Flexible Routes to Liquid Fuels from CO2 by Advanced Catalysis and Engineering

Lead Research Organisation: University of Liverpool
Department Name: Chemistry

Abstract

There is an urgent need to address the accelerating increase in global CO2 emissions and atmospheric CO2 levels while providing fuels to meet growing energy needs. The UK government has targeted an 80% reduction in emissions (from 1990 levels) by 2050 with an interim target of 34% reduction by 2020. Increasingly, it is becoming clear that a key approach to storage of variable sustainable energy sources such as solar or wind power is in the form of stored chemical energy, and that this is likely to be as a form of hydrogen. However, although hydrogen itself has excellent enthalpy content per unit weight, it is a low density gas, has storage difficulties, and requires relatively high compression energy. The present proposal is focused on the conversion of sustainably produced hydrogen to high energy density liquid fuels including methanol, DME and hydrocarbons which are more easily transported and are compatible with existing fuel distribution networks. These fuels are low in sulfur and flexible in their contribution to future low carbon-intensity fuel scenarios by displacing fossil sources from the liquid fuels pool. They can be used for transport fuels (where they are likely to remain the focus for some time to come), as blending components, as seasonal storage candidates (exploiting their permanence and energy density), for distributed power production or for local heating.

The synthesis of these liquid fuels will be achieved using CO2 as a vector to react with hydrogen from solar or wind inputs. We therefore aim to develop new technology to reduce the atmospheric CO2 burden by utilising only water as a source of this hydrogen, avoiding highly endothermic thermocatalytic steam reforming. The annual CO2 emissions from UK electricity generation (around 150x10^6 tonnes) is sufficient, in principle, to supply the UK requirement for liquid transportation fuels, or three times the amount required for the world annual production of methanol (around 45x10^6 tonnes). There are a number of possible attractive concentrated point sources of this CO2, including CO2 prepared for sequestration or from ammonia plants, which could be used to make liquid fuels in the medium term provided efficient catalytic technologies could be developed. Thus we will develop new catalytic technology for the production of synthesis gas (CO/H2) and simple fuel organics, ultimately driven by solar energy using CO2 and H2 sustainably produced from water. We will explore integration of hydrogen and syngas generation with production of syngas from biogenic sources such as waste or biomass to provide additional feed flexibility. Part of our work will develop novel and targeted catalysts for the thermocatalytic production of 'green' fuels from syngas with variable CO2, H2 and water content, focused by process systems engineering considerations that specifically address low-carbon aspects such as intermittency of primary renewable power in process design. Industry partners have endorsed the approach and will provide key input into the form of point source CO2 supply, catalyst manufacture, liquid fuel synthesis, electrolyser manufacture, sustainable hydrogen generation and technology integration, life cycle analysis and industrial fuel usage.

The proposal adopts a multidisciplinary catalyst discovery, deployment and process engineering approach to develop, evaluate and optimise thermal, photo- and electro-catalysed routes to liquid fuels from CO2 and water using solar energy (and, indirectly, wind or marine power). Direct thermal and solar-assisted paths to methanol and DME will be compared with stepwise solar/electrochemical syngas generation plus thermal DME or Fischer-Tropsch hydrocarbon synthesis paths. The novel catalyst chemistries enabling each route will be integrated on the basis of process systems modelling and analysis to identify optimised schemes that will be benchmarked by input from industry partners with key roles in potential supply chains.

Planned Impact

The main benefit is creation of value from CO2 by upgrading with renewable hydrogen to versatile liquid fuels with reduced carbon intensity, thereby reducing our dependence on primary fossil fuel resources and enhancing sustainability.

