Nano-structured Catalysts for CO2 Transformation to Fuels and Products

Lead Research Organisation: Imperial College London
Department Name: Dept of Chemistry

Abstract

This project will develop new nanometre-sized catalysts and (electro-) chemical processes for producing fuels, including methanol, methane, gasoline and diesel, and chemical products from waste carbon dioxide. It builds upon a successful first phase in which a new, highly controlled nanoparticle catalyst was developed and used to produce methanol from carbon dioxide; the reaction is a pertinent example of the production of a liquid fuel and chemical feedstock. In addition, we developed high temperature electrochemical reactions and reactors for the production of 'synthesis gas' (carbon monoxide and hydrogen) and oxygen from carbon dioxide and water. In this second phase of the project, we shall extend the production of fuels to include methanol, methane, gasoline and diesel, by integrating suitably complementary processes, using energy from renewable sources or off-peak electricity. The latter option is particularly attractive as a means to manage electricity loads as more renewables are integrated with the national power grid. In parallel, we will apply our new nanocatalysts to enable the copolymerization of carbon dioxide with epoxides to produce polycarbonate polyols, components of home insulation foams (polyurethanes). The approach is both commercially and environmentally attractive due to the replacement of 30-50% of the usual petrochemical carbon source (the epoxide) with carbon dioxide, and may be commercialised in the relatively near term. These copolymers are valuable products in their own right and provide a commercial-scale proving ground for the technology, before addressing integration into the larger scale challenges of fuel production and energy management.

The programme will continue to improve our catalyst performance and our understanding, to enable carbon dioxide transformations to a range of valuable products. The work will be coupled with a comprehensive process systems analysis in order to develop the most practical and valuable routes to implementation. Our goal is to continue to build on our existing promising results to advance the technology towards commercialisation; the research programme will focus on:
1) Catalyst optimization and scale-up so as to maximise the activities and selectivities for target products.
2) Development and optimization of the process conditions and engineering for the nanocatalysts, including testing and modelling new reactor designs.
3) Process integration and engineering to enable tandem catalyses and efficient generation of renewable fuels, including integration with renewable energy generation taking advantage of off-peak electrical power availability.
4) Detailed economic, energetic, environmental and life cycle analysis of the processes.

We will work closely with industrial partners to ensure that the technologies are practical and that key potential impediments to application are addressed. We have a team of seven companies which form our industrial advisory board, representing stakeholders from across the value chain, including: E.On, National Grid, Linde, Johnson Matthey, Simon Carves, Econic Technologies, and Shell.

Planned Impact

There is intense interest in devising uses for carbon dioxide (CO2) produced by power generation, steel and cement production, etc. for economically and environmentally useful purposes, both to decrease emission rates and to offset costs of carbon capture systems by converting captured CO2 into useful products. The challenges are two-fold: how to develop catalysts that activate relatively inert CO2, and how to provide the necessary energy to drive such reactions. Our proposed programme will design and scale up novel yet realistic chemical conversion processes for the conversion of CO2 to useful fuels and chemicals. Specifically, within the current project, the fuels will include methanol, methane, , dimethyl ether (DME), diesel and gasoline, whilst the chemicals will focus on controlled molecular weight distribution polycarbonate polyols suitable for polyurethane manufacturing.
These two strands share many common technological aspects, but have different characteristics and timescales for implementation. Polycarbonates (3 Mtonnes/year) and polyols for polyurethanes (4 Mtonnes/year) are important and valuable industrial products, but their scale is, of course, dwarfed by fuel production and electrical energy generation. On the other hand, the incorporation of CO2 in such polymers is relatively easy to implement, as the CO2 displaces a significant fraction of the existing, expensive, petrochemical monomer, whilst the remaining monomer has sufficient reactivity to drive the reaction without further energy input. These polymer conversion processes will be enhanced by the project and will provide a test-bed for proving the catalyst technology and methods of integration with industrial CO2 waste streams (now feedstocks). The experience derived will help to develop the more complex processes for producing fuels that require energy inputs from off-peak electricity, a resource increasingly associated with renewable energy sources for which supply is hard to match to demand. The project includes detailed analysis of the techno-economic aspects of the many options to identify and optimise the most promising processes and operating conditions.
Successful implantation of CO2 conversion processes will be benefit a wide variety of UK and multi-national stakeholders, including chemical companies, catalyst and process equipment manufacturers, energy companies, consumer goods manufacturers and ultimately UK consumers, who will eventually reap both financial and environmental benefits. By providing an efficient economic use for spare generating capacity, renewable electricity generation will become increasingly favourable; at the same time, a new range of low carbon products will be produced to displace petrochemically-derived incumbents, reducing net green house gas emissions and improving energy security. These new product families will support exports, attract inward investment, and help to create jobs and revenue, as well as enhancing the UK's reputation in the field. The project will both contribute towards environmental sustainability, and enhance the capacity of UK industry in this growing field. As energy prices continue to rise, efficient use of petrochemicals and increased use of renewables will become increasingly important for economic competitiveness, as will a strong industrial base in enabling technologies.
The project bridges between chemistry and chemical engineering, bringing together new catalyst synthesis and in situ characterisation techniques with process design and integration; it will provide new scientific knowledge, new methodologies, and high skilled trained researchers who will drive future developments in this field in both academic and industrial contexts. Most of the commercial stakeholder groups are represented by our project partners, providing a ready source of data and advice to guide the research programme, and the relevant expertise to drive the next phase of development, deployment and exploitation.

