Skip to main

Impact case study database

The impact case study database allows you to browse and search for impact case studies submitted to the REF 2021. Use the search and filters below to find the impact case studies you are looking for.

Search and filter

Filter by

  • Cardiff University / Prifysgol Caerdydd
   None selected
  • 8 - Chemistry
   None selected
   None selected
   None selected
   None selected
   None selected
   None selected
Waiting for server
Download currently selected sections for currently selected case studies (spreadsheet) (generating)
Download currently selected case study PDFs (zip) (generating)
Download tags for the currently selected case studies (spreadsheet) (generating)
Currently displaying text from case study section
Showing impact case studies 1 to 3 of 3
Submitting institution
Cardiff University / Prifysgol Caerdydd
Unit of assessment
8 - Chemistry
Summary impact type
Technological
Is this case study continued from a case study submitted in 2014?
No

1. Summary of the impact

Minimising carbon monoxide within challenging environments for the military, mining, and deep-sea exploration is key to keeping people safe. Fundamental research at Cardiff, on the relationship between preparation and performance of catalysts, resulted in improved catalysts, and robust processes for their manufacture, enabling exceptional air purification performance for low temperature carbon monoxide and organic vapour oxidation. Commercialisation of these materials by Molecular Products Group led to new products, increased sales, expansion into new markets, and jobs. This was enabled via use of the catalysts in a wide variety of critical life-support applications in mining, deep-sea diving, medicine and the military.

2. Underpinning research

Catalysts for the conversion of carbon monoxide (CO) to CO2 at ambient temperature and pressure is a critical process for respiratory protection and life support. They are widely adopted in a diverse range of industries including mining, medicine, deep sea diving, and the military. Addressing this challenge, copper manganese oxide (Hopcalite) heterogeneous catalysts can be used to remove CO and other vapours from life support systems used in these environments. Variability in catalyst performance, however, has hindered commercially available batches from achieving widespread success.

Molecular Products Group, a multi-national UK-based manufacturing company, sought to establish a fundamental understanding of catalyst structure and performance, thereby creating a commercial manufacturing process. Molecular Products collaborated with Cardiff, drawn to the University’s extensive heritage in catalyst research, which enabled enhanced knowledge of the underlying concepts in the preparation of Hopcalite catalysts.

2.1 Refining Hopcalite catalysts

Taylor and Hutchings directed and managed the research, exploring oxidation of CO to CO2 at ambient temperatures using Hopcalite catalysts, as an alternative to dominant technology established in the 1920s. The key research on the preparation of improved low temperature CO catalysts was carried out at Cardiff between 2000-2015, with Cardiff establishing new catalyst preparation protocols vital for manufacturing the most active catalysts, and Molecular Products facilitating specific application tests and large-scale catalyst manufacturing.

The study of preparation methods was based around the processes of co-precipitation [3.1], thermal calcination [3.1] and incorporating cobalt [3.2] or gold [3.3] to enhance catalyst activity. These preparation studies identified reliable methods of producing catalysts with the most active phases, and consequently the most active surfaces optimised. Maximising the preparation of copper manganese mixed metal oxide phases, avoiding production of separate phases of copper oxide and manganese oxide, is critical to producing the most active catalyst. The research resulted in low temperature catalysts that combined both higher activity and more durability than traditional commercial Hopcalite catalysts.

2.2. Developing improved manufacturing processes

The collaborative research expanded from the new Hopcalite catalyst towards developing more efficient catalyst preparation routes. The Cardiff team developed novel supercritical anti-solvent preparation methods for Hopcalite to increase understanding of the critical phases and surface structures required for highly active catalysts [3.4]. Additional research explored catalyst transformation during thermal manufacturing steps and the resulting impact of catalyst efficacy [3.5]. Too low a heat treatment and not much of the mixed phase will be produced, while too high a temperature and highly crystalline low surface area phases are formed: both cases produce poorer catalysts. The Cardiff team were able to identify thermal transformation conditions which optimise active phases and hence catalyst activity.

Additionally, new industry-viable preparation routes for Molecular Products’ high performance Sofnocat precious metal-based catalysts were established. An atom-efficient method for synthesising catalysts using tin oxalate was investigated [3.6] and, when found to perform favourably, was transferred to Molecular Products to develop a viable new manufacturing route. The Sofnocat catalyst can be used for CO oxidation under particularly demanding conditions, when a Hopcalite catalyst may not provide the required performance (e.g., in mining sites, creating a safe haven in the event of an emergency).

