulk and fine chemicals stone to mimic Nature. Using a similar approach, the are produced through metal-catalysed processes. A same group were able to achieve enhanced catalytic catalyst is generally used in sub-stoichiometric quantity activity of cytochrome c by a 15-fold increase in as it is regenerated after completion of each catalytic turnover rate relative to the state-of-the-art synthetic cycle. From a pharmaceuticals industry perspective, catalyst for C–Si bond forming reactions. The reaction it is equally important that the resulting product must proceeded with excellent yields and enantioselectivities be free from trace metal impurities which usually come over a broad substrate range. Such discoveries and from organometallic catalysts used in the process. developments represent a significant step forward for Thus, process chemists prefer to use such metal catalysts at early steps of the synthesis. However, sometimes it becomes more challenging to remove O O R S trace metal impurities, especially if the product is either R + SO2 an active pharmaceutical ingredient or its intermediate. This problem can be easily solved if there is a provision R = H, Me of more robust catalysts, requiring very low levels of Scheme III Switchable solvent approach. Piperylene sulfone loading in accordance with the notion ‘low in, low out’. as a DMSO equivalent Thus, catalyst loading is also a very crucial parameter

N H (a) 2 Rma cyt c V75T M100D M103E ORꞌꞌ ORꞌꞌ Si + Rꞌ Rꞌ R H Buffer (pH 7.4), Na2S2O4 Si O RT, 4 h R O 98–99% ee TON 210–8210 Representative examples: O O O

OEt OEt OEt Si Si Si S

TON 210, 98% ee TON 630, 99% ee TON 5010, >99% ee

O O O O n n (b) O O Enzyme P411BM3– Pr S Pr S n NH Pr S CIS-T438S-I263F + NH N3 25ºC, 12 h Me n-Pr Et 97% ee 99% ee Selectivity 95:5

Scheme IV Nature directed enzymatic catalysis. (a) Enantioselective carbon-silicon bond forming reactions; (b) enzyme controlled regiodivergent amination; (c) enantioselective synthesis of levomilnacipran via enzymatic cyclopropanation

for product purity, especially for pharmaceutical and A discovery of an artful RCM reaction by Dider material chemists. Villemin and its further development through There are many precedents for chemical Grubbs and Schrock catalysts provided a new transformations achieved with a very low catalyst route to synthesise cyclic hydrocarbons (66). loading (63, 64). However, many of them involve With low catalyst loading, it has been explored elevated temperature, microwave assistance, toxic on many substrates (Scheme V(b)). In his study, organic solvents, dry reaction conditions, no opportunity Kadyrov observed the efficiency enhancement with to recycle the catalyst, limited substrate scope or volatilisation of byproduct ethylene, leading to an excessive amounts of reactant. Despite these pitfalls, increase in turnover frequency (TOF) up to 4173 such contributions are steps toward sustainable per minute at 50 ppm catalyst loading (67). With catalysis. the catalyst loading between 50 and 1000 ppm, Doucet and co-workers reported a low catalyst 5‑ to 16-membered heterocyclic moieties have loading for ligand-free palladium-catalysed direct been synthesised. Key features of this methodology arylation of furans (Scheme V(a)) (65). Key features were its high TOF and broad substrate scope. A of this work include high reaction yield, better atom representative 7-membered cyclic ether was obtained economy than traditional Suzuki-Miyaura couplings, with 86% yield at 100 ppm loading of B. Similarly, very low catalyst loading, high turnover number 16- and 18-membered lactones were obtained at (TON), high reaction yield and greater functional 100–1000 ppm catalyst loading. However, yield of group tolerance with broad substrate scope. the 18-membered lactone was poor.

(a) Br 100–10,000 ppm Pd(OAc)2 + R O KOAc (2.0 equiv.) R O DMAc, 150ºC, 24 h NC

nBu nBu O O NC O CHO CHO 100 ppm Pd, 91% 1000 ppm Pd, 70% 1000 ppm Pd, 63%

(b) Catalyst Me Me

N N N N Mes Mes Mes Mes Ph Cl Cl Ru Ru Cl Cl S PCy3 PCy3 A B

O O

Representative O N O products: O O O O TOF 130 TOF 26 TOF 1100 86% yield 89% yield 24% yield Cat. loading 100 ppm B Cat. loading 1000 ppm A Cat. loading 100 ppm B

Scheme V Transition-metal catalysis at ppm levels of catalyst loading. (a) Direct arylation of furans; (b) ring-closing metathesis

Catalysis under mild conditions with low catalyst (XPS), atomic force microscopy (AFM) and transmission loading along with the opportunity for in-flask recycling electron microscopy (TEM). The reaction medium was of a reaction medium, all in a single package, is well also crucial for catalytic activity and TPGS-750-M developed by our team (68). A highly valuable and truly aqueous solution was the optimal choice with the general Suzuki-Miyaura cross-coupling catalysed by added benefit of being a greener solvent. Both the ppm levels of palladium is just the tip of the iceberg. catalyst and reaction medium were recycled without In one of our reports, a very general, high yielding any energy intensive separation processes. Extraction cross-coupling process with broad substrate scope of product with a minimum amount of organic solvent operating by way of an iron-based nanomaterial usually left the aqueous components containing the containing ppm levels of palladium impurity has been active catalyst. disclosed (Scheme VI) (69). A specific method of This technology is applicable to a wide range nanomaterial generation was crucial for the catalytic of substrates including a variety of aryl chlorides, activity, namely SPhos as an ancillary ligand, THF as bromides and iodides. Different boron nucleophiles a solvent for formation of nanoparticles, FeCl3 as the such as aryl boronic acids, boronic acid pinacol iron source, a Grignard reagent as a reductant, and (Bpin) esters, potassium trifluoroborate salts and above all, correct stoichiometry of all components. N-methyliminodiacetic acid (MIDA) boronate esters are Stability and composition of the nanomaterial was well tolerated. The beauty of this process lies in the very well established from the physical data including participation of earth-abundant metal, the small excess thermogravimetric analysis (TGA), scanning electron of boron nucleophile needed, mild reaction temperature, microscopy (SEM), X-ray photoelectron spectroscopy no trace metal contamination to the product and the

X X = Cl, Br, I Fe/ppm Pd*

+ K3PO4•H2O (1.5 equiv.) 2 wt% TPGS-750-M [B] = B(OH)2, Bpin, [B] 0.5 M, RT–45ºC BF3K, MIDA Fe/ppm Pd nanoparticles

Bn OMe O N OHC N O N N OPO(OEt) 2 N Me N N OMe Boc

X = Br, Y = Bpin X = I, Y = B(OH)2 X = Br, Y = B(OH)2 X = Cl, Y = B(MIDA), 40 h, 76% 24 h, 77% 24 h, 88% 20 h, RT, 94% X = Br, Y = B(MIDA), 33 h, 85% X = I, Y = B(MIDA), 29 h, 87%

COOMe F O N H OMe N O OMe CF CF Cy BnO 3 3 OMe O O OMe N N O O Ts N N F3C CF3 OBn O

X = I, Y = B(OH)2 X = Br, Y = B(MIDA) X = Br, Y = BF3K X = Br, Y = B(OH)2 48 h, RT, 81% 48 h, 80% 20 h, RT, 91% 26 h, 85%

Scheme VI Fe/ppm-Pd catalysed sustainable and truly general Suzuki-Miyaura couplings. *FeCl3 (5 mol%), SPhos (5 mol%), MeMgCl (6 mol%), K3PO4•H2O

recyclability of the catalyst as well as of the reaction such microwave assisted reaction conditions confirmed medium. Good functional group tolerance and high the involvement of palladium species in the catalytic reaction yields further lend to its practical application. cycle, albeit at parts per billion levels (71). Thus, Continuing the evolution of sustainable cross-coupling metal still appears necessary for these processes, but chemistry using ppm levels of palladium, ligand-based exceptionally low loadings are possible. technology has also been reported to facilitate low loading levels in water (68). In addition to the salient Metal-Free Catalysis features of the Fe/ppm palladium approach, this technology includes rational ligand design supported Another alternative to strengthen sustainable chemical by density functional theory (DFT) calculations, catalysis is the metal-free platform of organocatalysis operational simplicity, no elevated reaction temperature (72). However, organocatalyst-promoted reactions and no need for excess of coupling partners. In this suffer from many drawbacks including low catalyst methodology, the highly effective ligand HandaPhos efficiency, long reaction time, difficulty in recycling combined in a 1:1 ratio with palladium acetate leads the catalyst and almost no activity for activation to a precatalyst that upon in situ reduction yields a of challenging chemical bonds such as the mC–H very powerful catalyst to achieve the desired catalysis bond of an aryl ring. L-proline has been thoroughly at room temperature under micellar conditions explored in asymmetric organocatalysis, especially for (Scheme VII). conjugate addition reactions (73). The limitation of such Although transition-metal free Suzuki-Miyaura cross- transformations is the same as in typical organocatalyst- couplings have been claimed (70), reassessment of promoted reactions, and thus, not truly sustainable in

i O Pr P i Pr i O O Pr

O O F3C I 1000 ppm HandaPhos F C N 3 N O O N 1000 ppm [Pd], Et3N (2.0 equiv.) O N CF3 CF3 CF3 CF3 1.0 mmol 2 wt% Nok (0.5 M), RT, 18 h

+ CF3 CF3 0 1 2 3 4 B(MIDA) Run O Yield, % 90 90 89 91 90 1.0 mmol (99.9% pure)

Scheme VII Ligand-mediated sustainable Suzuki-Miyuara couplings at ppm level of palladium. No organic solvent is used for extraction or purification nature. Very cleverly, through mechanistic insights, and co-workers has eased the installation of the highly Wennemers and co-workers achieved catalyst loadings valuable trifluoromethyl group on various arenes down to 1000 ppm without affecting the ee and overall (Scheme IX) (76). So far, this is the most sustainable yield (Scheme VIII) (74). In their study, it was found that way to achieve such trifluoromethylation, especially at the presence of water slowed down the formation of gram scale under very mild conditions and with good the key enamine intermediate. Therefore, dry reaction functional group tolerance. However, there is still plenty conditions are required to achieve this metal-free of room for further advancement as this process is catalysis at ppm levels. The need for dry conditions is comparatively less efficient for electron-poor arenes. a major problem that chemists usually encounter while designing practical sustainable catalytic methods. Catalyst Recycling Recent growth in the area of photocatalysis is another step toward mimicry of natural catalysis (75). By definition, a catalyst facilitates reactivity without However, typical involvement of the scarce metal being consumed in the process. If it is not consumed, iridium may be an issue in the long run. Fortunately, then why is it predominantly treated as waste? many metal-free and main group element-promoted Sometimes, in systems where catalyst recycling is photoredox processes have been reported, helping to not attempted, it survives exactly the length of the address this concern (75). Elegant advancement in the process, at which point it is still promptly destroyed as area of metal and peroxide-free, scalable and clean waste! The obvious financial and environmental costs photoinduced trifluoromethylation of arenes by C.‑J. Li of such an unsustainable approach have long spurred

