Tuning Catalyst Surfaces to Control Aldol Reactions in Biomass Conversion
Lead Research Organisation:
Aston University
Department Name: Research Support Office
Abstract
Oil is the most important source of energy worldwide, accounting for some 35% of primary energy consumption and the majority of the chemical feedstocks; tackling the current world energy crisis is recognised as a top priority for both developed and developing nations, with sustainable sources of chemicals and fuels urgently sought in response to both diminishing world oil reserves and increasing environmental concerns over global climate change. Sustainable 'carbon-neutral' energy sources derived from biomass can play a major role in achieving this goal, with projections suggesting annual greenhouse gas emissions could be reduced by up to 12.4 Gtons. Transportation fuels can be generated from bio-oils which are readily obtained from sustainable biomass resources such as waste agricultural crops, forestry products, high yielding inedible plants such as Switchgrass, however, bio-oils cannot be used directly as transportation fuels and require catalytic upgrading before use. Likewise the US Department of Energy identified 12 'Platform Chemicals' that can be produced directly from sugars via chemical or biochemical transformation of lignocellulosic biomass and provide the basic feedstocks for sustainable chemicals manufacture. These molecules are highly oxygenated and contain a range of desirable functional groups such as acid, alcohol, carboxyl groups often required in synthetic materials. Thus in contrast to current chemicals synthesis starting from oil where oxygen insertion is required to generate functional materials, biomass derived building blocks necessitate new technology to selectively isomerise and/or 'deoxygenate' these highly functional molecules to reach the target molecule.
Catalysis has a rich history of facilitating energy efficient selective molecular transformations and contributes to 90% of chemical manufacturing processes and to more than 20% of all industrial products. In a post-petroleum era catalysis will be central to overcoming the engineering and scientific barriers to economically feasible routes to bio-fuels and chemicals. This proposal will address the major technological challenge of selectively converting sugars to platform chemicals or fuels and bio-oil to fuels; both of which involve common reactions, namely a combination of condensation and deoxygenation reactions to produce alkanes. Current commercial catalysts are not designed for such applications and have inherently poor lifetimes and selectivity. The specific goal of our research will be to improve catalyst selectivity and efficiency via a combination of materials design (at Cardiff) to create controlled pore architectures containing interconnected macro- and mesopores specifically aimed to reduce diffusion limitation of bulky and viscous feedstocks common to biomass. The design of materials will be guided by in-situ spectroscopic analysis of working catalysts (at Oklahoma) which will allow us to identify key features that lead to improved performance and thus allow the nature of the active site to be tailored accordingly. These samples will be tested in both laboratories under liquid (Cardiff) and vapor phase (Norman) conditions. We will use the acquired knowledge to design improved solid catalysts for aldol condensations, which are crucial for the conversion of biomass to chemicals and fuels. The proposed research thus addresses national and global needs for sustainability.
Catalysis has a rich history of facilitating energy efficient selective molecular transformations and contributes to 90% of chemical manufacturing processes and to more than 20% of all industrial products. In a post-petroleum era catalysis will be central to overcoming the engineering and scientific barriers to economically feasible routes to bio-fuels and chemicals. This proposal will address the major technological challenge of selectively converting sugars to platform chemicals or fuels and bio-oil to fuels; both of which involve common reactions, namely a combination of condensation and deoxygenation reactions to produce alkanes. Current commercial catalysts are not designed for such applications and have inherently poor lifetimes and selectivity. The specific goal of our research will be to improve catalyst selectivity and efficiency via a combination of materials design (at Cardiff) to create controlled pore architectures containing interconnected macro- and mesopores specifically aimed to reduce diffusion limitation of bulky and viscous feedstocks common to biomass. The design of materials will be guided by in-situ spectroscopic analysis of working catalysts (at Oklahoma) which will allow us to identify key features that lead to improved performance and thus allow the nature of the active site to be tailored accordingly. These samples will be tested in both laboratories under liquid (Cardiff) and vapor phase (Norman) conditions. We will use the acquired knowledge to design improved solid catalysts for aldol condensations, which are crucial for the conversion of biomass to chemicals and fuels. The proposed research thus addresses national and global needs for sustainability.