3. References to the research

[3.1] C. Jones, K. Cole, S.H. Taylor, M.J. Crudace, G.J. Hutchings, Copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation: effect of calcination on activity. J. Mol. Catal. A: Chem., 2009, 305, 121-124. https://doi.org/10.1016/j.molcata.2008.10.027

[3.2] C. Jones, S.H. Taylor, A. Burrows, M.J. Crudace, C.J. Kiely, G.J. Hutchings, Cobalt promoted copper manganese oxide catalysts for ambient temperature carbon monoxide oxidation. Chem. Commun., 2008, 1707-1709. https://doi.org/10.1039/B800052M

[3.3] K.J. Cole, A.F. Carley, M.J. Crudace, M. Clarke, S.H. Taylor, G.J. Hutchings, Copper manganese oxide catalysts modified by gold deposition: the influence on activity for ambient temperature carbon monoxide oxidation. Catal. Lett., 2010, 138(3-4), 143-147. https://doi.org/10.1007/s10562-010-0392-2

[3.4] Z. Tang, S.A. Kondrat, C. Dickinson, J.K. Bartley, A.F. Carley, S.H. Taylor, T.E. Davies, M. Allix, M.J. Rosseinsky, J.B. Claridge, Z. Xu, S. Romani, M.J. Crudace, G.J. Hutchings, Synthesis of high surface area CuMn2O4 by supercritical antisolvent precipitation for the oxidation of CO at ambient temperature. Catal. Sci. Technol., 2011, 1(5), 740-746. https://doi.org/10.1039/c1cy00064k

[3.5] Z. Tang, C.D. Jones, T.E. Davies, J.K. Bartley, A.F. Carley, S.H. Taylor, M. Allix, C. Dickinson, M.J. Rosseinsky, J.B. Claridge, Z. Xu, M.J. Crudace, G.J. Hutchings, New nanocrystalline Cu/MnOx catalysts prepared using supercritical antisolvent precipitation. ChemCatChem., 2009, 1(2), 247-251. https://doi.org/10.1002/cctc.200900195

[3.6] J.K. Aldridge, L.R. Smith, D.J. Morgan, A.F. Carley, M. Humphreys, M.J. Clarke, P. Wormald, S.H. Taylor, G.J. Hutchings, Ambient temperature CO oxidation using palladium–platinum bimetallic catalysts supported on tin oxide/alumina. Catalysts 2020, 10, 1223. https://doi.org/10.3390/catal10111223

4. Details of the impact

Cardiff research established commercially viable CO-removal catalysts based on robust understanding of relationships between preparation, catalyst structure and activity. These have been sold around the world to produce a breathable atmosphere for people working in extreme environments, including miners, submariners and hospital patients under anaesthesia.

4.1 Commercialising research for Molecular Products

The primary economic beneficiary of the Cardiff-based research is the Molecular Products Group, which has a turnover of £14.4M and over 130 staff (2018). Dr Mandy Humphreys, former Technical Director of Molecular Products from 2003-14, stated that the research was “ pivotal for our business” [5.1]. As a result, the company adopted the technique of co-precipitation and optimised the formulation and preparation of the Hopcalite-based catalyst, Moleculite [5.2], which is sold worldwide for the oxidation of CO and volatile organic vapours.

Prior to the Cardiff research, the manufacturing process for Moleculite was susceptible to delivering batches of catalyst with varying performance, an unacceptable risk given the planned applications. Molecular Products stated that: “ Prolonged control of low levels of carbon monoxide in breathing systems is often considered the 'holy grail' from an industrial perspective, and this formed a corner stone strategic goal for the business. The fundamental research at Cardiff was required to crack this very difficult nut[5.1].

With Cardiff’s involvement, Molecular Products achieved a “ step change in the efficacy of our catalytic products[5.1]. The research supported a significant expansion of Molecular Products’ product range and enabled penetration into new markets and novel utilisations of current technology (as noted in Section 4.2, below). Cardiff involvement was also credited with increasing client confidence in the catalysts as Molecular Products stated: “ The research from Cardiff University was essential to allow us to engage with new markets and customers across the globe, which led to forming long-term sustainable relationships leading to strategic contracts for military and commercial applications[5.1].

Molecular Products’ catalysts business continues to expand at a faster rate than other areas of their business, driving a strong increase in revenue. The collaboration with Cardiff, supporting improved product design and access to expert knowledge, “significantly contributed to the financial viability of the business” [5.1]. [Text redacted] Molecular Products’ financial reports for 2014-2020 reveal that sales and profits continued to increase throughout the REF period, increasing total turnover to £99M between 2014 and 2020, an increase of 14% over the previous seven years [5.3]. In 2017, the company won the Sunday Times ‘Ones to Recognise’ award as one of Britain’s top 100 private companies with the fastest-growing profits [5.4].