O O R2 0.1 mol% catalyst 2 H + R H NO NO2 CHCl :iPrOH 9:1, RT 2 R1 3 R1

O H 1 2 N R R ee, % Yield, % N NH 2 Et Ph 97 87 O O NH nPr Ph 96 98 CO2H Catalyst Bn C6H4-2-CF3 92 99

Scheme VIII Asymmetric organocatalysis with ppm level of a catalyst

CF F3C hn >400 nm 3 + CF SO Na 3 2 R R Acetone R EtOAc:diacetyl (4:1)

O Me OMe O Me OH t t H CF3 CF Me Bu Bu 3 N N N N CF3 CF3 CF3 O N N N N MeO OMe MeO OMe N H OMe CN Me CF3 81%, gram scale 71%, gram scale 71% 65% 75% 65%

Scheme IX Clean, peroxide- and metal-free trifluoromethylation

chemists to seek ways to reuse these catalysts across existing homogeneous technology into a recyclable multiple reactions (77). Strategies for catalyst recovery gross reaction medium. The extent of the generality is generally involve catalyst immobilisation on separable so great that multiple, diverse transformations can be supports or in biphasic solvent systems (78). performed sequentially in one pot. Heterogenisation is a widely-employed technique that often comes at the cost of catalytic activity, selectivity Environmental Metrics and metal leaching, which can limit the extent of recyclability. A compelling illustration of the potential Environmental metrics are important evaluation tools for this approach to overcome these limitations for any chemical process, especially from an industrial was recently provided by Tu and co-workers, who point of view (81). Micellar chemistry is an important reported the development of a robust ruthenium- development in the field of synthetic methods to NHC coordination polymer for solvent-free reductive address issues pertaining to sustainability. Indeed, a aminations (79). The solid catalyst could be easily most outstanding feature of this chemistry is the overall recovered by centrifugation and decanting. It was able high mass efficiency. This approach, particularly to to catalyse the synthesis of 5-methyl-2-pyrrolidone novices, appears as counterintuitive, but the micellar from levulinic acid at a 1500 ppm catalyst loading environment in which the chemistry occurs possesses through 37 recycles without significant loss of activity. some remarkable features. A second strategy, magnetic-metal nanoparticles, There are two key components responsible for the represents an alternative ‘semi-heterogeneous’ system efficiency of methods involving micellar chemistry. for organometallic catalysts that is easily separable Firstly, reactions are usually best facilitated by very from the bulk reaction medium by use of an external high concentrations of substrates and catalyst. While magnet. Catalysts anchored to metal nanoparticles transformations in traditional organic solvents tend to have competitive activities and enantioselectivities proceed at concentrations of 1% to 20% by weight, compared to their homogeneous analogues (80). with 5% being routine after optimisation, corresponding A third strategy, biphasic solvent system, allows reactions in water under micellar conditions are for recovery of unmodified homogeneous catalysts typically achieved at 10% to 50% by weight, and by dissolving the products in one layer while routine use of 20% is possible with limited effort. The retaining the catalyst in another. As noted above, dynamic exchange between the medium and the a similar but distinct approach is micellar catalysis. micelles, a site where actual chemistry takes place Micellar catalysis has been advanced as a viable whether at the interface or inside the micelles, makes strategy to both recover catalysts and minimise the chemical transformation possible, despite the very solvent waste (12). A key appeal of this strategy is minute solubility of reaction partners. Secondly, such its generality: rather than requiring development of transformations typically exhibit very high reactivity a new immobilised catalyst system for each specific and selectivity. Hence, they require very minimal post- reaction, this approach readily accommodates reaction processing. Sometimes after the reaction

241 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695866 Johnson Matthey Technol. Rev., 2017, 61, (3) completion, only a simple filtration of almost pure identification of the most efficient synthesis with regard solid product is required; otherwise, a simple one-time to atom economy and reaction yields, the use of safe extraction with a minimum amount of solvent for direct and less hazardous chemicals, the elimination or isolation of the product is usually sufficient. Perfect reduction of waste and the number of operations, all reaction selectivity is possible due to the very mild with the additional goal of reduced presence of toxic reaction conditions with almost ideal stoichiometry of materials. These basic principles, the foundations reactants. The simple filtration procedure is typically of green chemistry, are well known to the scientific favoured for catalytic transformations where a limited community (42). However, practical examples that amount of side-products are formed. Due to the very illustrate their relevance are still scarce. We, therefore, limited excess of reaction partners and very low wanted to demonstrate quantitatively the relevance of catalyst loading, this approach requires limited effort in some of the well-accepted green chemistry metrics. product processing. Extraction is the preferred option As a result of this work, it has proven possible to for stoichiometric transformations where the amount of replace commonly used polar aprotic solvents, which side-products formed is still substantial. suffer from reprotoxicity. The overall cycle time also Standard catalytic and stoichiometric processes improved dramatically due to a much-reduced number performed on scale in our laboratories and production of operations and streamlined workup protocols. facilities highlight the performance of the technology, In addition, the new process increased the overall as can be exemplified by Scheme X with standard yield, mostly due to reduced mechanical losses (loss depiction of the key operations in processes, and their of material in the workup and purification steps in corresponding metric analyses (Table I). Efforts were the original synthesis and during the isolation and made to find better practical ways of addressing the purification operations). Finally, the streamlined safety and environmental impact of the process. Our synthesis minimised the need to handle potentially efforts span over a range of concerns such as the toxic material.

CHO F H B(OH)2 H N B(MIDA) 1.05 equiv. O O 1.05 equiv. Cl Cl PdCl2(dtbpf) (1 mol%) Et3N (2 equiv.) RT Et3N (3 equiv.) N N N N 2 wt% TPGS-750-M/H2O (0.5 M), 2 wt% TPGS-750-M/H2O (0.5 M), N THF (5%), RT THF (5%), RT N Cl N F

75% Scheme X One-pot double Suzuki-Miyaura couplings

Table I Comparisons of Environmental Metrics for One-Pot Double Suzuki-Miyaura Couplings shown in Scheme X Metrics Standard process in organic solvents after optimisation Process in surfactant PMIa 110 72 PMI solvents 57 30 PMI aqueous 38 35 PMI reagents 15 7

E factor 109 71 aPMI = process mass intensity

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The Authors

Justin D. Smith studied chemistry at the University of Kansas, USA, where he received a dual BS degree in cooperation with the University of Regensburg, Germany, as part of the Atlantis exchange programme. He is presently pursuing a PhD in chemistry under the direction of Professor Sachin Handa at the University of Louisville, USA.

Fabrice Gallou received his PhD from The Ohio State University, USA, in 2001 in the field of natural products total synthesis. He then joined Chemical Development at Boehringer Ingelheim, USA. He subsequently moved in 2006 to the Chemical Development group at Novartis, Switzerland, where he is now responsible for global scientific activities worldwide, overseeing development and implementation of practical and economical chemical processes for large scale production of active pharmaceutical ingredients (APIs).

Sachin Handa received his PhD in chemistry from Oklahoma State University, USA, in 2013 and subsequently worked as a postdoc at the University of California, Santa Barbara, USA, with Professor Bruce H. Lipshutz. In August 2016, he moved to Louisville, Kentucky, where he is an assistant professor in the Department of Chemistry at the University of Louisville. His research interests include sustainable photoredox chemistry, ligand design and catalyst development.

JOHNSON MATTHEY TECHNOLOGY REVIEW www.technology.matthey.com

Industrial Low Pressure Hydroformylation: Forty-Five Years of Progress for the LP OxoSM Process A long standing collaboration between Johnson Matthey and Dow continues to sustain the high standing of their oxo technology through innovative solutions to address the changing needs of the global oxo alcohol market

By Richard Tudor Introduction Retired, Reading, UK The LP OxoSM Process is the rhodium-catalysed Atul Shah* hydroformylation process in wide use today in a variety Johnson Matthey, 10 Eastbourne Terrace, London, W2 of industrial applications. These applications have been 6LG, UK developed, co-marketed and licensed as a cooperation between affiliates of The Dow Chemical Company *Email: [email protected] (‘Dow’) and Johnson Matthey or their predecessors, for over 45 years. The LP OxoSM Process first made an impact in the 1970s when its technical elegancy, environmental Since the mid-1970s when the ‘Low Pressure Oxo’ footprint and economics attracted huge attention by process (LP OxoSM Process) was first commercialised, the world’s producers of normal butyraldehyde for it has maintained its global position as the foremost conversion to the plasticiser alcohol 2-ethylhexanol oxo process, offering particular appeal to independent (2EH). producers of commodity plasticisers facing increasing regulatory pressure. The story of this important The Early Dominance of Cobalt Catalysis industrial process is told from its early beginnings when laboratory discoveries by independent groups of Hydroformylation is the reaction of an unsaturated researchers in USA and UK revealed the remarkable olefinic compound with hydrogen and carbon ability of organophosphine containing rhodium monoxide to yield an aldehyde. In the case of the compounds to catalyse the hydroformylation reaction, widely practised hydroformylation of propylene, the and describes how its development, exploitation olefin (usually present in chemical or polymer grade and continuing industrial relevance came about by propylene) is reacted with a mixture of hydrogen and collaboration between three companies: The Power- carbon monoxide (in the form of synthesis gas), to Gas Corporation, which later became Davy Process produce two aldehyde isomers (normal butyraldehyde Technology before becoming part of Johnson Matthey; and iso-butyraldehyde) according to Equation (i): Union Carbide Corporation, which became a wholly owned subsidiary of The Dow Chemical Company; and 2CH3CH=CH2 + 2CO + 2H2 → Johnson Matthey. CH3CH2CH2CHO + (CH3)2C(H)CHO (i)