The benefits across many industrial sectors including transport, energy generation, manufacturing and chemical industries are reflected in the range of industrial partners and supporters of the project. The new catalytic processes address conversion of CO2 emissions to drop-in replacement hydrocarbon fuels that can use existing capital infrastructure and distribution networks, integration with renewable feedstock markets including renewable hydrogen generation essential for this CO2 valorisation, catalyst development and manufacture and new prospects in process engineering and systems integration including reducing the carbon footprint of the notoriously high impact construction sector and other manufacturing activity. The Decarbonisation and Energy Efficiency Roadmaps (March 2015) set out by DECC and BIS for the eight most heat-intensive industrial sectors to reduce greenhouse gas emissions and improve energy efficiency by 2050 recognises the importance of research in enabling technology options and removing barriers. This project will deliver benefits by loading the development pipeline for technology options based on catalysis science and process engineering as candidates for scale up and demonstration. Our industry partners have a track record of developing research-based technology platforms via public-private partnerships, which dramatically increases the chances of success in the long term. The influence of our industry partners across supply chains in, for example, the built environment, will accelerate the adoption of successful technologies and therefore the number and scope of business beneficiaries. In addition, each industry partner has a significant UK presence and will directly benefit from the research outcomes. These benefits include manufacturing and sales of new catalysts, hydrogen electrolysers, fuels and reduction of manufacturing costs. The University partners have significant experience in generating and protecting intellectual property from multi-partner projects, and transferring this to UK industry. These benefits all arise from the multidisciplinary approach to flexible routes to low carbon-intensity fuels taken by the project consortium.

Society will benefit from increased security of energy supply, and from reduced CO2 emissions. The proposal also offers the prospect of lower overall fuel costs for transportation, households and industry. This will improve the competitiveness of UK manufacturing in global markets, especially where commoditisation (and therefore margin erosion) has occurred, resulting in greater productivity, job creation and a better standard of living. Society will additionally benefit from jobs created in new technologies, and from the high quality researchers (RAs and associated PhD students) with a multidisciplinary skill set emerging from the project. This makes them highly valued in academia, industrial research and technical consultancies, and helps build critical mass in CO2 valorisation and low carbon technologies for the future.

The proposed research is ideally placed to inform DECC and Innovate UK policy and the activity of the main regulator the Environment Agency, and also seed translational activity of promising technologies through establishments such as the UKCCSRC Pilot-Scale Advanced CO2-Capture Technology facilities by CO2 valorisation. This policymaker engagement is further facilitated by the role of our project partners in government advisory bodies such as the Green Construction Board and the Low Carbon Innovation Group, and our connectivity to the Knowledge Transfer Network via the Knowledge Centre for Materials Chemistry.

Publications

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Bahruji H (2018) Hydrogenation of CO 2 to Dimethyl Ether over Brønsted Acidic PdZn Catalysts in Industrial & Engineering Chemistry Research

 
Description New supported molecular catalysts for electrocatalytic reduction of CO2 have been identified and incorporated into demonstration devices. Development of other (thermal methanol and Fischer-Tropsch, photo-) catalysts has been achieved, with new high-throughput routes to stabilise preferred metal polymorphs and access multimetallic catalyst compositions identified. A new route to supported catalysts for methanol synthesis from CO2 and hydrogen has been identified [Topics in Catalysis (2018) 61:144-153], and this has been further developed for dimethyl ether synthesis [Ind. Eng. Chem. Res. 2018, 57, 6821] and even further for higher oxygenate and hydrocarbon production [Faraday Discuss., 2021, 230, 52 ;Topics in Catalysis (2021) 64:965-973] . Life cycle analyses are being developed to understand current processes and set targets for the development of new catalysts. A methodology based on Bayesian estimation for discriminating among alternative kinetic rate models of catalytic routes has been implemented and tested for methanol and DME synthesis [1]. Application of this methodology is underway using data arising from the various experimental programmes. A comparative enviro-economic assessment of methanol, DME and Fischer-Tropsch liquids is being carried out using detailed process simulation to understand the effect of syngas composition, so far showing superiority of methanol and DME in the present economic context [2,3]. Novel life cycle assessment methods are also being developed to understand current processes and set targets for the new catalysts we are developing [4]. 1. Bernardi A, Gomoescu L, Wang J, Pantelides CC, Chadwick D, Chachuat B, 2019, Kinetic model discrimination for methanol and DME synthesis using Bayesian estimation, IFAC-PapersOnLine 52(1):335-340 2. Bernardi A, Graciano JEA, Chachuat B, 2019, Production of chemicals from syngas: an enviro-economic model-based investigation, Computer Aided Chemical Engineering 46:367-372 3. Bernardi A, Chen Y, Chadwick D, Chachuat B, 2020, Direct DME synthesis from syngas: a techno-economic model investigation, Computer Aided Chemical Engineering (to appear) 4. Rodríguez-Vallejo DF, Galán-Martín Á, Guillén-Gosálbez G, Chachuat B, 2019, Data envelopment analysis approach to targeting in sustainable chemical process design: application to liquid fuels, AIChE Journal 65(7):e16480
Exploitation Route In the design and application of new catalysts and processes for transformation of CO2, and in the assessment of lifecycle implications of these processes.
Sectors Chemicals,Energy,Environment,Transport