4.2 Widespread applications and benefits for end users

Catalysts for the conversion of CO are widely adopted in mining, medicine, deep sea diving, and the military. Dr Patricia Wormald, Development Chemist at Molecular Products, stated: “ The Moleculite and Sofnocat catalysts underpin our life-maintaining products in a wide variety of applications, which must be of the highest reliability and robustness due to their application in life-supporting activities[5.5].

The catalysts are sold by Molecular Products as-is [5.2, 5.6] or combined with oxygen-enriching and CO2-scrubbing catalysts in a single, all-purpose, atmosphere-treatment product. The enhanced Moleculite formulation has been incorporated within air purification systems such as HiCap CO™ [5.7] which can be bought as a single product and deployed to create a breathable atmosphere in emergency situations, such as a mining cave-in, or used in self-contained breathing apparatus, such as those used by firefighters.

Molecular Products stated that HiCap CO™ “ has been a key product for us due to its established status as a comprehensive air-purification system with our customers” [5.5]. Molecular Products also consult on bespoke solutions for their clients, such as atmosphere chambers for a diving company in South Africa, or life support systems for submarines sold to the Malay, Indian and Chinese navies. As the method of alleviating CO poisoning, the Moleculite and Sofnocat catalysts are utilised in the majority of these designs [5.5].

The catalysts developed at Cardiff, therefore, underpin worldwide activity in hazardous environments, and the solutions offered by Molecular Products are “ used every day, across the world, to ensure a survivable atmosphere for end-users[5.5]. Example applications include:

a. Military use

41 countries operate military submarines, with many more using civilian exploratory and research vessels. Consequently, thousands of people globally are reliant on air purification catalysts. Molecular Products noted: “ We are unable to confirm which navies are currently supplied by our products for reasons of national security. However, I can confirm that the catalysts created by Cardiff research are currently in submersible vessels in use all over the world.” [5.5]

b. The mining sector

High-profile mining incidents (including the 2010 Chilean gold-copper mine cave-in) highlighted the need for secure life support systems within this hazardous sector. Molecular Products developed emergency backup systems using advanced catalysts (including Sofnocat), which prevent CO poisoning in these environments. The systems can be activated in the event of a cave-in to supply breathable air until the mine can be secured and any trapped miners rescued [5.5].

c. Healthcare, hospital, and laboratory safety

Moleculite is also used in the sterilisation of hospital equipment that would otherwise be damaged by traditional heat- or moisture-based sterilisation procedures (e.g., those comprising plastic or rubber). These devices are sterilised with ethylene oxide gas, which must then be treated with Moleculite to render it inert. This application is routinely used in hospitals and laboratories worldwide to remove the danger of toxic gases being released [5.5].

In summary, Cardiff’s research was integral to enabling commercialisation of Molecular Products’ catalytic life-support products. This underpinned increased success for Molecular Products’ catalytic sector, which grew (as described by the company) “ from an embryo to a sustainable ‘third leg’ of the business[5.1].

5. Sources to corroborate the impact

[5.1] Testimonial: Dr Mandy Humphreys, former Technical Director, Molecular Products (2003 – 2014)

[5.2] Details of Moleculite. Moleculite: copper manganese oxide-based carbon monoxide removal catalyst. Molecular Products website

[5.3] Molecular Products’ Financial Reports 2014 – 2020 (Obtained from Companies House)

[5.4] Details of Molecular Products wins Sunday Times ‘Ones to Watch’ award. Latest News: Molecular Products is one to watch in the List of UK’s fastest Growing companies (2017). Molecular Products website

[5.5] Testimonial: Dr Patricia Wormald, Development Chemist at Molecular Products (2017 – present)

[5.6] Details of high-performance Sofnocat catalysts for carbon monoxide removal. Sofnocat 423. Molecular Products website

[5.7] Details of Moleculite cannisters for carbon monoxide removal applications. Hi-Cap Co Absorber. Molecular Products website

Submitting institution
Cardiff University / Prifysgol Caerdydd
Unit of assessment
8 - Chemistry
Summary impact type
Technological
Is this case study continued from a case study submitted in 2014?
Yes

1. Summary of the impact

Despite the immediate and environmental dangers of mercury, it remains integral to polyvinyl chloride (PVC) manufacture in China, the world’s largest producer. Cardiff researchers developed and optimised a gold-based catalyst system for use in vinyl chloride monomer manufacture, the precursor to PVC, replacing mercury-based catalysts. Global chemicals company, Johnson Matthey, now operates an industrial-scale factory producing this catalyst and are replacing the use of mercury-based catalysts in PVC production facilities across China. This is the first time in over 50 years a complete overhaul in catalyst formulation has been implemented to produce a commodity chemical.