Planned Impact
This project seeks to provide new mechanistic insight into surface mechanism of aldol condensation and associated production of biofuels. By evaluating catalytic materials and obtaining fundamental understanding via a combination of in-situ and detailed kinetic information we hope to tailor the catalyst surfaces to improve lifetime and selectivity thus generating new knowledge of catalytic systems and designing materials optimised for the transformation of biomass to fuels and chemicals. The resulting structure activity correlations and fundamental adsorption properties identified from the insitu studies will be of interest to materials and catalytic and surface chemists looking to develop new catalytic materials, while the kinetic work will interest chemical engineers involved in process design.
At a fundamental level this research will be of interest to both materials and catalytic scientists who will gain access to new classes of tailored materials for liquid phase acid and base catalysis. Such materials could be employed more widely in Organic Synthesis for condensation reactions (as well as other classes of reaction (e.g. esterification, alkylation, isomerisation). The development of selective heterogeneous catalysts will also be of wider interest to the synthetic community looking to apply green chemistry principles and replace conventional homogeneous reagents with cleaner technologies
The proposed activities will also advance discovery and promote scientific education within the US by involving senior and junior faculty, postdoctoral researchers, and graduate, undergraduate and high school students. The students will be exposed to the fundamental questions associated with the conversion of biomass to fuels, including the challenges posed by the high oxygen content of biomass, the thermodynamically feasible ways to reduce the oxygen content, and the challenge in developing catalysts that promote such reactions selectively, economically and with minimal environmental impact. Additionally, the students will be: 1) familiarized with the concepts of homogeneous and heterogeneous catalysis, and their application for chemicals processing; 2) will learn how the disciplines of Chemical Engineering and Chemistry are combined to work towards implementation of a novel process; 3) provide cutting-edge cross-disciplinary scientific and technical training and an international exchange experience for the involved researchers, including knowledge transfer in respective areas of spectroscopy and materials synthesis.
Society will benefit through the results and in the training of researchers who will become part of the workforce in sustainable technologies. The research will provide the scientific foundation for (i) future catalytic processes that would reduce the U.S. (and global) dependence on foreign fossil feedstock as well as CO2 emissions and for (ii) replacement of currently used caustic catalysts by environmentally sound, solid materials. The proposed research thus addresses national and global needs for sustainability.
At a fundamental level this research will be of interest to both materials and catalytic scientists who will gain access to new classes of tailored materials for liquid phase acid and base catalysis. Such materials could be employed more widely in Organic Synthesis for condensation reactions (as well as other classes of reaction (e.g. esterification, alkylation, isomerisation). The development of selective heterogeneous catalysts will also be of wider interest to the synthetic community looking to apply green chemistry principles and replace conventional homogeneous reagents with cleaner technologies
The proposed activities will also advance discovery and promote scientific education within the US by involving senior and junior faculty, postdoctoral researchers, and graduate, undergraduate and high school students. The students will be exposed to the fundamental questions associated with the conversion of biomass to fuels, including the challenges posed by the high oxygen content of biomass, the thermodynamically feasible ways to reduce the oxygen content, and the challenge in developing catalysts that promote such reactions selectively, economically and with minimal environmental impact. Additionally, the students will be: 1) familiarized with the concepts of homogeneous and heterogeneous catalysis, and their application for chemicals processing; 2) will learn how the disciplines of Chemical Engineering and Chemistry are combined to work towards implementation of a novel process; 3) provide cutting-edge cross-disciplinary scientific and technical training and an international exchange experience for the involved researchers, including knowledge transfer in respective areas of spectroscopy and materials synthesis.
Society will benefit through the results and in the training of researchers who will become part of the workforce in sustainable technologies. The research will provide the scientific foundation for (i) future catalytic processes that would reduce the U.S. (and global) dependence on foreign fossil feedstock as well as CO2 emissions and for (ii) replacement of currently used caustic catalysts by environmentally sound, solid materials. The proposed research thus addresses national and global needs for sustainability.
Publications
Ciddor L
(2015)
Catalytic upgrading of bio-oils by esterification
in Journal of Chemical Technology & Biotechnology
Creasey J
(2014)
Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production
in Catal. Sci. Technol.