Publications

10 25 50
 
Description We have demonstrated that it is technically possible to develop new catalysts to convert carbon dioxide to useful fuels and chemicals such as methanol and polycarbonate polymers. This provides a value chain for CO2 and encourages its capture and re-use. We have also performed economic analyses of these processes.
Exploitation Route The processes can be scaled up to be evaluated at pilot scale.
Sectors Chemicals,Energy

 
Description they have supported engagement with BEIS on carbon capture and utilisation and formed input to a key report.
First Year Of Impact 2017
Sector Chemicals
Impact Types Economic,Policy & public services

 
Description BEIS - CCU
Geographic Reach National 
Policy Influence Type Participation in a advisory committee
Impact Supporting evidence for policy in carbon dioxide utilisation.
 
Description Shell
Amount £120,000 (GBP)
Organisation Shell International Petroleum 
Department Shell UK Ltd
Sector Private
Country United Kingdom
Start 03/2017 
End 07/2018
 
Description Collaboration to study the properties of polymers from carbon dioxide 
Organisation University of Minnesota
Country United States 
Sector Academic/University 
PI Contribution A collaboration to study the properties (mechanical) of polymers from carbon dioxide/epoxide and ring-opening copolymerizations Our contribution is the preparation of the polymers and the catalytic method.
Collaborator Contribution The partners are expert in materials characterization
Impact A publication is in progress
Start Year 2013
 
Description Collaboration with Prof. Micheal Meier, KIT, Germany: biobased polymers 
Organisation Karlsruhe Institute of Technology
Country Germany 
Sector Academic/University 
PI Contribution A collaboration to investigate new biobased polymers was started in 2014. It involved a secondment of Mr Mathias Winkler to our labs in London and resulted in a publication (Green CHemistry, 2014)
Collaborator Contribution Partners: prepared a new monomer Us: discovered how to polymerize the monomer and to prepare new bio-based polymers
Impact Publication: "Renewable polycarbonates and polyesters from 1,4-cyclohexadiene." Winkler, M.; Romain, C.; Meier, M. A. R.; Williams, C. K. Green Chemistry 2014.
Start Year 2014
 
Description Collaboration with Professor Cor Koning to evaluate coating applicaitons 
Organisation Eindhoven University of Technology
Country Netherlands 
Sector Academic/University 
PI Contribution The collaboration is to apply our carbon dioxide derived polymers to prepare new coatings. Our group prepare the polymers
Collaborator Contribution The partner is an expert in coating fabrication and in testing of properties
Impact Publications in preparation
Start Year 2015
 
Description Collaboration with Professor Robert Mathers, Penn State University 
Organisation Penn State University
Department Department of Chemistry
Country United States 
Sector Academic/University 
PI Contribution We have tested new bio-derived monomers in CO2 epoxide copolymerizations. The monomers behave well and give high thermal resistance materials.
Collaborator Contribution The partner has prepared the new monomer from terpenes
Impact Publication in preparation
Start Year 2014
 