2. Underpinning research

The production of polyvinyl chloride (PVC) requires the precursor material vinyl chloride monomer (VCM). The world’s largest PVC producer, China, synthesises VCM from its extensive coal reserves via acetylene hydrochlorination. Until now, this process required the use of mercury-based catalysts, resulting in substantial pollution of mercury in the environment.

Due to dangers from mercury poisoning (including brain damage, kidney failure, and potentially death), the 128 signatories of the Minamata Convention on Mercury (including China in 2016) committed to phasing out its use in products, processes, and industries. Hutchings’ catalysis research revealed the high catalytic activity of clusters of gold atoms [3.1], greatly increasing their potential for commercial exploitation by providing a replacement approach to the use of the mercury-based catalyst.

2.1 Determining the catalytic properties of gold

The presence of atomically dispersed gold cations in the proposed catalyst are crucial to the synthesis of VCM from acetylene. Studies of the hydrochlorination of acetylene and higher alkynes [3.2] and gold-based bimetallic catalysts revealed that gold is by far the most active and most selective catalyst [3.3]. The high cost of gold, however, necessitated a reduction in gold content for the proposed catalyst to be commercially viable.

Following Hutchings’ research, and based on its track record in gold-based catalyst formation, Cardiff was approached by Johnson Matthey to address this challenge. In a study sponsored by the company and the World Gold Council [G3.1], the Cardiff team found that dilution of the gold led to untenably low activity in all cases, which was shown to scale with the standard electrode potential of mixed metal compositions. This research also revealed that viable catalysts did not result from alloying with a second metal [3.3].

These fundamental studies showed that gold-only catalysts were superior to other mixed compositions, including mixed metal catalysts, and provided full mechanistic understanding on which to base new catalyst formulations. The research also demonstrated that it is essential to maximise the dispersion of the gold so that the maximum amount of gold can be maintained in the most active state (cationic species) in the working catalyst [3.4].

2.2 Creating the catalyst

Working closely with Johnson Matthey, the Cardiff team devised a catalyst system consisting of a carbon core with a gold ‘shell’, maximising dispersion of the gold. This catalyst has a very low gold concentration (0.1%) that gives superior performance to the standard mercuric chloride catalyst, extensively used by industry for acetylene hydrochlorination over the last 60 years.

Once the key catalyst features were established, following small-scale tests at Cardiff in 2008, the method of catalyst preparation became the critical means of improving the catalyst. Originally, the carbon-supported gold catalysts were prepared by depositing gold using a strong acid solvent (aqua regia) to produce a 1-2% metal content. For commercial application, a non-aqua regia based route was needed to reproducibly generate catalysts with a controllable, lower gold content.

Research on this problem led to a new water-based route employing small molecule sulphur complexes of gold [3.5]. Once this new formulation was established, fundamental studies were undertaken to confirm the nature of the active site of well-dispersed supported gold cations [3.6]; an atomic level of understanding that enabled the development of highly active catalysts, readying their commercialisation.

Cardiff research was central in changing the way in which gold catalysts were designed greatly increasing their potential for commercial exploitation by meeting the key innovations required for successful translation to PVC manufacturing.

3. References to the research

[3.1] A.A. Herzing, C.J. Kiely, A.F. Carley, P. Landon, G.J. Hutchings, ‘Identification of active gold nanoclusters on iron oxide supports for CO oxidation’, Science, 2008, 321, 1331-1335. http://dx.doi.org/10.1126/science.1159639

[3.2] M. Conte, A.F. Carley, C. Heirene, D.J. Willock, P. Johnston, A.A. Herzing, C.J. Kiely, G.J. Hutchings, ‘Hydrochlorination of acetylene using a supported gold catalyst. A study of the reaction mechanism’, J. Catal., 2007, 250, 231-239. http://dx.doi.org/10.1016/j.jcat.2007.06.018

[3.3] M. Conte, A.F. Carley, G. Attard, A.A. Herzing, C.J. Kiely, G.J. Hutchings, ‘Hydrochlorination of acetylene using supported bimetallic Au-based catalysts’, J. Catal., 2008, 257, 190-198. http://dx.doi.org/10.1016/j.jcat.2008.04.024