Dierks M
(2018)
Impact of Hydrophobic Organohybrid Silicas on the Stability of Ni 2 P Catalyst Phase in the Hydrodeoxygenation of Biophenols
in ChemCatChem
Dos Santos V
(2017)
A new application for transition metal chalcogenides: WS2 catalysed esterification of carboxylic acids
in Catalysis Communications
Frattini L
(2017)
Support enhanced a-pinene isomerization over HPW/SBA-15
in Applied Catalysis B: Environmental
Manayil J
(2017)
Octyl Co-grafted PrSO 3 H/SBA-15: Tunable Hydrophobic Solid Acid Catalysts for Acetic Acid Esterification
in ChemCatChem
Manayil J
(2016)
Mesoporous sulfonic acid silicas for pyrolysis bio-oil upgrading via acetic acid esterification
in Green Chemistry
Manayil JC
(2017)
Impact of Macroporosity on Catalytic Upgrading of Fast Pyrolysis Bio-Oil by Esterification over Silica Sulfonic Acids.
in ChemSusChem
Description | Methods to quantify the hydrophobicity of catalyst materials and correlate this parameter with their catalyst activity in reactions where water has a detrimental effect of catalyst performance have been developed. This research has led to the development of catalysts that are potential replacements for liquid acids that are used in biomass transformation. This will increase the efficiency and reduce the production of aqueous waste in chemical conversions by allowing reactions to be performed in continuous processes with the avoidance of corrosive liquid acids. The catalyst materials exhibit superior activity to commercial acid resins that are often used by industry in acid catalysed processes offering improved lifetime and hopefully more cost effective processes where acid catalysis is employed, spanning biomass conversion to fine chemicals synthesis. |
Exploitation Route | The analytical method and catalyst synthesis methods can be applied to a range of catalytic processes spanning fine and commodity chemicals synthesis to catalytic bio-refining. The availability of more efficient catalysts tailored for biomass conversion should help increase the economic viability of synthesis of replacement bio-derived chemicals for use in industry. Such advances could contribute to the manufacture of low carbon products by UK industry. The source of biomass for such processes can be agricultural or food waste and we are working closely with such industries to apply these catalysts in the production of high value chemicals from such waste resources. |
Sectors | Agriculture, Food and Drink,Chemicals,Energy,Environment,Manufacturing, including Industrial Biotechology |
Description | The development of high efficiency catalysts tailored for the conversion of bulky polar molecules derived from Biomass is essential to improve the viability of low carbon products produced from biorefining. While the main target of this project was development of catalysts to improve biofuel production, the catalysts developed have attracted interest from industry where waste sugars (e.g. Food processing industry, Organic recovered fraction from Municipal Solid Waste) are produced that are a potential feedstock for the production of high value chemical products. This has led to collaboration with companies including Chemoxy, Premier Foods/Hovis and Fiberight in which potential applications are being investigated. Ultimately the impact of this research could be on the development of new low carbon chemical feedstocks for use in Manufacturing processes including coatings and polymers. This project has also helped develop further international collaborations and laid the foundation for the funded proposal to the Global Innovation Initiative, GB3-NET which involves partners from Brazil, US and China (http://www.aston.ac.uk/eas/research/groups/ebri/projects/gb3net/) |
First Year Of Impact | 2016 |
Sector | Chemicals,Energy,Manufacturing, including Industrial Biotechology |
Impact Types | Societal,Economic |
Description | Global Innovation Initiative |
Amount | £150,000 (GBP) |
Organisation | British Council |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 04/2015 |
End | 05/2017 |
Description | Collaboration with Prof Taufiq Yap on biofuel synthesis |
Organisation | Putra Malaysia University |
Country | Malaysia |
Sector | Academic/University |
PI Contribution | Collaborative research exchange project funded through the Royal Society |
Collaborator Contribution | Catalyst synthesis, Bio-oil upgrading using real feedstocks and student training in analytical techniques |
Impact | Collaboration in multi-disciplinary at the chemical - chemistry engineering interface Knowledge exchange though research seminars and networking with PhD and postdoctoral researchers |
Start Year | 2017 |
Description | Collaboration with the University of Rey Juan Carlos, Madrid |
Organisation | King Juan Carlos University |
Country | Spain |
Sector | Academic/University |
PI Contribution | A number of researchers have been seconded to our laboratory to work on the development of catalysts for biodiesel synthesis |