 
Description Project investigators played key (including leadership) roles in the Royal Society's policy briefings to UK government on carbon dioxide utilisation in 2017 and on sustainable synthetic liquid fuels for transport in 2019. This drew on research results and perspectives developed in the project. The outcomes of these briefings and the associated future opportunities for industry and society were discussed at a meeting in Liverpool in February 2020 attended by a cross-sector UK academic/industry/government group featuring international academic and UK industry presentations. Discussions from this meeting led to a Royal Society Net Zero Aviation Workshop in December 2020 attended by UK academic and industry researchers and Government Departmental Scientific Advisors. These discussions have now led the Royal Society to fund a Policy Briefing document in the area of Sustainable Aviation Fuels, led by and including investigators from this grant, with a workshop bringing together academia, industry, policy organisations and government in March 2022 as part of the development of this brief for UK Government leading to the publication of the report in February 2023. Methods developed in the project for high-throughput catalyst synthesis have attracted the attention of industry for separate support in the synthesis of chemicals from waste CO2, which has led to a major project in this area. The electrochemical reactor for syngas production is to be used in two future projects with industry partners to test the feasibility of using this reactor and the electrodes developed in this project for conversion of CO2 streams with typical contaminants found in industrial sources. High throughput methods for catalyst testing have been developed and are now used in a large collaboration with UK industry. This funding has led to a multicentre C2C collaboration with the Netherlands and Germany.
First Year Of Impact 2017
Sector Chemicals,Energy,Transport
Impact Types Societal,Policy & public services

 
Description Chair Royal Society Policy Briefing
Geographic Reach Multiple continents/international 
Policy Influence Type Implementation circular/rapid advice/letter to e.g. Ministry of Health
URL https://royalsociety.org/topics-policy/projects/low-carbon-energy-programme/sustainable-synthetic-ca...
 
Description Work on this project informed and influenced the Royal Society policy briefing for the GCSA on "The potential and Limitations of using carbon dioxide", chaired and led by the PI
Geographic Reach National 
Policy Influence Type Implementation circular/rapid advice/letter to e.g. Ministry of Health
URL https://royalsociety.org/topics-policy/projects/low-carbon-energy-programme/potential-limitations-ca...
 
Description Work on this project informed and influenced the Royal Society policy briefing presented to DfT and BEIS on "Sustainable synthetic carbon based fuels for transport", chaired and led by CI Hutchings.
Geographic Reach National 
Policy Influence Type Implementation circular/rapid advice/letter to e.g. Ministry of Health
URL https://royalsociety.org/topics-policy/projects/low-carbon-energy-programme/sustainable-synthetic-ca...
 