[3.4] M. Conte, C.J. Davies, D.J. Morgan, T.E. Davies, D. J. Elias, A.F. Carley, P. Johnston, G.J. Hutchings, ‘Aqua regia activated Au/C catalysts for the hydrochlorination of acetylene’, J. Catal., 2013, 297, 128-136. http://dx.doi.org/10.1016/j.jcat.2012.10.002

[3.5] P. Johnston, N. Carthey, G.J. Hutchings, ‘Discovery, development and commercialisation of gold catalysts for acetylene hydrochlorination’, J. Am. Chem. Soc., 2015, 137, 14548-14557. https://doi.org/10.1021/jacs.5b07752

[3.6] G. Malta, S.A. Kondrat, S.J. Freakley, C.J. Davies, L. Lu, S. Dawson, A. Thetford, E.K. Gibson, D.J. Morgan, W. Jones, P.P. Wells, P. Johnston, C.R.A. Catlow, C.J. Kiely, G.J. Hutchings, ‘Identification of single-site gold catalysis in acetylene hydrochlorination’, Science, 2017, 355, 1399-1403. https://doi.org/10.1126/science.aal3439

Selected grant:

[G3.1] G. J. Hutchings; Replacing mercury-based catalysts for acetylene hydrochlorination using supported gold catalysts; Johnson Matthey Davy Technologies Limited, World Gold Council; 2010-2019, £60,000; ID: 502874

4. Details of the impact

China is the world’s largest producer of the ubiquitous material polyvinyl chloride (PVC), and its production is reliant on the precursor material vinyl chloride monomer (VCM). While other countries typically use oil or natural gas to produce VCM, China relies on their coal reserves to produce VCM, necessitating the use of mercury-based catalysts and asserting the country as the biggest global consumer of mercury, chiefly for VCM production (over 800 tonnes a year) [5.1]. Cardiff research enabled the development of an alternative gold-based catalyst for VCM production, which is replacing the mercury use in Chinese VCM production and has been recognised through multiple international awards.

4.1 Development of a mercury-free catalyst for VCM production

Since 2007, international chemical company Johnson Matthey PLC collaborated with Cardiff to develop a new series of gold-based catalysts for VCM production. Following over 10 years of research and development costing millions of pounds, the company developed the PRICAT™ MFC (Mercury Free Catalyst) [5.2]. Cardiff’s role in developing this commercial gold-based catalyst was highlighted by Sebastiaan van Haandel, the New Technologies Licensing Manager at Johnson Matthey as “ critical in optimisation of the catalyst and enabled further improved second generation catalysts to be developed[5.2]. Johnson Matthey further noted that the new catalyst “is the first time in over 50 years that a complete overhaul in catalyst formulation has been implemented to produce any commodity chemical[5.2].

The intellectual property for PRICAT™MFC was initially shared between Johnson Matthey and Jacobs Engineering Group. After recognising the significant value of the catalyst, as evidenced by research findings, in March 2014, Johnson Matthey made the strategic decision to purchase sole ownership of the catalyst patents for £7.5M [5.2].

4.2 Establishing production and use of the catalysts in China

In 2013, as confirmed by Johnson Matthey, the first full reactor test of the PRICAT™ MFC was commissioned by a major Chinese VCM producer, followed by several further full-scale reactor trials at other major Chinese producers [5.2]. These trials demonstrated the acetylene conversion rate and catalyst productivity outperformed the mercury-based catalyst [5.2].

Alongside purchasing the patents for the catalyst in 2014, Johnson Matthey secured the process technology required for building VCM plants, in order to give the company strategic capability to roll out a mercury-free VCM production process across China [5.2]. The full product offering became the DAVY™ VCM Process, which utilises PRICAT™ MFC and is the only mercury-free process currently offered for licence [5.3].

In 2015, Johnson Matthey invested in a new manufacturing plant in Shanghai to produce the PRICAT™ MFC catalyst at industrial scale, positioning the catalyst as *“one of the major growth engines for Johnson Matthey over the next 10 years” [5.2]**. The plant is designed to meet 20-30% of China’s annual VCM demand, and Johnson Matthey anticipates that “ a significant part of the Chinese market will have converted to PRICAT® MFC” within two years [5.2].

In August 2016, China ratified the Minamata Convention on Mercury, a United Nations Environment Programme treaty committed to the removal of mercury in industrial processes. Particularly, Annex B, Article 5 (v) of the Convention commits members to withdraw mercury-based methods for the production of VCM, and that member states will cease mercury mining by 2032 [5.4, p.25 ]. The signing of the Convention by China signalled its intention to adopt new and economically-viable mercury-free processes.