The hydroformylation reaction was first reported become a winner of the Nobel Prize for Chemistry) at by Dr Otto Roelen of Ruhrchemie AG, Germany, in Imperial College London, UK, found independently that 1938 and was given by German researchers the rhodium compounds containing organophosphines description of ‘oxo’ synthesis. Alcohols synthesised could catalyse the hydroformylation reaction at mild by the hydrogenation of aldehydes produced from temperatures and pressures and with high selectivity hydroformylation tend therefore to be called oxo to linear aldehydes (2, 3). Wilkinson’s research alcohols. Roelen’s discovery was to lay the foundation was supported by the precious metal refiner and for bulk organometallic chemistry and the application processor Johnson Matthey who supplied rhodium of homogeneous catalysis on an industrial scale. He through a loan scheme inaugurated in 1955 that did originally employed as a catalyst a mixture containing much to foster university research in platinum group cobalt, thorium and magnesium oxide that was metals chemistry in the UK and overseas. Wilkinson commonly used for Fischer-Tropsch synthesis and later later proposed that the rhodium complex responsible speculated that cobalt hydridocarbonyl (HCo(CO)4) for catalysing hydroformylation reactions was was the catalytically active species. He realised that tris(triphenylphosphine)rhodium(I) carbonyl hydride the catalytic mechanism was homogeneous in nature (RhH(CO)(PPh3)3) and that high selectivities to normal (for example (1, 2)). The Second World War hindered aldehyde could be achieved using a large excess of Ruhrchemie’s attempts to complete the construction of phosphine ligand (for example (4, 5)). In the late 1960s a first industrial oxo plant for producing fatty alcohols Johnson Matthey and The Power-Gas Corporation from Fischer-Tropsch olefins, and in the following decided to seek worthwhile opportunities to collaborate years Ruhrchemie commercialised a number of in research projects. The Power-Gas Corporation was a hydroformylation processes using homogeneous full services engineering and construction contractor of cobalt catalyst for use in the production of detergent considerable international repute with a strong process and plasticiser alcohols. By the end of the 1960s engineering base, and had recently restructured its most plants were using the ‘classic’ cobalt process research and development activities meaning it was employing HCo(CO)4, operating at very high pressures looking for process development projects. By early 1970, in the range of 200 to 450 bar and temperatures The Power-Gas Corporation had broadly confirmed in between 140ºC and 180ºC, although a modification of its Stockton-on-Tees laboratory Wilkinson’s proposition this catalyst, cobalt hydridocarbonyl trialkylphosphine that high n:i ratios can be obtained with a large excess

(HCo(CO)3PR3), had been commercialised enabling of phosphine. Further encouraged by preliminary the hydroformylation of propylene to occur at about process engineering evaluation work, The Power-Gas 50 bar. This phosphine modified cobalt catalyst also Corporation concluded in a 1970 letter to Johnson gave improved selectivity to the preferred normal Matthey that a proposition for a low pressure propylene butyraldehyde, the isomer ratio (normal:branched hydroformylation process using a homogeneous aldehyde or ‘n:i ratio’) being about 7:1 rather than the rhodium based catalyst would be “economically 3:1 that was typical of the classic cobalt process. To this attractive when compared with what we currently know day, cobalt catalysts are still being used industrially of processes as they are operated today”. By the in some hydroformylation applications, especially in middle of the year, Johnson Matthey and The Power- the manufacture of detergent alcohols from long chain Gas Corporation had entered into a new, but far more olefins produced by ethylene oligomerisation and the wide-reaching collaboration aimed at developing a production from butene dimers and propylene trimer commercial, licensable hydroformylation process of the plasticiser alcohols iso-nonyl alcohol (INA) and initially directed at the conversion of propylene to iso-decyl alcohol (IDA) respectively. 2EH. The agreement was followed by co-ordinated programmes of further research, testing and studies The Beginnings of the LP OxoSM Process of reaction kinetics in the laboratories of both companies. The Power-Gas Corporation did process In the 1960s researchers at the chemicals producer scale-up work and process designs based on predicted Union Carbide Corporation (now a wholly owned optimum reaction conditions. Johnson Matthey subsidiary of The Dow Chemical Company, USA) investigated how it would manufacture commercial in Charleston, West Virginia, USA, and a group led quantities of a suitable rhodium catalyst precursor and by the late Professor Sir Geoffrey Wilkinson (later to also economically manage the recovery of rhodium

247 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3) from used catalyst. Based on information describing modified rhodium catalyst discovered by Union Carbide Union Carbide Corporation’s activity found in literature Corporation and proposed by Wilkinson. Union Carbide searches, Johnson Matthey and The Power-Gas Corporation took the precaution of building a pilot plant Corporation decided to visit Union Carbide Corporation at Ponce so that operating data could be available in the USA in October 1970. It became evident from during the construction of the main plant. The choice early discussions that Union Carbide Corporation had of location meant the catalyst could be tested using the made significant progress on the experimental front commercial feedstocks that were to be used in full-scale but also that Wilkinson’s results complemented the operations. Data from the pilot plant tests calibrated the Union Carbide Corporation findings. After confidential process engineering design of the commercial plant disclosures had been made between them, three that was being carried out by Davy Powergas (another independent companies in different, but overlapping, name change!) in London. Following its decision to fields found they had mutual and complementary build a butyraldehyde plant, Union Carbide Corporation interests and contributions to make in developing decided to fast-track an ethylene hydroformylation potentially revolutionary chemical technology: project at Texas City, USA. The plant started operations • Union Carbide Corporation: A chemicals producer in April 1975 ahead of the Ponce plant, which started having experience in the operation of cobalt oxo in January 1976. The commissioning of both plants systems with their huge shortcomings. Union went smoothly and plant performance was better than Carbide Corporation regarded the potential for expected. At Ponce, the rhodium catalyst operated rhodium with guarded excitement and in the early at less than 20 bar and at a temperature between 1970s was awaiting market conditions to improve 90ºC and 100ºC, much milder conditions compared before deciding whether or not to develop a to cobalt. The isomer ratio, comfortably above 10, commercial rhodium process for its own use in a showed a more than threefold improvement and the new oxo plant lower reaction temperature resulted in significantly less • Johnson Matthey: A precious metal refiner and byproduct formation. The product aldehyde was much processor seeking opportunities to increase its ‘cleaner’, resulting in cost savings in product work-up product range and market reach and eliminating the effluent treatment measures that • The Power-Gas Corporation: A process engineering were needed during cobalt operations (6). With the contractor with wide experience in chemical Ponce plant continuing to operate well and very reliably, projects, international sales and marketing, uncertainties about the robustness of the rhodium which saw the potential relationship between oxo catalyst and the reliability of kinetic models developed synthesis chemistry and the design and supply of in the laboratory abated. Projections of catalyst life plants for producing gases, notably hydrogen and and rhodium related costs were looking much more carbon monoxide, on which it had a long history. favourable than had been assumed. The expected In August 1971, the parties agreed to collaborate to large improvements in yield to desired product normal develop and market low pressure rhodium catalysed butyraldehyde, utility costs and environmental impact oxo technology for use with certain olefinic feeds. were confirmed. A new propylene oxo process was heralded that was far superior to the cobalt process Commercialisation and Start of Licensing Union Carbide Corporation had built and operated at Ponce – which shared many of the characteristics A collaborative process engineering and plant of the cobalt technology then being used by most of design exercise by Power-Gas Ltd (the new name the world’s 2EH producers. The investment capital of The Power-Gas Corporation) and Union Carbide needed for a LP OxoSM Process plant was less than Corporation resulted in even better economics of the for a cobalt plant equivalent because of a simpler flow- propylene LP OxoSM Process than previous studies. sheet, cleaner product and other factors. The lower An upturn in the market was followed by a decision by operating pressure meant in most cases expensive Union Carbide Corporation to build a plant at Ponce, compression of the incoming synthesis gas could be Puerto Rico having a nameplate capacity of 136,000 avoided. tonnes per year of normal and iso-butyraldehydes to In 1977, Union Carbide Corporation, Davy Powergas replace a cobalt catalysed plant. The new plant would Ltd and Johnson Matthey won the prestigious use the homogeneous triphenylphosphine (TPP) Kirkpatrick Chemical Engineering Achievement

Award “for outstanding group effort in new chemical The Early Licensed Plants engineering technology commercialised in the last two In May 1980, the first two licensed plants to be completed years”. In its dissertation the award sponsor, Chemical went into operation – in Sweden and in the Federal Engineering, stated the new LP OxoSM Process “yields Republic of Germany (Figures 2 and 3). These had a a better product mix and also features low capital needs, combined nameplate capacity of over 300,000 tonnes effective use of feed, and negligible environmental per year of butyraldehydes. Ten years on, nine further impact” (7). With such a testimonial the Ponce plant plants had started: three in Japan, two in China and became the target of numerous client visits and by plants in the Republic of Korea, the USA, Poland and the end of 1978 several companies had committed to France. By 1990, the LP OxoSM process was producing build LP OxoSM process plants under licences granted about 1.5 million tonnes per year of butyraldehydes, by Davy Powergas in conjunction with Union Carbide about half of this from seven cobalt ‘conversion’ Corporation. projects. By 2000, no butyraldehyde was being Behind the successful commercialisation of the LP produced by cobalt technology anywhere except in OxoSM Process, both Union Carbide Corporation Russia, which remains so today. All the licensed plants and Davy had intensified their development work used the TPP-modified rhodium catalyst giving typical in laboratories in the UK and the USA. This was n:i ratios of circa 10:1 to 12:1. The catalyst existed in initially aimed at improving the LP OxoSM Process for the same medium as the feedstocks and liquid reaction propylene applications, then the single focus of market products in stirred, back-mixed reactors. The plants interest. An early effort was made in the laboratory by used the ‘gas recycle flow-sheet’ employing in situ gas Union Carbide Corporation to find a way to mitigate stripping to separate reaction products from catalyst to the negative cost impact of what was termed ‘intrinsic’ provide a simple and affordable process design. In Part catalyst deactivation. This was predictable deactivation I of a two-part article (6), Tudor and Ashley explained attributable to the formation of clusters of monomeric the thinking behind this choice of flowsheet. Central to rhodium species, as distinct from deactivation caused this was uncertainty and concerns regarding catalyst by external causes such as the presence of poisons deactivation and the containment or loss of expensive in the feedstocks (6). Union Carbide Corporation’s rhodium. Union Carbide Corporation operators found efforts were to pay dividends (see later). Away from it easy to operate gas recycle reactors to achieve the laboratory, Davy process engineers had visited smooth, stable and dependable plant performance Union Carbide Corporation plants to gather design and without undue concerns about the life or security of the operating data on the industrial scale conversion of rhodium catalyst, and gas stripping was accordingly butyraldehydes to alcohol end products. This led to the adopted as the norm for all of the first generation of two companies agreeing the process basis of alcohol plants using the LP OxoSM Process. Laboratory work technology offerings sought by licensees wishing to by Union Carbide Corporation on intrinsic deactivation use ‘Union Carbide Corporation and Davy’ technology had led to the discovery of a catalyst reactivation for both the propylene hydroformylation step and the technique that could in effect reverse in days the effect conversion of butyraldehydes to 2EH and possibly of months of progressive activity decline because of normal and iso-butanols. See Figure 1. rhodium clustering (6). Most of the early licensees