Description Harwell research complex 
Organisation Research Complex at Harwell
Country United Kingdom 
Sector Public 
PI Contribution We have been allocated beam time for EXAFS and XANES measurements on our catalysts at the research complex at Harwell (national facility). This has allowed detailed catalyst characterization experiments to be run.
Collaborator Contribution Partners are experts in EXAFS and XANES
Impact publication: Brown, N. J.; Garcia-Trenco, A.; Weiner, J.; White, E. R.; Allinson, M.; Chen, Y.; Wells, P. P.; Gibson, E. K.; Hellgardt, K.; Shaffer, M. S. P.; Williams, C. K. ACS Catalysis 2015, 5, 2895-2902.
Start Year 2014
 
Description Shell 
Organisation Shell International Petroleum
Department Shell UK Ltd
Country United Kingdom 
Sector Private 
PI Contribution Development of new approaches to designing CO2 utilisation systems.
Collaborator Contribution Provision of data
Impact A new proposal
Start Year 2016
 
Description ZnO nanoparticles for Antimicrobial applications, collaboration with Ivan Parkin (UCL) 
Organisation University College London
Department Department of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution We have used the nanoparticles developed for catalysis in a new collaboration with Chemistry (Ivan Parkin), Physics (Sandy McRobert) and Micro-Biology (Elaine Allan) at UCL. The particles are used to prepare new photoactive antimicrobial polymers, including hospital tubing, which when activated by visible light results in destruction of common bacteria (including resistant wild-type strains). The particles show high efficacy and promise in this application. our contribution is to synthesise the particles and characterize them
Collaborator Contribution Antimicrobial testing, bio-physics and extensive experience of material formulation.
Impact A paper has been published: Noimark, S.; Weiner, J.; Noor, N.; Allan, E.; Williams, C. K.; Shaffer, M. S. P.; Parkin, I. P. Advanced Functional Materials 2015, 25, 1367-1373. More publications are in preparation.
Start Year 2014
 
Title Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent 
Description SEE TITLE 
IP Reference WO2013034750 
Protection Patent application published
Year Protection Granted
Licensed Yes
Impact COMMERCIALLY SENSITIVE INFORMATION BUT LICENSED TO ECONIC TECHNOLOGIES
 
Title Process for producing nanoparticles 
Description SEE TITLE 
IP Reference WO2013164650 
Protection Patent application published
Year Protection Granted
Licensed No
Impact LICENSE DISCUSSIONS UNDERWAY WITH INTERESTED PARTIES
 
Company Name econic technologies 
Description see company website for more information: http://www.econic-technologies.com/ polymers from CO2 
Year Established 2011 
Impact see website
Website http://www.econic-technologies.com/
 
Description 250th American Chemical Society and Meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Three lectures were given at the ACS meeting in Boston by the Williams group
Year(s) Of Engagement Activity 2015
 
Description 8th Workshop on Fats and Oils as Renewable Feedstock for the Chemical Industry 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact keynote lecture at the meeting in Karlsruhe Germany
Year(s) Of Engagement Activity 2015
 
Description Bio-Environmental Polymer Society BEPS 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited keynote lecture at the BEPS 2015 in Karlsruhe
Year(s) Of Engagement Activity 2015
 
Description Carbon Dioxide Utilization, Farady Discussion Meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited lecture and paper at the Faraday Meeting Sheffield
Year(s) Of Engagement Activity 2015
 
Description Catalysis Improving Society 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Lecture at the Royal Society Meeting and subsequent Satellite Meeting
Year(s) Of Engagement Activity 2015
 
Description Conference International Conference on Carbon Dioxide Utilization 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Dr Garcia trenco lectured at the conference in Singapore
Year(s) Of Engagement Activity 2015
 
Description Conference: Advanced Complex Inorganic Nanomaterials 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Presentation given by Dr Seb Pike at the conference in Belgium
Year(s) Of Engagement Activity 2015
 
Description Congrès 2015 de la Société Chimique de France 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited (keynote) lecture at the SCF in Lille
Year(s) Of Engagement Activity 2015
 