Johnson Matthey noted that the successful testing and implementation of the PRICAT™ MFC catalysts “ is starting to facilitate the widespread transformation of Chinese VCM production”, with the expectation that within a few years a significant amount of VCM production in China will have discontinued use of mercury-based catalysts [5.2].

4.3 Awards and Recognition

The development of the new catalyst, underpinned by Cardiff research, achieved global recognition as a significant step in enabling the reduction of mercury-based PVC manufacturing processes:

  • The Innovative Product of the Year Award at the 2015 Institution of Chemical Engineers (IChemE) Global Awards [5.5], awarded to Johnson Matthey and Cardiff University [5.5];

  • The GSK Innovation Award at the 2016 Chemical Industry Awards for the successful commercialisation of the PRICAT™ MFC for mercury-free VCM production [5.6];

  • The Industry-Academia Collaboration Award at the 2017 Royal Society of Chemistry awards for the development of the mercury-free catalyst for VCM production [5.7];

  • In recognition of the beneficial impact of gold catalysts on the environment, in 2017 Hutchings was awarded the Eni Awards’ Advanced Environmental Solutions Prize for his work creating and optimising the catalyst [5.8].

5. Sources to corroborate the impact

[5.1] Special Policy Study on Mercury Management in China – presentation by the China Council for International Cooperation on Environment and Development

[5.2] Testimonial: Sebastiaan van Haandel, Licensing Manager New Technologies, Johnson Matthey Plc.

[5.3] Confirmation of process and license, Johnson Matthey website on DAVY Process VCM Technology

[5.4] The Minamata Convention on Mercury, Annex B, p.25

[5.5] Johnson Matthey with Cardiff University, winner of the Innovative Product of the Year, footage of IChemE’s Global Awards 2015 from IChemE Youtube channel

[5.6] Johnson Matthey wins GSK Innovation Award at the 2016 Chemical Industry Awards, Johnson Matthey website

[5.7] Professor Graham Hutchings and Dr Peter Johnston, Industry-Academia Collaboration of the Year, Royal Society of Chemistry Prizes and awards 2017, RSC Website

[5.8] Eni Award 2017 for Advanced Environmental Solutions awarded to Professor Graham Hutchings, press release, Eni website

Submitting institution
Cardiff University / Prifysgol Caerdydd
Unit of assessment
8 - Chemistry
Summary impact type
Technological
Is this case study continued from a case study submitted in 2014?
Yes

1. Summary of the impact

Poly(methyl methacrylate), or Perspex®, is a commercial material employed in almost all industries, but supply constraints have hampered production in recent years. Cardiff research, through close collaboration with industry partner Lucite International, synthesised the key ligand of the ALPHA process, which enabled industrial-scale manufacture of methyl methacrylate (MMA), the precursor to Perspex®. The ALPHA process achieved greater efficiency than competing MMA production methods, reducing costs by 40%, while removing environmentally harmful process chemicals and subsequently reducing waste. This led to a US$1.1 billion investment to construct a new production plant, and the process now underpins 10% of the world’s total MMA production, approximately 370 thousand tonnes per annum.

2. Underpinning research

Since the invention of Perspex® (poly(methyl methacrylate), PMMA) in the 1930s by Imperial Chemical Industries (ICI), its precursor material, methyl methacrylate (MMA), has become a globally traded commodity. Historically MMA was created using toxic and corrosive chemicals, such as hydrogen cyanide and sulphuric acid, which raised production costs and limited the scale of industrial manufacture. Lucite International (formally ICI Acrylics, and now part of the Mitsubishi Group) sought the expertise of Edwards and Newman at Cardiff University, who have over 20 years’ experience working on the underpinning chemistry of MMA production. The company wished to establish a new economically and environmentally viable catalytic route for the future manufacture of MMA.

2.1 Refining the ALPHA process

Edwards and Newman’s research in the late 1990s led to the development of the ALPHA process: a highly efficient synthetic route to the key catalyst ligand component, 1,2-bis(di-t- butylphosphinomethyl) benzene. Once the process had been identified in principle, continuing research at Cardiff then explored the applied chemistry to enable an efficient and cost-effective application of the ALPHA process at industrial scale. Research explored the feedstock of two competing materials, namely ethylene or acetylene. Although both were viable, only one could be taken forward to pilot scale and eventually to MMA production.