Hydrogen n-Butyraldehyde Aldolisation Hydrogenation Product refining 2-Ethylhexanol Propylene LP OxoSM Syngas n-Butanol Hydrogenation Product refining n- + iso-Butyraldehyde iso-Butanol Hydrogen

Fig. 1. Schematic showing the production of oxo alcohols from propylene by the LP OxoSM Process

Liquid Recycle Opens Up New Horizons In the first half of the 1980s, with original concerns about catalyst life and security largely behind them, Union Carbide Corporation and Davy turned their attention to a new flowsheet concept employing the ‘liquid recycle’ principle. This involved separating the reaction products from the catalyst solution in equipment outside the oxo reactor, using a proprietary design of vaporiser (8). By decoupling the hydroformylation reaction step from the physical process of product and catalyst separation, it became possible to choose a reaction regime to optimise the reaction conditions without, for example, having to use temperatures high enough to ensure Fig. 2. Butyraldehyde plant built by Chemische Werke Huels effective product removal by gas stripping. Liquid at Marl, Federal Republic of Germany, taken in 1980 recycle would also enable designers to significantly reduce the size of reactors, which for gas recycle had to be large enough to accommodate expansion of the liquid phase by the entrainment of bubbles from a large recycle gas flow. Such were its benefits that nearly all plants designed after the late 1980s used liquid recycle. Several of the earlier licensees, eager to exploit freed-up reactor volume, switched from gas to liquid recycle operation, in some cases nearly doubling the outputs of their oxo units from the same reactors. Liquid recycle technology is today extensively used with enormous success across all applications of the LP OxoSM Process. It has provided designers greater scope for chemical engineering creativity when evaluating flow-sheet options for catalyst innovations and new non-propylene developments.

Polyorganophosphite-Modified Rhodium

The early 1990s saw the emergence of a more advanced polyorganophosphite-modified catalyst that would offer considerable appeal over its TPP counterpart, giving a much improved n:i ratio and other benefits (8). Polyorganophosphite-modified rhodium catalysts are very reactive and show good Fig. 3. The Davy, Union Carbide Corporation and regioselectivity (selectivity to the straight chain Johnson Matthey start-up advisory team at the Marl plant, aldehyde) in comparison with phosphine-modified taken in 1980 catalysts such as TPP. Union Carbide Corporation overcame a major limitation of these new ligands, included in their plants the equipment needed to namely their instability in the presence of aldehydes, achieve such catalyst reactivation and used it to good through the discovery and development of ligand effect to carry out repeated reactivations on what stabilisation systems. Union Carbide Corporation first was essentially a single rhodium catalyst charge. used the new ligand in 1995 in a new butanol plant This drastically reduced the need for off-site rhodium at St Charles, Louisiana, USA, in the anticipation recovery and the reprocessing of recovered rhodium to it would deliver an n:i ratio of about 30:1. The the catalyst precursor. design of this plant, with certain improvements and

250 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3) accumulated operating know-how became the basis use of liquid phase hydrogenation in place of vapour of an advanced propylene LP OxoSM Process using phase which was used in earlier designs, eliminating polyorganophosphite-modified catalyst. Compared the need for a cycle compressor and simplifying the to TPP, it offered significant improvements to reactors. feedstock utilisation efficiency, selectivity to normal butyraldehyde, rhodium inventory and catalyst life. The Non-Propylene Applications of the LP OxoSM success of technology, design and operating measures Technology that Union Carbide Corporation had developed in the laboratory to overcome concerns about the stability By the early 1990s, shifts in markets and client enquiries of the polyorganophosphite-modified catalysts had called for a broader reach of possible applications for pleased Union Carbide Corporation enormously, the the LP OxoSM technology. In response, Union Carbide catalyst at St Charles showing remarkable robustness Corporation and Davy set new development trajectories and no signs of activity loss over a prolonged period, that eventually resulted in new licence offerings for with hardly any rhodium usage. A significant gain several non-propylene applications. (by about 7%) in yield to normal butyraldeyde and the reduced operator attention and plant down-time C7 and Longer Chain Alpha Olefins needed to operate the polyorganophosphite catalyst and manage its life cycle stood out as particular cost The first non-propylene applications were two plants benefits compared to TPP. licensed and built by Sasol at Secunda in South Africa. Today, two Union Carbide Corporation owned butanol Both of them produced alcohols from alpha olefins plants use the polyorganophosphite-modified catalyst sourced from fuel product streams from Sasol’s coal using ‘LP OxoSM SELECTORSM 30’ technology, so based ‘Synthol’ Fischer Tropsch operations. The named to reflect its proven capability of achieving ann:i first started production in 2002 of C12–C13 ‘Safol®’ ratio of at least 30:1. Seven of nine propylene plants so detergent alcohols using a C11–C12 olefin fraction far licensed to use SELECTORSM 30 are in operation, as feed (Figure 4). The second was commissioned in including two examples of where existing licensees 2008 for producing octanol from a 1-heptene fraction for elected to retrofit the technology into TPP plants subsequent conversion to co-monomer grade 1-octene. originally built many years earlier to use (retrospectively The designs of both plants resulted from development called) ‘SELECTORSM 10’ technology. Some of these programmes by Davy at their Technology Centre in plants now achieve n:i ratios greater than 30:1. Teesside, UK, tightly tailored to Sasol’s requirements.

The Propylene LP OxoSM Process Today

The introduction of the polyorganophosphite- modified catalyst system in place of TPP has boosted propylene efficiencies and cut costs needed for seeing out the complete rhodium life cycle. In addition, various patented process enhancements have been introduced and the economics of practically all areas of the flow-sheet improved. Today the process is the source of about 70% of the world’s butyraldehyde and about 90% of licensed-in propylene oxo technology. Nearly all licensees convert butyraldehyde products to 2EH or butanols, and the aldehyde to alcohols part of the flow-sheet has been progressively improved through studies, development projects and catalyst programmes. These have improved the aldol condensation step, and for hydrogenation introduced Fig. 4. Surfactant alcohol plant built by Sasol at Secunda, improved catalysts and reactor designs. On the latter, Republic of South Africa major capital savings have been made by making more

The detergent alcohol development, being the first, was and had assembled sufficient data to provide a the most demanding and at the outset two areas stood platform for the design of the commercial plant as out as being crucial to a successful outcome. Both well as projections of its performance, including stemmed from the characteristics of the designated the expected rhodium usage. Davy subsequently Sasol C11–C12 alpha olefins feed. Firstly, Davy’s used data on reaction kinetics and other information lack of familiarity with such feeds and the uncertainty obtained from the proving run to do the process design of how the Sasol feed would perform over time under of a commercial plant with a throughput about 20,000 hydroformylation conditions suggested innovative times greater. techniques would be needed to identify and remove Before the start-up of the Safol plant, Davy and Sasol impurities that could harm the rhodium catalyst. discussed the potential benefits of a patented proprietary Secondly, there would be a need for continuous purging rhodium recovery process that was being developed of high boiling ultra-heavy reaction byproducts and this by Davy. The proposition was a process that would could be a source of significant rhodium ‘loss’ placing remove and recover most of the largely deactivated an undue burden on the economics of the process. rhodium present in the ultra-heavies purge stream This could be so despite Sasol engaging a third party before recycling that rhodium for reuse in the reaction precious metal refiner to recover and reprocess that system as active catalyst. Tests done by Davy later rhodium off-site. confirmed the effectiveness of the patented technology In the commercial plant, the feed was to be separated and a compelling economic case emerged for it being as a C11–C12 cut in a fractionation system before adopted by Sasol. Its use would eliminate much of being treated primarily to remove impurities known to the cost burden of having to engage a precious metal be detrimental to the oxo catalyst. Early screening tests refiner to extract the rhodium in the purge. Sasol built done by Davy on the reactivity of representative samples the rhodium recovery process to work in conjunction of the pre-treated C11–C12 cut were promising, but with both the Safol plant and the new octanol plant, it became evident that amongst the huge number of which have shared its large benefits since. chemical constituents of the feed was at least one ‘bad actor’, possibly several, affecting the rhodium catalyst. Normal Butenes to 2PH It took considerable experimentation – some of it very conjectural – and then further testing in the mini-plant In the 1980s the phthalate ester of the ‘workhorse’ C8 proving run (see below) to develop and prove a further plasticiser alcohol 2EH – the ‘C8’ plasticiser di-octyl pretreatment step for removing suspected offenders phthalate (DOP) (or di-2-ethylhexyl phthalate (DEHP)) – from the feed to acceptable levels. A need to address was coming under increasing regulatory pressure and the extent of rhodium loss in the ultra-heavies’ purge polyvinyl chloride (PVC) plasticiser producers were stemmed from the high molecular weights of aldehyde paying increasing attention to higher molecular weight products and the very high boiling, undesirable ‘C9’ and ‘C10’ phthalate plasticisers produced from byproducts formed from aldol condensation and C9 and C10 alcohols. These phthalates, containing 9 other reactions. This meant that whatever operating and 10 carbon atoms in each ester chain respectively, regime was adopted to effect the physical separation had better migration and volatility (fogging) properties of desired aldehyde product from catalyst and reaction and were seen as being more suitable for PVC uses byproducts, rhodium catalyst would be present in the where these and other properties, such as their good necessary ultra-heavies’ purge. This too got much weathering behaviour, were especially required. A few attention during the mini-plant run and data collected oxo operators were manufacturing INA or IDA from on the extent of purging needed provided the basis butene dimers and propylene trimers – produced by of projections of the economic implications for the oligomerisation of refinery light olefins – respectively. commercial plant. Market outlets for their corresponding phthalate Davy custom built a ‘mini-plant’ that was configured to plasticisers, diisononyl phthalate (DINP) and diisodecyl simulate the entire olefin to alcohol processing scheme phthlate (DIDP), had been established, and some of proposed by Davy when fed with Sasol supplied C11– them were niche applications that could bear a price C12 feed. This was used for a four-month demonstration premium compared to DOP. Overall however, their run of the process, at the end of which Davy had done usages were small compared to DOP partly because all the testing and evaluation considered necessary of the wide availability of the latter. DOP was also