Title CO2 hydrogenation to CH3OH over PdZn catalysts, with reduced CH4 production - data 
Description Metallic Pd, under CO2 hydrogenation conditions (> 175 °C, 20 bar in this work), promotes CO formation via the reverse water gas shift (RWGS) reaction. Pd-based catalysts can show high selectivity to methanol when alloyed with Zn, and PdZn alloy catalysts are commonly reported as a stable alternative to Cu-based catalysts for the CO2 hydrogenation to methanol. The production of CH4 is sometimes reported as a minor by-product, but nevertheless this can be a major detriment for an industrial process, because methane builds up in the recycle loop, and hence would have to be purged periodically. Thus, it is extremely important to reduce methane production for future green methanol synthesis processes. In this work we have investigated TiO2 as a support for such catalysts, with Pd, or PdZn deposited by chemical vapour impregnation (CVI). Although titania-supported PdZn materials show excellent performance, with high selectivity to CH3OH + CO, they suffer from methane formation (> 0.01 %). However, when ZnTiO3 is used instead as a support medium for the PdZn alloy, methane production is greatly suppressed. The site for methane production appears to be the TiO2, which reduces methanol to methane at anion vacancy sites. This data set contains an excel file with the catalyst characterisation (XRD for supports, annealed and reduced samples, in situ XRD reduction for Pd/ZnO; XPS for Pd(3d), Zn(2p) and Zn(LM2); BET surface area; TEM images and particle count; CO2 hydrogenation data including CO2 conversion, product selectivity and productivity). 
Type Of Material Database/Collection of data 
Year Produced 2020 
Provided To Others? Yes  
URL https://research.cardiff.ac.uk/converis/portal/detail/Dataset/116381908?auxfun=&lang=en_GB
 
Title IMPROVEMENTS IN ELECTROCHEMICAL REDUCTION OF CARBON DIOXIDE 
Description An electrochemical cell comprising a gas diffusion electrode for the electrochemical reduction of carbon dioxide. The gas diffusion electrode comprises a gas diffusion layer and a nickel or manganese-based molecular catalyst comprising an organic ligand. The gas diffusion electrode may provide a selective electrochemical reduction of carbon dioxide to carbon monoxide, in preference to hydrogen, and may be useful for the production of carbon monoxide from industrial waste gas streams of carbon dioxide. A nickel-based molecular catalyst and a method of electrochemical reduction of carbon dioxide are also disclosed. 
IP Reference WO2022129895 
Protection Patent / Patent application
Year Protection Granted 2022
Licensed No
Impact patent published seekign exploitation pathways with university ip team. Ongoing develoment of ip occurign with 2nd filing underway
 
Description 2nd Joint Solar Fuels Network-SuperSolar Workshop 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Ms Verity Piercy presented a poster at the 2nd Joint Solar Fuels Network-SuperSolar Workshop, London, 10 December 2019, titled "Band gap engineering of carbon nitrides - understanding reactivity trends" which generated interest and questions from the attendees
Year(s) Of Engagement Activity 2019
 
Description 7th Solar Fuels Network Symposium 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Ms Verity Peircy presented a poster at the 7th Solar Fuels Network Symposium, 28 March 2018 in Cambridge, titled "Band gap engineering of carbon nitrides - understanding reactivity trends" which generated interest and discussion amongst the attendees
Year(s) Of Engagement Activity 2019
 
Description Chair, breakout session, RS Net Zero Aviation Workshop, December 2020 
Form Of Engagement Activity A formal working group, expert panel or dialogue
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact • Chair, breakout session on the opportunities and challenges of using Efuels (Sustainable Aviation Fuel) in powering aviation in a net zero-carbon future for both short and long haul, RS Net Zero Aviation Workshop, December 2020
Year(s) Of Engagement Activity 2020
 
Description EPSRC workshop on low carbon fuels 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact The workshop took place at the University of Liverpool on Monday 3 February 2020 brought together the four project teams funded by EPSRC under the low carbon fuel call. In the first session, each project team presented their key developments and outcomes and they discussed opportunities for future collaborations. The second session was open to external collaborators and invited speakers from academia and industry to provide their perspective in the production of sustainable and synthetic fuels. Overall this workshop provided the opportunity to researchers with different backgrounds to create a common understanding on the topic and foster new synergies, and also included Research Council and Government (BEIS, DFT) delegates. Presentations were given by Professor Robert Schlogl (Fritz Haber Institut, Berlin) and senior representatives of BP and Rolls Royce, followed by a panel discussion with interactive engagement from the audience.
Year(s) Of Engagement Activity 2020
 