In 2004, Cardiff’s research demonstrated that the acetylene pathway is, in principle, more efficient since the phosphine used was cheaper and air stable, and its production of MMA was a single-step process, as opposed to two when using ethylene. The catalyst longevity, however, was lower than that used in the ethylene process, as it was poisoned by allene, an impurity present in acetylene feedstocks. This poisoning was irreversible and removal of allene from the acetylene feedstock was not viable. As such, the ethylene route was ultimately selected for development of MMA [3.1].

2.2 Synthesising the Alpha Ligand

The ALPHA process was an entirely new approach to MMA production, but reliant on the synthesis of a phosphine ligand known as the ‘ALPHA Ligand’ for which the existing synthesis was prohibitively expensive. Lucite International continued to fund the research of the Edwards/Newman group between 2000 and 2010 to further refine the patented ligand synthesis developed during their earlier work, in the hopes of translating the Alpha process into industrial production.

In 2004, the Cardiff team developed a cost-effective synthesis of the Alpha Ligand that could support the industrial application of the ALPHA process **[**see 5.3]. As highly sensitive commercial work, this research could not be made publicly available at the time; it was partly published after 2010 [3.2]. The key to the process is the remarkable efficiency of the catalyst for the addition of carbon monoxide to ethylene, which is fast (producing 13kg of methyl propanoate from 0.001kg of palladium metal per hour of operation) and cost efficient with regard to the amount of palladium metal consumed (10,000kg of product produced for 0.001kg of metal consumed).

The Alpha Ligand system was extremely efficient, with Cardiff research concluding that its performance could not be matched by any other palladium/phosphine combination [3.3], and that continuing to investigate alternate catalyst structures would likely be fruitless. As such, the optimised synthetic procedure for Alpha Ligand production became the commercial route implemented in 2008.

3. References to the research

[3.1] M.J. Green, K.J. Cavell, P.G. Edwards, R.P. Tooze, B.W. Skelton, A.H. White, ‘Palladium(II) complexes of new OPN phosphine ligands and their application in homogeneously catalysed reactions of CO with alkenes or alkynes’. Dalton Trans. , 2004, 3251-3260. https://doi.org/10.1039/b405586c

[3.2] P.G. Edwards, J.C. Knight, P.D. Newman, ‘Synthesis of (1R,4S,6R)-5,5,6-trimethyl-2-phosphabicyclo[2.2.2]octane and derivatives’. Dalton Trans. , 2010, 39, 3851-3860. https://doi.org/10.1039/b924983d

[3.3] D. Coleman, P.G. Edwards, B.M. Kariuki, P.D. Newman, ‘Coordination chemistry of cis,cis and trans,trans 1,1'-[1,2-phenylenebis(methylene)] bis(2,2,3,4,4-pentamethylphosphetane)’. Dalton Trans., 2010, 39, 3842-3850. https://doi.org/10.1039/b924982f

4. Details of the impact

A more efficient method of producing methyl methacrylate monomer (MMA), the precursor material for Perspex® and acrylic resins, required a crucial phosphine ligand. Cardiff’s research determined a cost-effective method to synthesise the required ligand, which enabled the industrial scale production of MMA. Since the inception of the ligand in 2008, Cardiff’s research continues to produce a cheaper, less environmentally damaging and higher quality MMA product, and in 2014 led to a US$1.1 billion investment to create the world’s largest MMA plant. The new method now accounts for 10% of the world’s annual production of MMA, a market share that continues to grow.

  1. Enabling the efficient production of MMA

Lucite International is a global leader in the design, development, and manufacture of acrylic products, with 22 plants across 14 locations worldwide and annual revenues of US$1.7 billion. Lucite is the owner of the ALPHA process: a process technology for MMA production that offers significant advantages over existing production methods. Until 2004, however, the potential of the ALPHA process was restricted by the limited availability of an essential phosphine ligand. Dr Jonathan Runnacles, Business Research Director at Lucite International, stated that “ methods of producing this phosphine ligand were at the time prohibitively expensive[5.1].

As noted in Section 2, Cardiff’s research resulted in a cost-effective synthesis of the phosphine ligand, as well as carbonylation and ligand optimisation needed to support the ALPHA process. Lucite stated: “ Without the development research undertaken at Cardiff by the Edwards-Newman group rendering the Alpha process ligand synthesis commercially feasible, the very substantial economic and environmental benefits of the Alpha process would not have been realized as effectively as they have been[5.1].