252 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3) cheaper, largely because of the low production cost of slice of the C4 feed-stream to 2PH, meaning higher 2EH compared to INA and IDA. With market interest in normal butene conversion efficiencies while preserving these higher molecular weight plasticisers increasing relative isomer selectivities. Eventually, as the pull because of their perceived environmental, health and from PVC producers seeking greater versatility and safety performance advantages, several companies, improved long-term property retention in plasticisers most of them 2EH producers, contacted Union Carbide intensified, several oxo producers instigated projects Corporation and Davy with an interest in the production to build the first 2PH plants. In 2007, and after Davy from normal butenes of 2-propylheptanol (2PH), a C10 Process Technology had become part of Johnson alcohol. No 2PH was then being made industrially Matthey, Dow and Johnson Matthey licensed a normal but Union Carbide Corporation and Davy saw the butenes hydroformylation facility in Europe using a results of tests from a number of sources showing the proprietary ligand modified rhodium catalyst system promise of the phthalate ester of 2PH, DPHP, as a PVC to produce mixed valeraldehyde from a C4 raffinate plasticiser. DPHP displayed some of the performance feed for conversion to 2PH. Following the successful characteristics of DINP and DIDP and was also start of this plant in 2009, a second licensed plant seen as a potential substitute for DOP in some PVC started in Asia in 2012. Soon afterwards two Chinese applications. companies launched 2PH projects, both incorporating Before these early signs of market interest, Union Dow and Johnson Matthey hydroformylation, aldol Carbide Corporation and Davy had anticipated and hydrogenation technology. The first of these, with the potential attractions of a 2PH process and had a capacity of 60,000 tonnes per year, successfully conducted hydroformylation trials in the laboratory with started operations in 2014. The second is being built by 1-butene using TPP-modified rhodium catalyst. The a licensee in the Shaanxi Yanchang Petroleum group proposed 2PH process was similar to the 2EH process for producing 80,000 tonnes per year of 2PH in tandem Davy had already licensed with a notable exception. with butanols. Experimental work had shown the ratio of normal to Since 2008, the global use of 2PH has increased branched valeraldehyde product achievable with TPP more strongly than either of the other higher plasticiser was about 20:1 compared to the 10:1 to 12:1 typical of alcohols INA and IDA. Its C10 phthalate ester has been propylene. The expensive aldehyde isomer separation widely accepted as a PVC plasticiser in Europe, the step needed for 2EH production was therefore omitted USA and China. By 2019, the global annual production before aldol condensation and hydrogenation steps of 2PH is expected to exceed 500,000 tonnes, of and product 2PH refining. This meant the commercial which over two thirds will be made using a butene fed 2PH product would actually contain 2-propylheptanol LP OxoSM facility. Commercial C4 streams suitable as the principal component (meaning >85%) in an for feeding to plants utilising the Dow and Johnson isomeric mixture of C10 alcohols. And with butene Matthey 2PH technology include raffinate streams feeds other than higher value co-monomer grade from steam naphtha crackers: either raffinate 2 largely 1-butene then having transfer prices typically between depleted of iso-butene, such as streams available from 55 and 70% of the price of purchased propylene, methyl tert-butyl ether (MTBE) plants or raffinate 3 rich early studies had indicated that 2PH produced from a in 2-butene, the latter being raffinate 2 after its more refinery sourced raffinate-2 stream could be produced highly valued 1-butene component has been removed. with a significant cost advantage over 2EH. This TPP Another possible C4 source is the waste 2-butene based technical platform formed the basis of the stream from a methanol to olefins plant. The very responses to early market interest in 2PH, but later fact that a 2-butene stream can be an economically on it was further enhanced following the introduction viable feed is proof of the high activity and versatility of more advanced proprietary ligands. Potential 2PH of the Dow and Johnson Matthey catalyst, especially producers tabled C4 feed-stream specifications with when one considers the reactivity in hydroformylation significant concentrations of 1-butene and 2-butene of 2-butene (cis- and trans-) is as low as one fiftieth (both cis- and trans-) as well as non-reactive butanes. that of 1-butene. Other potential feed sources could The use of the much more reactive proprietary ligand conceivably be C4 olefinic fractions from Fischer- in place of TPP meant the less reactive 2-butene Tropsch plants. All of the above sources are likely to component was now able to contribute significantly to be cheaper than the olefins feeding 2EH, INA or IDA product yield. It could therefore convert a much larger plants.

Where there is interest from a 2EH or butanols in various coatings, floor polishes, textiles and as a producer in making 2PH if market conditions suit, gasoline additive. Johnson Matthey can design cost effective flexible Iso-butyraldehyde has a multitude of uses as an LP OxoSM plants capable of using propylene and intermediate – to name a few, pharmaceuticals, butene as separate feedstocks either continuously or crop protection products and pesticides. A key intermittently. outlet is neopentylglycol (NPG) or 2,2-dimethyl-1,3- propanediol, produced by the aldol condensation of The Alcohol Products from C3 and C4 iso-butyraldehyde and formaldehyde. NPG is mainly Hydroformylation and their Uses used as a building block in polyester resins for coatings, unsaturated polyesters, lubricants and plasticisers. Butyraldehyde is mainly used in the production Iso-butanol has similar properties to normal butanol of 2EH and butanols. Of the two isomers, normal and may be used as a supplement or replacement butyraldehyde is the more valuable, because unlike for it in some applications. More specific uses include iso-butyraldehyde, it can be used to produce 2EH. Also, industrial coatings and cleaners, de-icing fluids, normal butanol usually offers solvent and derivative flotation agents, textiles and as a gasoline additive. It value superior to that of iso-butanol. A small outlet for is also an intermediate for agricultural chemicals and normal butyraldehyde is trimethylolpropane used as a for glycol ethers and esters. An outlet for iso-butyric building block in the polymer industry. acid, the oxidation product from iso-butyraldehyde, is a Large quantities of 2EH are esterified with phthalic monoester of trimethyl pentanediol which has a use as anhydride to produce the PVC plasticiser DEHP, often a coalescing agent for latex paints. referred to as DOP. While strong demand for DEHP in The main component of commercially produced Asia has sustained a global growth rate of about 2.5%, 2PH is 2-propylheptane-1-ol derived from the normal regulatory pressures have meant Western Europe valeraldehyde present in the product from the and the USA now together account for less than 5% hydroformylation of normal butenes. Other lesser of world usage, with demand in the former practically components are 4-methyl 2-propyl 1-hexanol and zero. In recent years increasing amounts of 2EH have 5-methyl 2-propyl 1-hexanol, derived from branched been used to produce di(2-ethylhexyl) terephthalate aldehyde isomers in the aldol condensation feed. The (DEHTP) or dioctyl terephthalate (DOTP), using phthalate ester of 2PH is di-(2-propylheptyl) phthalate dimethyl terephthalate or purified terephthalic acid as as its principal component, giving the plasticiser the the other primary input. Not being an ortho-phthalate generic name DPHP. It is a versatile PVC plasticiser plasticiser like DEHP, DOTP has a growing use as with impressive weathering and low fogging properties a replacement for DEHP, in particular, without any making it particularly suitable for tough outdoor uses negative regulatory pressure. Increasing amounts of such as roofing membranes and tarpaulins, automotive, 2EH are being esterified with acrylic acid to produce wires and cables and cable ducts. 2-ethylhexylacrylate, used in the production of homopolymers, copolymers for caulks, coatings and LP OxoSM Technology Today pressure-sensitive adhesives, paints, leather finishing and textile and paper coatings. 2EH is also used to In 2001 Union Carbide Corporation became a wholly produce 2-ethylhexyl nitrate, a diesel fuel additive and owned subsidiary of The Dow Chemical Company. also lubricant additives. In 2006 Davy Process Technology became part of Normal butanol is used industrially for its solvent Johnson Matthey. The process development and properties, but by far its largest use is as an industrial marketing collaboration today between Johnson intermediate. Butyl acrylate is widely used in the Matthey and Dow Global Technologies, Inc, has its production of homopolymers and copolymers for use roots in the historic 1971 agreement between Union in water-based industrial and architectural paints, Carbide Corporation, Johnson Matthey and The enamels, adhesives, caulks and sealants, and Power-Gas Corporation, but now spans more olefins textile finishes. Butyl methacrylate’s uses include the giving it a broader market reach. To date, 53 LP OxoSM manufacture of acrylic sheet, clear plastics, automotive technology projects have now been licensed, six of coatings and other lacquers. n-Butyl acetate is an them for non-propylene applications. The collaboration industrial solvent and artificial flavourant and is used is as close and focused as it ever was, and the resolve

254 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695875 Johnson Matthey Technol. Rev., 2017, 61, (3) of Dow and Johnson Matthey is to sustain the place for LP OxoSM Technology as the premier oxo technology in the world through safe, innovative, low environmental impact and cost advantaged technical solutions, forever pushing the boundaries of the technology even further. Germane to many further developments will be the role for advanced ligand systems that have already boosted propylene and butene efficiencies and cut costs needed for seeing out the complete rhodium life cycle. Some new developments are already at the stage where they can be licensed for commercial use.

Examples of New Developments Propylene n:i Ratio Flexibility Fig. 5. Johnson Matthey oxo pilot plant for INA process development at Stockton-on-Tees, UK In those instances where operators are seeking a wide flexibility in the butyraldehyde isomer ratio, ‘Variable SELECTORSM’ Technology has been developed that sourced C3 and C4 olefins, building a single, highly enables the n:i ratio to be adjusted on-line within the flexible, LP OxoSM facility using advanced, dependable range of 2:1 and 30:1 to suit market conditions by technologies to selectively deliver any and all of 2EH, adjusting operating parameters. INA and 2PH – as well as butanols. Collectively, the three higher alcohols supply more than two thirds of a INA from Butene Dimer and, the “All Singing, very diverse plasticiser market. SM SM All Dancing” Oxo Plant? LP Oxo and SELECTOR are service marks of The Dow Chemical Company (“Dow”) or an affiliate of The global plasticiser market is currently about 8 million Dow. tonnes per year and is growing at around 3 to 4% per year. The market share of the C9 phthalate DINP Acknowledgements has increased in recent years and the consequential The photographs taken at the Chemische Werke Huels growing global demand for INA, currently about 1.4 plant and of the Safol plant are included with the kind million tonnes per year, is being met by new projects permissions of Evonik Industries (Figures 2 and 3) and announced for Asia. A first INA plant in China started Sasol Ltd (Figure 4) respectively. production in 2015. The superior migration and fogging References properties and more favourable toxicological profiles of C9 and C10 phthalate plasticisers compared to DEHP 1. G. Frey, ‘75 Years of Oxo Synthesis’, Speciality should ensure sustained growth in the use of both Chemicals Magazine, 8th October, 2013 DINP and DPHP. 2. F. J. Smith, Platinum Metals Rev., 1975, 19, (3), 93 To meet the growing demand for INA, Dow and 3. M. J. H. Russell, Platinum Metals Rev., 1988, 32, Johnson Matthey have developed a new low pressure (4), 179 rhodium catalysed INA process in pilot plants at 4. G. Wilkinson, Platinum Metals Rev., 1968, 12, (4), 135 Dow and Johnson Matthey (see Figure 5) using 5. M. L. H. Green and W. P. Griffith, Platinum Metals commercially produced butene dimer feedstock. One of Rev., 1998, 42, (4), 168 its key attributes is it can be retrofitted to existing 2EH 6. R. Tudor and M. Ashley, Platinum Metals Rev., 2007, SM or butanol plants built by licensees of the LP Oxo 51, (3), 116 Process, creating for them and for new licensees the 7. ‘Low-Pressure Oxo Process Yields a Better Product opportunity to run flexible product oxo plants to best Mix’, Chemical Engineering (New York), 5th December, exploit market conditions. And with the 2PH process 1977, 110 being similarly retrofittable, one can now envisage an 8. R. Tudor and M. Ashley, Platinum Metals Rev., 2007, oxo producer having flexible access to say, refinery 51, (4), 164

The Authors

Richard Tudor retired from Davy Process Technology in 2011 as Vice President, Oxo Business following an involvement of over 35 years in the company’s oxo licensing activities, initially in a technical capacity becoming Process Manager. His first commercial role was a broad remit as the company’s Licensing Manager, following which he ran the oxo business for over 20 years. He graduated in Chemical Engineering from the University of Manchester, UK, and is a Fellow of the Institution of Chemical Engineers and a former member of the Licensing Executives Society. Between 2011 and 2016 he continued working for Johnson Matthey as licensing consultant.