Description Dalton Young Researchers Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Pike lectured on his research at the conference
Year(s) Of Engagement Activity 2015
 
Description Demonstration Lecture at Lowther School Summer Fair - It's all about science 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Lecture given at the summer fair of a local primary school - lots of enthusiasm from parents and children

see above
Year(s) Of Engagement Activity 2014
 
Description Frontiers in Green Materials Symposium 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact 2 lectures at the symposium in London and posters to present our findings
Year(s) Of Engagement Activity 2015
 
Description Gordon Research Conference: Organometallic Chemistry 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Two posters presented at the GRC and GRS (lecture) in USA in 2015
Year(s) Of Engagement Activity 2015
 
Description Imperial College Festival 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact The Williams group ran an interactive 'stall' at the imperial college festival. We demonstrated how carbon dioxide can be transformed into products using a series of show-case examples, experiments and hands-on demonstrations for the general public. The total participation at the festival was 15,000 people.
we also participated in a special 'schools' event just before the festival opened where we demonstrated our science to primary school children
Year(s) Of Engagement Activity 2015
 
Description Invited Keynote lecture at Canadian Chemistry Congress Quebec City (Green Chemistry) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Interview with a journalist
Collaborations
Academic discussions
Discussions with companies

See above
Year(s) Of Engagement Activity 2013
URL http://www.csc2013.ca/
 
Description Invited and keynote lecture at 21 st Bioenvironmental Polymer Society Conference (Warwick) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussions with academics and industrialists

New collaboration formed with Michael Meier which resulted in a research exchange of Dr Mathias Winkler to Imperial College in 2014
Year(s) Of Engagement Activity 2013
URL http://www.beps.org/warwick.html
 
Description Invited lecture at 10th IUPAC International Conference on Advanced Polymers via Macromolecular Engineering (Durham); 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact New collaborations with academics in Sweden
discussions

see above
Year(s) Of Engagement Activity 2013
URL http://www.iupac.org/publications/ci/2012/3405/ca4_18.08.13.html
 
Description Keynote lecture at Macro Group Young Researcher's Symposium, Nottingham 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Discussions with students

New applications to my research group
Year(s) Of Engagement Activity 2013
URL http://www.macrogroup.org.uk/meeting/
 
Description Lecture at Sustainable Polymers Conference (ACS and RSC co-organising) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussion and new collaborations formed (Stefan Mecking, germany).

Raised academic profile of the group
Year(s) Of Engagement Activity 2013
URL http://polyacs.net/Workshops/13sustainable/program.htm
 
Description Lecture at the graduate school professional skills course for Imperial College London and MIT PG students 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Discussions about an academic career and about entrepreneurship

see above
Year(s) Of Engagement Activity 2014
 
Description Outreach lecture at primary school 
Form Of Engagement Activity Participation in an open day or visit at my research institution
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Schools
Results and Impact Lecture with demonstrations to primary school children - KS 1

Children very much enjoyed the visit and expressed an enthusiasm to study science
Year(s) Of Engagement Activity 2014
 
Description Presentation at the American Chemical Society National Meeting special symposium on Green Polymer Chemistry: Biobased Materials and Biocatalysis 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other academic audiences (collaborators, peers etc.)
Results and Impact Discussions with industrialists and academics

Book Chapter written in collaboration with other speakers - for the ACS symposium series
New collaborations likely
Invitations to collaborate
Year(s) Of Engagement Activity 2014
URL http://abstracts.acs.org/chem/248nm/meetingview.php?page=session&par_id=713
 
Description RSC Main Group Conference 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Lecture at the conference
Year(s) Of Engagement Activity 2015
 
Description The Science behind CO2 Capture and Conversion 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact invited lecture at the conference in Cuba
Year(s) Of Engagement Activity 2015
 
Description UK Catalysis Conference 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Presentation at the Uk Catalysis Conference, 2016, Loughborough
Year(s) Of Engagement Activity 2016
 
Description Uk Catlaysis Conference 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Garcia Trenco gave a lecture at the conference in 2015 in Loughborough
Year(s) Of Engagement Activity 2015