  1. Improved product quality and reduced waste

The ALPHA process has several significant advantages over the competing acetone-cyanohydrin (ACH/C3) MMA process used in the USA and Europe [5.2], or the isobutylene-based (C4) process used in Asia [5.2]. Lucite estimate that the cost of running the ALPHA process is 40% cheaper to operate than their previous ACH-based plants [5.3]. Crucially, the feedstock for the ALPHA process (ethylene, methanol and carbon monoxide) are cheaper and more widely available than feedstock for other processes, allowing greater operational flexibility for supply chains and plant locations [5.1].

The ALPHA process has additional environmental benefits as the required feedstock are much less toxic and corrosive than those required for the ACH/C3 process, which are reliant upon hydrogen cyanide and concentrated sulphuric acid [5.1]. The atom-efficiency of the ALPHA process also means that there are no toxic wastes or by-products [5.1], in contrast with the stoichiometric ammonium sulphate by-product produced by ACH methods [5.2].

Perspex® with high optical clarity is in demand for applications such as mobile phones, televisions, and computer monitors, and offers maximum light transmission without surface hot spots. Perspex® production has traditionally required an additional step to achieve this clarity, however. Lucite stated that: “ MMA derived through the ALPHA process produces the required quality as an end product, removing the significant manufacturing costs involved for this extra step[5.1].

  1. Investment and launch of the world’s largest MMA plant

The first ALPHA-based MMA Production Plant (named Alpha 1) went online in 2008. Following the success of Alpha 1, a joint venture was formed between Lucite, Mitsubishi Chemical Company, and Saudi Basic Industries Corporation to establish the world’s largest MMA production plant. As a result, in 2014 the joint venture invested US$1.1 billion to begin construction of the Alpha 2 plant in Saudi Arabia [5.1]. The Alpha 2 plant began full production in 2018 and produces 250,000 tonnes of MMA annually [5.1]. Alongside the continuing production from Alpha 1 (120,000 tonnes per annum), Lucite confirmed that since Alpha 2 came online, the combined current output has “ contributed approximately 10% of the world’s MMA demand[5.1], approximately 370,000 tonnes per annum, significantly helping to relieve global supply constraints [5.3, 5.4].

A key advantage of the ALPHA process is that it removes scale limitations, “ enabling large single stream scale plants” such as Alpha 1 and 2 [5.1]. The ALPHA process removed constraints on plant size experienced by other MMA production processes (e.g. maximum 80,000 tonnes per annum for the C4 Process), allowing significantly improved economies of scale [5.2]. Lucite have since confirmed their intention to construct an even larger plant on the Gulf of Mexico, USA [5.5]; the Alpha 3 plant has a planned capacity of 350,000 tonnes per annum and is due to begin operations in 2025 [5.1].

In summary, Cardiff research changed the landscape of global Perspex® production via enabling the industrial scale application of the ALPHA process. This provided the global Perspex® industry with a cost-effective approach at scale, delivering significant economic and environmental benefits.

5. Sources to corroborate the impact

[5.1] Testimonial: Dr Jonathan Runnacles, Business Research Director, Lucite International

[5.2] A Winning Process. Chemistry & Industry: 20 (2009). Society of Chemistry and Industry website

[5.3] Methyl Methacrylate (MMA) Production and Manufacturing Process (2010). Independent Commodity Intelligence Services website

[5.4] Katherine Sale. EPCA ’17: Global MMA supply constraints may put Europe at its tightest year to date (2017). Independent Commodity Intelligence Services website

[5.5] New ALPHA MMA plant to be constructed on the US Gulf Coast (2020). Company News. Lucite International website

Showing impact case studies 1 to 3 of 3

Filter by higher education institution

UK regions
Select one or more of the following higher education institutions and then click Apply selected filters when you have finished.
No higher education institutions found.
Institutions

Filter by unit of assessment

Main panels
Select one or more of the following units of assessment and then click Apply selected filters when you have finished.
No unit of assessments found.
Units of assessment

Filter by continued case study

Select one or more of the following states and then click Apply selected filters when you have finished.

Filter by summary impact type

Select one or more of the following summary impact types and then click Apply selected filters when you have finished.

Filter by impact UK location

UK Countries
Select one or more of the following UK locations and then click Apply selected filters when you have finished.
No UK locations found.
Impact UK locations

Filter by impact global location

Continents
Select one or more of the following global locations and then click Apply selected filters when you have finished.
No global locations found.
Impact global locations

Filter by underpinning research subject

Subject areas
Select one or more of the following underpinning research subjects and then click Apply selected filters when you have finished.
No subjects found.
Underpinning research subjects