Atul Shah is Licensing Development Director at Johnson Matthey, London, UK. He has worked on many oxo alcohol projects globally and has played a leading role in Johnson Matthey’s oxo alcohols licensing business for over 30 years, both in technology and business development. Atul graduated from the University of London with a BSc (Eng) in Chemical Engineering and joined Davy in 1984, which became part of Johnson Matthey in 2006. He holds an MBA and is a Fellow of the Institution of Chemical Engineers.

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Two Hundred Proud Years – the Bicentenary of Johnson Matthey Origins of the company and of today’s research activities in science and technology

W. P. Griffith some of Johnson Matthey’s considerable recent Department of Chemistry, Imperial College, London non‑pgm activities. SW7 2AZ, UK The Johnsons of Maiden Lane Email: [email protected] The forebears of Percival Norton Johnson, who in 1817 became the founder of the precursor of Johnson The story of the first 200 years of Johnson Matthey is Matthey, came from a family well acquainted with metal told. The firm was started in 1817 by Percival Johnson, assaying and refining (4, 5). His grandfather John but in 1851 George Matthey became a partner and the Johnson (1737–1786) had since 1777 been an assayer present name was derived from these two partners. of ores and metals, mostly silver, gold and some base A number of milestones in its illustrious history are metals, at No. 7, Maiden Lane (now part of Gresham reviewed, and some of the current activities of the Street between Wood Street and Foster Lane, London company are brought up to date, in this short article. EC2). His son, also John Johnson (1765–1831) was apprenticed to him in 1779, and on his father’s death Introduction took over his business, becoming the only commercial assayer in London. Around 1800 he became involved Thirty-five years ago a magisterial volume was published with the rapidly developing platinum metals industry, by Johnson Matthey on “A History of Platinum and using crude ‘platina’ smuggled to Britain via Jamaica its Allied Metals”, but despite its title that book is also from what is now Colombia. His biggest early customer a history of the firm itself from 1817 to 1982 (1). The was probably William Hyde Wollaston (1766–1826) present account marks Johnson Matthey’s bicentenary, (6), who made many purchases of platina between and is much indebted to that volume; many aspects of 1802–1819 from Johnson. Wollaston developed a the story have also been chronicled by Platinum Metals secret process for isolating platinum so pure that it could Review and its 2014 successor, the Johnson Matthey be fashioned into crucibles, chalices and other vessels Technology Review. Appropriate references to these and drawn into wires much thinner than a human hair; journals are given wherever possible. A Platinum Metals this business made him wealthy. In addition to isolating Review paper marking the firm’s sesquicentenary was rhodium and palladium in 1802 (6, 7), he sold to his published in 1967 (2), and a recent paper notes that friend and partner Smithson Tennant some ore from Johnson Matthey is one of the oldest British chemical which Tennant in 1804 isolated iridium and osmium firms still in existence (3). In this survey we concentrate (8, 9). on the firm’s formative years and, while highlighting its Percival Norton Johnson (1792–1866), was born on activities with platinum group metals (pgms), include 29th September 1792 at 6–7 Maiden Lane and was

257 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695884 Johnson Matthey Technol. Rev., 2017, 61, (3) apprenticed to his father John Johnson. In 1812, aged persuaded a reluctant Johnson to exhibit samples of only 19, he established his scientific credentials in a platinum, palladium, rhodium and iridium at the Great paper showing that platinum alloyed with silver and gold Exhibition of 1851, for which they were awarded a would dissolve in nitric acid (10, 11). prize. Johnson took him into partnership in the same year and renamed the firm Johnson and Matthey. In The Early Years of Percival Johnson’s New Firm 1846 Percival Johnson was elected a Fellow of the Royal Society (FRS), his election being supported by The date of foundation of what 34 years later Michael Faraday (to whom the firm had given an ingot would be called Johnson Matthey is established as of platinum and some platinum wire for a famous Royal January 1st 1817 (1, 2). On that day Percival Johnson Institution discourse). left his father’s business and set up his own business In 1852 Johnson Matthey was appointed official as an ‘Assayer and Practical Mineralogist’ with his assayer to the Bank of England followed by official brother John Frederick as assistant, although he would refiner in 1861. A key event in the firm’s history was later collaborate with his father (2). The year 1817 was Matthey’s collaboration with Jules Henri Debray also that in which Humphry Davy showed that a platinum (1827–1888) for melting platinum on a large scale (18). wire (almost certainly provided by Johnson) would At the Paris Exhibition of 1867, Johnson Matthey was catalyse the combination of oxygen and hydrogen – the awarded two gold medals for its fine display of some first demonstration of heterogeneous catalysis (12, 13). 15,000 ounces of pgms in many forms, and as a result In 1818 Percival moved to 8 Maiden Lane and in George Matthey became a Chevalier of the Légion 1822 to 79 Hatton Garden, the latter being expanded in d’Honneur, one of France’s highest honours. In 1874 1850. In 1826 he brought in another talented assayer, the firm made the first standard metre and standard John Stokes, renaming the firm Johnson and Stokes in kilogram in 10% iridium-90% platinum alloy for the 1832. When Stokes died in 1835, William John Cock International Metric Commission. This kilogram is still (1813–1892), like Percival Johnson a founder member the standard measure and will be so until late 2018 of the Chemical Society in 1841 (14), joined Percival when it will be defined using a more modern technique. in the firm which was now called Johnson and Cock. It is now held in the the Bureau international des poids et William was the son of Thomas Cock (1782–1842), mesures in Sèvres (19). In a rare departure at the time Percival’s brother-in-law, also an assayer. from pgms, Johnson Matthey almost certainly provided William Cock was a considerable chemist and the high purity aluminium for the statue known as Eros, metallurgist, devising a new procedure for increasing erected in 1892 in Piccadilly Circus (20). the malleability of platinum, and published ‘On In 1879 Matthey was awarded an FRS: like Johnson Palladium – Its Extraction, Alloys &c.’ (15, 16) in and Cock he had published several papers, including one of the earliest of the Chemical Society’s papers. an important one on the removal of rhodium and iridium Johnson and Cock produced a platinum medal for from platinum, and the preparation of a platinum-iridium Queen Victoria’s coronation in 1838, and in 1844 made alloy (21). Both he and Johnson are commemorated the platinum from which the standard pound weight in the new “Oxford Dictionary of National Biography” was made. Cock resigned in 1845 from ill-health, but (22, 23). Like Johnson, George Matthey was a great continued collaboration; Johnson’s firm was now called supporter of the Chemical Society, thus continuing a P. N. Johnson & Co (1). long and still current association between the Society (now the Royal Society of Chemistry) and Johnson Johnson’s Firm Renamed Johnson and Matthey (14). Matthey In 1860 George Matthey’s brother Edward (1836–1918) was appointed a junior partner: he In 1838 Johnson and Cock apprenticed the second had studied under Hofmann at the Royal College of person commemorated in the present firm’s name, Chemistry. Another partner was John Scudamore George Matthey (1825–1913) (17). Just thirteen when Sellon (1836–1918), a nephew of Johnson’s wife, they first employed him, he quickly became interested who had commercial experience; the firm was now in platinum and Cock took him under his wing. Matthey renamed Johnson Matthey and Co (1). On 1st June had a shrewd business mind as well as an excellent 1866 Percival Johnson died (22); George Matthey knowledge of chemistry and metallurgy, and he wrote an obituary (published in the Anniversary meeting

258 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695884 Johnson Matthey Technol. Rev., 2017, 61, (3) of the Chemical Society, March 30th, 1867, page 392 of platinum and other pgms, and though admired, (24)). George Matthey retired in 1909 after a 70-year particularly in France, was relatively little known abroad. career; and died on 14th February 1913 (23, 25). John It is now a major international company dealing with Sellon replaced him as chairman, but died in 1918 as many aspects of pgm and non-pgm technologies. Major did Edward Matthey. The Matthey succession on the factors leading to this were the establishment of a company’s board was secured by George’s son Percy plentiful source of pgms, the foundation of an outstanding St. Clair Matthey (1862–1928) and, from 1928, by research department, and its later diversification with Edward Matthey’s son Hay Whitworth Pierre Matthey non-pgm technology. (1876–1957), chairman until 1957 (1). Johnson Matthey became a limited company in 1891 Johnson Matthey’s Research Department, and and its ordinary shares were first listed on the London Collaboration with Academic Institutions Stock Exchange in 1942. It subsequently opened businesses in the USA (1927); Australia and New In 1918 Alan Richard Powell (1894–1975) established Zealand (1948); across Europe (in the 1950s); India a research department at Johnson Matthey and was (1964); Japan (1969); Mexico and Malaysia (1995) for 36 years its Research Manager; he was awarded and in China (2001). There are now Johnson Matthey an FRS in 1953 (28). The department initially occupied operations in over 30 countries. two rooms at Hatton Garden but in 1938 moved to Wembley, and then in 1976 to its present location at Sources of Platinum Group Metals Sonning Common, near Reading (29). Powell wrote an account of the first fifty years of his department (30). John and Percival Johnson used platina smuggled into Early in the 20th century Johnson Matthey launched Britain by speculators from the Choco district of what an unusual initiative, later called the Johnson Matthey is now Colombia from ca. 1780–1830. After Colombia Loan Scheme, of which the author was for many years became independent of Spain less platina found its a beneficiary, as were many others in university and way to Europe and Johnson Matthey seems to have other departments worldwide. Compounds of rare used Russian supplies from around 1850 (1) and, early materials, mainly pgms, were given, without charge, to in the 20th century, Canadian sources from Ontario bona fide researchers for work on innovative science. (2). Everything changed though with the discovery Researchers were free to publish their material, the only of huge reserves of pgm-bearing ore in South Africa, stipulation being that the residues of material used were first found there in 1906 (26). In 1925 the huge South returned to Johnson Matthey (31). Much useful work African Merensky Reef which contains some 80% of the resulted from this; a good example being that of the world’s reserves of pgms was discovered, and by 1931 late Sir Geoffrey Wilkinson (FRS and Nobel laureate) Johnson Matthey took and continued to take pgms whose extensive work on synthesis and homogeneous from the mines in the Rustenburg region, 100 km west catalysis by pgm complexes would have been of Pretoria (27), for many years. In 1925 the ground- impossible without the scheme (32, 33). The scheme breaking Powell-Deering smelting and refining process has been replaced by one in which Johnson Matthey for Rustenburg ore was developed by Johnson Matthey. continues to collaborate with universities and others, A refinery was set up in Brimsdown, near Enfield, UK, and often provides research materials. in 1928. This is still in use, though primary refining of In 1957 the quarterly Platinum Metals Review South African pgm-containing ores is done in South was founded by Johnson Matthey; after 58 years of Africa. Some primary refining is carried out by Johnson production it became the Johnson Matthey Technology Matthey. However the company remains the world’s Review in mid-2014, partly to signal that much of the largest secondary refiner of pgms, with refineries in company’s current research and applications are no Royston and Brimsdown in the UK, West Deptford in longer pgm-based. Volume numbers remain as for the USA and in China. Platinum Metals Review.