Description High Throughput Methods for Catalyst Discovery. Poster presentation at the Women in Chemistry: Conference and Careers Event, Nottingham, UK, March 2020. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Carrillo, P., Alvarado, L., Katsoulidis, A., Zanella, M., Manning, T., Claridge, J., Rosseinsky, M. J., High Throughput Methods for Catalyst Discovery. Poster presentation at the Women in Chemistry: Conference and Careers Event, Nottingham, UK, March 2020.
Year(s) Of Engagement Activity 2020
 
Description Joint UK&Ireland/Spain Semiconductor Photochemistry meeting 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Ms Verity Piercy gave a talk at the Joint UK&Ireland/Spain Semiconductor Photochemistry meeting in Gran Canaria, 11-12 September 2018 titled "Band gap engineering of carbon nitrides - understanding reactivity trends" which generated questions from the audience
Year(s) Of Engagement Activity 2018
 
Description Oral presentation 12th IFAC Symposium on Dynamics & Control of Process Systems (DYCOPS) 2019 by A. Bernardi 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation at 12th IFAC Symposium on Dynamics & Control of Process Systems (DYCOPS) 2019 by A. Bernardi on kinetic model discrimination for methanol and DME synthesis using Bayesian estimation. There was keen interest in the presentation as it demonstrated the utility of Bayesian estimation in the area of kinetic model discrimination. The authors were invited to write an article on the topic for Journal of Process Control.
Year(s) Of Engagement Activity 2019
 
Description Oral presentation by Andrea Bernadi at ISCRE25: Model-based investigation of methanol and DME synthesis 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation on modelling kinetics of methanol/DME synthesis at ISCRE25, the premier conference in chemical reaction engineering. Attendance in excess of 100. A further presentation will be given at DYCOPS2019
Year(s) Of Engagement Activity 2018
 
Description Prof Rosseinsky gave an invited lecture at Center for Electronics and Microtechnology (CSEM), Neuchatel, Switzerland, 4 November 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited lecture at Paul Scherrer Intitut, Villigen, Switzerland, 4 November 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited lecture at the CDT-PV Summer School & Showcase Event, University of Bath, 12 September 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited lecture at the Centre for Dielectrics and Piezoelectrics, University of Sheffield May 14-15 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited lecture at the Swiss Federal Laboratories for Materials Science and Technology (EMPA), Dubendorf, Switzerland 8 November 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited lecture at École polytechnique fédérale de Lausanne, Switzerland, 7 November 2019, 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description Prof Rosseinsky gave an invited talk at the University of Fribourg, Switzerland, 6 November 2019 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Presented on the topic of "Design of advanced materials?" for dissemination of results and academic discussion
Year(s) Of Engagement Activity 2019
 
Description RSC Early Career symposium, August 2018 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Gaia Neri presented a poster at the 5th RSC Early Career symposium, Liverpool, August 2018, title "CO2 reduction intermediates with in-situ SFG spetroelectrochemistry" generating interest and questions from the attendees.
Year(s) Of Engagement Activity 2018
 
Description Solar Fuels Gordon Conference, Ventura, January 2018 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Dr Gaia Neri presented a poster at the Renewable Energy Solar Fuels Gordon Conference, Ventura USA, January 2018, title CO2 reduction intermediates with in-situ SFG spectroelectrochemistry generating interest and discussion from the attendees.
Year(s) Of Engagement Activity 2018
 
Description UK Solar Fuel Network-SuperSolar workshop 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Dr Gaia Neri gave a talk at the Joint UK Solar Fuels Network-SuperSolar workshop on Solar Energy Conversion and Storage, London, December 2019, titled "Mn(bpy)(CO)3Br: CO2 reduction in water, scale-up and study of the mechanism using SFG spectroscopy" generating discussion and questions from the audience.
Year(s) Of Engagement Activity 2019