Johnson Matthey in the 20th and 21st Centuries Areas of Prime Development in Johnson Matthey Until the late 19th century Johnson Matthey was mainly concerned with relatively small-scale applications The company is actively involved with many areas

259 © 2017 Johnson Matthey https://doi.org/10.1595/205651317X695884 Johnson Matthey Technol. Rev., 2017, 61, (3) including automotive emission control catalysts, carbon dioxide and hydrogen) to methanol; oxo alcohols homogeneous and heterogeneous catalysis for from hydroformylation reactions involving alkene petroleum refining, oxidation of ammonia to nitric acid, oxidations with syngas; and the production of biodiesel. manufacture of active pharmaceutical ingredients, components for glass manufacture, thermocouples and advanced battery materials, fuel cells and water Health: Chemotherapy purification, and much more. Johnson Matthey states that its focus today as it celebrates its 200th year is on Another area in which Johnson Matthey played an the global priorities of cleaner air, the efficient use of important early and continuing part was the use of pgm natural resources and improved health (34, 35). Here complexes, particularly of platinum, in the treatment of we briefly note some aspects of Johnson Matthey’s malignant cancers, starting in 1983. First-generation research and production in these areas. (cisplatin), and many second- and third-generation drugs have been made and investigated by the Clean Air: Automotive company, and very recently reviewed (42). In 1993 Johnson Matthey bought Meconic, a holding company Johnson Matthey was and is a leader since the 1960s for the pharmaceutical company MacFarlan Smith, and in conversion of the toxic components of vehicle this became part of Johnson Matthey; a major interest exhaust gases – hydrocarbons, carbon monoxide and now is the synthesis of pharmaceuticals often without oxides of nitrogen (NOx) – to carbon dioxide, water and pgm-based technology. nitrogen; there has also been much progress with diesel emissions and particulates (36–38) and with removal Conclusions of alkenes and alkynes from automotive emissions. In 1977 Johnson Matthey was presented with the Queen’s The origins of Johnson Matthey – founded in 1817 Award for Technological Achievement for its pioneering by Percival Johnson and later strengthened by the work in emissions control (39). The company now appointment of George Matthey – have been described accounts for one in three of the catalysts on cars around with some of its principal achievements over the last the world. two centuries. The focus of the company in the 21st A non-pgm area of research and production is the century which has grown to include many non-pgm design and manufacture of low-power low-capacity technologies has been highlighted. batteries for industrial and leisure uses and high-power high-capacity batteries for automotive applications, Acknowledgement such as high performance hybrid and plug-in hybrid vehicles. Most of these are lithium-ion based. The first The author thanks Dan Carter and Ian Godwin for their themed issue of Johnson Matthey Technology Review help in providing information on some of the latest in 2015 was devoted to battery technologies (40, 41). initiatives at Johnson Matthey.

Efficient Use of Natural Resources References 1. D. McDonald and L. B. Hunt, “A History of Platinum In 2002 ICI sold its Synetix process catalysts business and its Allied Metals”, Johnson Matthey, London, UK, along with its Tracerco subsidiary to Johnson Matthey. 1982, pp 450 The process catalysts business provided Johnson 2. D. McDonald, Platinum Metals Rev., 1967, 11, (1), 18 Matthey with a strong global position in non-precious metal catalysts used in a wide range of major chemical 3. A. Extance, Chemistry World, 2017, 14, (5), 22 manufacturing processes, an area that has been 4. D. McDonald, “The Johnsons of Maiden Lane”, strengthened by further acquisitions. In 2006 Johnson Martins Publishers Ltd, London, UK, 1964, 180 pp Matthey bought Davy Process Technology (DPT), thus 5. D. McDonald, “Percival Norton Johnson, the strengthening its position as a catalyst and technology Biography of a Pioneering Metallurgist”, Johnson supplier to the world’s chemical and energy industries. Matthey, London, UK, 1951, 224 pp Some of the many processes involved include the 6. M. C. Usselman, “Pure Intelligence: The Life of catalysed conversion of syngas (carbon monoxide, William Hyde Wollaston”, The University of Chicago,

Chicago, USA, 2015, pp 424 at Imperial College: A History 1845–2000”, World 7. W. P. Griffith,Platinum Metals Rev., 2003, 47, (4), 175 Scientific Publishing Europe Ltd, London, UK, 2017, 584 pp 8. W. P. Griffith,Platinum Metals Rev., 2004, 48, (4), 182 34. ‘Johnson Matthey at 200 – Aligned for Growth’, 9. L. B. Hunt, Platinum Metals Rev., 1987, 31, (1), 32 Johnson Matthey, London, UK, 20th April, 2017 10. P. Johnson, Phil. Mag., 1812, 40, (171), 3 35. ‘A New Brand, 200 Years in the Making: Johnson 11. D. McDonald, Platinum Metals Rev., 1962, 6, (3), 112 Matthey Reveals Refreshed Identity’, Johnson 12. H. Davy, Phil. Trans. R. Soc. Lond., 1817, 107, 77 Matthey, London, UK, 8th May, 2017 13. L. B. Hunt, Platinum Metals Rev., 1979, 23, (1), 29 36. A. Raj, Johnson Matthey Technol. Rev., 2016, 60, (4), 14. W. P. Griffith,Platinum Metals Rev., 2013, 57, (2), 110 228 15. W. J. Cock, Mem. Chem. Soc., Lond., 1843, 1, 161 37. C. Morgan, Johnson Matthey Technol. Rev., 2014, 58, (4), 217 16. L. B. Hunt, Platinum Metals Rev., 1983, 27, (3), 129 38. M. V. Twigg and P. R. Phillips, Platinum Metals Rev., 17. L. B. Hunt, Platinum Metals Rev., 1979, 23, (2), 68 2009, 53, (1), 27 18. W. P. Griffith,Platinum Metals Rev., 2009, 53, (4), 209 39. Platinum Metals Rev., 1977, 21, (3), 84 19. T. J. Quinn, Platinum Metals Rev., 1986, 30, (2), 74 40. M. Green, Johnson Matthey Technol. Rev., 2015, 59, 20. D. McDonald, “The History of Johnson, Matthey & Co. (1), 2 Limited”, Volume 1, Johnson Matthey, London, UK, 196X 41. P. Miller, Johnson Matthey Technol. Rev., 2015, 59, (1), 4 21. G. Matthey, Proc. R. Soc. Lond., 1878, 28, (190–195), 463 42. C. Barnard, Johnson Matthey Technol. Rev., 2017, 61, (1), 52 22. I. E. Cottington, ‘Johnson, Percival Norton (1792– 1866)’, “Oxford Dictionary of National Biography”, Oxford University Press, Oxford, UK, 2004 23. I. E. Cottington, ‘Matthey, George (1825–1913)’, “Oxford Dictionary of National Biography”, Oxford The Author University Press, Oxford, UK, 2004 Bill Griffith is an Emeritus Professor 24. J. Chem. Soc., 1867, 20, 385 of Chemistry at Imperial College, 25. L. W. Stansell, F. S. Kipping, A. G. Perkin, C. A. Keane, London, UK. He has much A. P. Laurie, A. R. Ling and T. K. Rose, J. Chem. Soc., experience with the platinum group Trans., 1914, 105, 1189 metals, particularly ruthenium 26. R. G. Cawthorn, Platinum Metals Rev., 2006, 50, (3), and osmium. He has published 130 over 270 research papers, many 27. J. T. Bruce, Platinum Metals Rev., 1996, 40, (1), 2 describing complexes of these 28. G. V. Raynor, Biogr. Mems. Fell. R. Soc., 1976, 22, metals as catalysts for specific 307 organic oxidations. He has written 29. I. E. Cottington, Platinum Metals Rev., 1976, 20, (3), eight books on the platinum metals, 74 and has published, with Hannah 30. A. R. Powell, Platinum Metals Rev.,1968, 12, (1), 22 Gay, a history of the 170-year old 31. D. T. Thompson, Platinum Metals Rev., 1987, 31, (4), chemistry department at Imperial 171 College (33). He is responsible for 32. M. L. H. Green and W. P. Griffith, Platinum Metals Membership at the Historical Group Rev., 1998, 42, (4), 168 of the Royal Society of Chemistry. 33. H. Gay and W. P. Griffith, “The Chemistry Department

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Johnson Matthey Highlights A selection of recent publications by Johnson Matthey R&D staff and collaborators

Structural Changes in Cartilage and Collagen Studied higher mean particle size than those prepared using the by High Temperature Raman Spectroscopy organic solution at the same O2 dispersion. In this case M. Fields, N. Spencer, J. Dudhia and P. F. McMillan, a mixture of type II La2O2CO3 and La2O3 was attained. Biopolymers, 2017, 107, (6), e23017 The materials were assessed for oxidative coupling of methane (OCM) and the authors were able to show High temperature Raman spectra for freeze-dried that by changing the synthesis parameters, the OCM cartilage samples which demonstrate a rise in performance of the materials could be altered. laser-excited fluorescence interpreted as conformational changes corresponding to denaturation above 140ºC Reforming Biomass Derived Pyrolysis Bio-oil Aqueous are reported. Spectra for separated collagen and Phase to Fuels proteoglycan fractions extracted from cartilage show the C. Mukarakate, R. J. Evans, S. Deutch, T. Evans, A. changes are linked with collagen. At high temperature K. Starace, J. ten Dam, M. J. Watson and K. Magrini, peptide hydrolysis occurs suggesting that molecular Energy Fuels, 2017, 31, (2), 1600 H2O is retained within the freeze-dried tissue as shown by the Raman data. Thermogravimetric analysis The catalytic conversion of the biogenic carbon in pyrolysis aqueous phase streams to produce supports this hypothesis and shows 5–7 wt% H2O remaining within freeze-dried cartilage that is gradually hydrocarbons using a vertical microreactor coupled to released upon heating up to 200ºC. The capacity of the a molecular beam mass spectrometer (MBMS) was denatured collagen to re-absorb water is diminished investigated. Real-time analysis of products and tracking and is shown by the spectra attained after exposure to catalyst deactivation are provided by the MBMS. The high temperature and re-hydration following recovery. HZSM-5 catalyst was used in this work, which improved the oxygenated organics in the aqueous fraction Tailoring the Physical and Catalytic Properties of from noncatalytic fast pyrolysis of oak wood to fuels Lanthanum Oxycarbonate Nanoparticles containing small olefins and aromatic hydrocarbons. C. Estruch Bosch, M. P. Copley, T. Eralp, E. Bilbé, J. The HZSM-5 catalyst showed higher activity and coke W. Thybaut, G. B. Marin and P. Collier, Appl. Catal. A: resistance during processing of the aqueous bio-oil Gen., 2017, 536, 104 fraction compared to similar experiments using biomass or whole bio-oils. Decreased coking was possible due Lanthanum oxide and its carbonate analogues were to a release of coke precursors from the catalyst pores synthesised by flame spray pyrolysis (FSP). Two that was improved by excess process water available different feeds were investigated: an organic solution for steam stripping. and an aqueous organic microemulsion. The properties of the materials prepared are effected by a key Lithium and Boron as Interstitial Palladium Dopants for experimental parameter of FSP, the O2 dispersion i.e. Catalytic Partial Hydrogenation of Acetylene the flow rate of the dispersing gas in the FSP nozzle. I. T. Ellis, E. H. Wolf, G. Jones, B. Lo, M. M.-J. Li, A. P. When a lanthanum containing organic solution was E. York and S. C. E. Tsang, Chem. Commun., 2017, 53, used as FSP feed, a rise in the level of O dispersion led 2 (3), 601 to a rise in surface area and a reduction in mean particle size and basicity. Lanthanum can form different phases, It has been shown that light elements, including for example, oxides, hydroxides, oxycarbonates and lithium and boron atoms, can reside in the octahedral carbonates. The rise of O2 dispersion also initiated (interstitial) site of a Pd lattice by altering the electronic a phase change, going from a mixture of type Ia and properties of the metal nanoparticles, and therefore the type II La2O2CO3 and La2O3 to pure La2O3. Using adsorptive strength of a reactant. The obstruction of the an aqueous or organic microemulsion feed which sub-surface sites to H in the altered materials resulted had a higher viscosity compared to the organic feed, in substantially increased selectivity for the partial produced materials with a lower surface area and a catalytic hydrogenation of acetylene to ethylene.

Structure–Activity Relationship of Different Cu–Zeolite observed in an ordered ABC-6 material. Elemental 13 Catalysts for NH3–SCR analysis, C MAS NMR, computer modelling and M. P. Ruggeri, I. Nova, E. Tronconi, J. E. Collier and A. Rietveld refinement were combined to obtain models P. E. York, Top. Catal., 2016, 59, (10–12), 875 for the location of the templates within cages of the framework. Three different catalytic materials for NH3-SCR applications were investigated and its activities and selectivities towards undesired products (for example, N2O and NH4NO3) were compared. The selected materials included a large pore Cu-BETA catalyst and two small pore structures: a Cu-CHA and a Cu-SAPO material, and were characterised by the same Cu loading. The objective was to study the potential impact of the microporous structure of the catalyst on the SCR performances.

Effect of Graphene Support on Large Pt Nanoparticles L. G. Verga, J. Aarons, M. Sarwar, D. Thompsett, A. E. Russell and C.-K. Skylaris, Phys. Chem. Chem. Phys., Reprinted with permission from (A. Turrina, R. Garcia, A. 2016, 18, (48), 32713 E. Watts, H. F. Greer, J. Bradley, W. Zhou, P. A. Cox, M. D. Pt clusters with up to 309 atoms interacting with single Shannon, A. Mayoral, J. L. Casci and P. A. Wright, Chem. graphene supports with up to 880 carbon atoms Mater., 2017, 29, (5), 2180). Copyright (2017) American were simulated by large-scale DFT calculations. The Chemical Society adsorption, cohesion and formation energies of two and three-dimensional Pt clusters interacting with Enhancing the Thermoelectric Properties of Single and the support, including dispersion interactions via a Double Filled p-Type Skutterudites Synthesized by an semi-empirical dispersion correction and a vdW Up-Scaled Ball-Milling Process functional were computed. When interacting with the support, three-dimensional Pt clusters are more stable J. Prado-Gonjal, P. Vaqueiro, C. Nuttall, R. Potter and A. than the two-dimensional and the difference between V. Powell, J. Alloy. Compd., 2017, 695, 3598 their stabilities increases with the system size. As Mechanical alloying was used to prepare single and the nanoparticle size is increased, the dispersion double filled p-type skutterudites Ce0.8Fe3CoSb12 interactions are more pronounced and this is crucial and Ce0.5Yb0.5Fe3.25Co0.75Sb12. It is a rapid method to a reliable description of larger systems. The overall for preparing skutterudites that could be scaled up charge is transferred from the Pt clusters to the support to industrial level. Enhanced figures of merit ZT as interatomic expansion (contraction) on the closest were found for large-scale samples prepared by (farthest) Pt facets from the graphene sheet and charge ball-milling compared with those prepared by redistribution were observed. conventional solid-state reaction. ZT rises ca. 19% at room temperature due to reduced grain size leading to STA-20: An ABC-6 Zeotype Structure Prepared by reduced thermal conductivity. Effect of microstructure Co-Templating and Solved via a Hypothetical Structure on thermoelectric properties, stability in air and Database and STEM-ADF Imaging performance after multiple heating and cooling cycles A. Turrina, R. Garcia, A. E. Watts, H. F. Greer, J. Bradley, are presented. Improved resistance to oxidation are W. Zhou, P. A. Cox, M. D. Shannon, A. Mayoral, J. L. found in the densified samples prepared by ball-milling Casci and P. A. Wright, Chem. Mater., 2017, 29, (5), starting at 694 K for Ce0.8Fe3CoSb12 and at 783 K for 2180 Ce0.5Yb0.5Fe3.25Co0.75Sb12. Dual templating by diDABCO-C6A and trimethylamine A New Type of Scaling Relations to Assess the Accuracy was used to prepare a novel microporous of Computational Predictions of Catalytic Activities silicoaluminophosphate with topology STA-20 Applied to the Oxygen Evolution Reaction (see Figure). A hypothetical zeolite database and L. G. V. Briquet, M. Sarwar, J. Mugo, G. Jones and F. ADF-STEM with Rietveld refinement were used to Calle-Vallejo, ChemCatChem, 2017, 9, (7), 1261 resolve its structure. The zeotype structure STA-20 is a member of the ABC-6 family and it has trigonal symmetry, Explicit water solvation and functionals that account P-31c, with a = 13.15497(18) Å and c = 30.5833(4) Å in for van der Waals interactions were used to modify the calcined form. The stacking sequence is 12 layers of the adsorption energies included in a DFT model to 6-rings (6Rs), AABAABAACAAC(A), containing single improve predictions for the overpotentials for the oxygen and double 6R units. STA-20 has a 3D-connected pore evolution reaction (OER) on RuO2 and IrO2. These are system limited by 8R windows and the longest cage known experimentally to be similar and quite low but

263 © 2017 Johnson Matthey http://dx.doi.org/10.1595/205651317X695910 Johnson Matthey Technol. Rev., 2017, 61, (3) widely used computational electrochemistry models A Cu/ZnO catalyst was prepared from a zincian georgeite based on adsorption thermodynamics do not show this. precursor synthesised by co-precipitation from acetate In such models IrO2 is usually predicted to have low salts and ammonium carbonate. The presence of Zn overpotentials while RuO2 is predicted to have large plus mild ageing conditions inhibits crystallisation into overpotentials. The results of the present study explain zincian malachite or aurichalcite. The catalyst exhibits the discrepancy and successfully predicted both oxides better performance for methanol synthesis and low to be highly active. temperature water-gas shift (LTS) reaction than a On the Motion of Linked Spheres in a Stokes Flow zincian malachite derived catalyst. It is suggested that F. Box, E. Han, C. R. Tipton and T. Mullin, Exp. Fluids, alumina may not need to be added as a stabiliser. Alkali 2017, 58, (4), 29 metals, which are known to act as catalyst poisons, are excluded from the synthesis procedure which is thought Inspired by the mechanics of swimming microorganisms, to account for the improved performance. the motion of linked spheres at low Reynolds number is being investigated. In the present study small Harvesting Renewable Energy for Carbon Dioxide permanent magnets were embedded in the spheres Catalysis and an external magnetic field was applied to generate A. Navarrete, G. Centi, A. Bogaerts, Á. Martín, A. York torques. Pairs of neutrally buoyant spheres connected by glass rods or thin elastic struts were found to move and G. D. Stefanidis, Energy Technol., 2017, 5, (6), 796 in a reciprocal orbit driven by an oscillatory field. Three Renewable energy can be used to transform spheres linked by elastic struts were observed to carbon dioxide into commodities (CO2 valorisation). buckle in a periodic, non-reciprocal fashion. This effect Technological advances in the field are reviewed along propels the elemental swimmer with swimming direction with socioeconomic implications and the chemical basis determined by the geometrical asymmetry of the device. of the transformation. Use of microwaves, plasmas and The technique may be suitable for miniaturisation. light to activate CO2 are introduced and their fundamental A New Class of Cu/ZnO Catalysts Derived from Zincian phenomena discussed. The present state-of-the-art Georgeite Precursors Prepared by Co-Precipitation has inherent limitations. To solve these, the current P. J. Smith, S. A. Kondrat, P. A. Chater, B. R. Yeo, G. M. catalytic concepts will need to be redesigned and a new Shaw, L. Lu, J. K. Bartley, S. H. Taylor, M. S. Spencer, conceptual approach for an energy-harvesting device is C. J. Kiely, G. J. Kelly, C. W. Park and G. J. Hutchings, proposed. The future challenges in efficient conversion Chem. Sci., 2017, 8, (3), 2436 of CO2 using renewable energy sources are described.

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