Collaborator Contribution | Large scale synthesis of mesoporous materials for biodiesel synthesis and the evaluation of hydrophobic catalysts for converting high water content waste oil to biodiesel. |
Impact | The collaboration is mulit-disciplinary spanning Chemistry and Chemical Engineering. The main outputs to date are 5 publications and also 1 FP7 proposal (Cascatbel) led by Prof David Serrano of IMDEA and URJC |
Start Year | 2010 |
Description | visit by Prof F Jentoft to Aston University 13-17th March |
Organisation | Imperial College London |
Department | Department of Chemical Engineering |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | Visit by Prof Jentoft to identify areas for collaboration in the area of heterogeneous catalysis for biomass conversion. Research exchange visits planned for Ms Lucia Frattini to UMass Amherst and Mt Koushik Ponnuru to Aston in August 2016. Meetings were also had with Academic staff and PhD students including Dr Marta Granollers, Dr Jude Onwudilli, Ms Ravneet Kaur, Dr George Kyriakou, Dr Chris Parlett, Dr Mark Isaacs and Mr James Hunns. |
Collaborator Contribution | See above |
Impact | Current EPSRC/NSF proposal on aldol condensation Exchange visits planned for researchers. |
Description | Catalysing Sustainable Chemical Synthesis - ISEMN 2014 Wuhan, China |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Type Of Presentation | keynote/invited speaker |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Stimulated discussion in catalyst design and energy materials New contacts and potential international collaborators identified |
Year(s) Of Engagement Activity | 2014 |
Description | Designing Catalysts for Biorefining |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Invited lecture at the EPSRC Catalysis Hub and BBSRC BIOCATNET conference 'Working at the Bio Chemo interface' |
Year(s) Of Engagement Activity | 2016 |
Description | Designing solid acids and bases for biofuel synthesis - Oral presentation at the 2nd International Congress on Catalysis for Biorefineries - CatBior 2013 conference in Dalian, China |
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 | Oral presentation entitled 'Designing solid acids and bases for biofuel synthesis' at the 2nd International Congress on Catalysis for Biorefineries - CatBior 2013 conference in Dalian, China Increased visibility in China and developments of new collaborations |
Year(s) Of Engagement Activity | 2013 |
URL | http://catbior2013.dicp.ac.cn/dct/page/1 |
Description | Invited speaker at Industry and Parliament Trust, Parliamentary Programme on the diversification of energy sources and energy mix (Portcullis House, Westminster, 2015) ? |
Form Of Engagement Activity | A formal working group, expert panel or dialogue |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Policymakers/politicians |
Results and Impact | Invited speaker at Industry and Parliament Trust, Parliamentary Programme on the diversification of energy sources and energy mix (Portcullis House, Westminster, 2015). Breakfast meeting with Industrialists, policy makers and politicians. ? |
Year(s) Of Engagement Activity | 2015 |
URL | https://www.energy-uk.org.uk/publication.html?task=file.download&id=5488 |
Description | Oral presentation at the Workshop Biomass Resources for Renewable Energy Production, 2nd-3rd June, 2016 IMDEA Energy Institute Móstoles - Madrid |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Prof Karen Wilson, Catalyst design for biorefining - Workshop BIOMASS RESOURCES FOR RENEWABLE ENERGY PRODUCTION, 2nd-3rd June, 2016 IMDEA Energy Institute Móstoles - Madrid |
Year(s) Of Engagement Activity | 2016 |
Description | Plenary Lecture 'Catalytic Technologies for the Production of Bioproducts and Biofuels' at CCESC 2016 'Catalysts for Clean Energy and Sustainable Chemistry', (Madrid 2016) |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Plenary lecture at international conference |
Year(s) Of Engagement Activity | 2016 |
URL | http://www.ccesc2016.net/ |
Description | Smart Biorefinery: Outlook and Prospects (University of Warwick workshop) July 2016 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Professional Practitioners |
Results and Impact | Oral presentation vy Dr Amin Osatiashtiani entitled 'Designing heterogeneous catalysts for biorefining' at University of Warwick workshop on the 'Smart Biorefinery: Outlook and Prospects Date: 7 July 2016 Led to increased interest in the potential of tailored catalysts in biorefinery applications. |
Year(s) Of Engagement Activity | 2016 |
Description | Tailoring Solid Acid Catalysts for Biomass Conversion |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Type Of Presentation | keynote/invited speaker |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Oral presentation that the 2nd International Symposium and Workshop of the Global Green Chemistry Centres (G2C2); 24th-26th August 2014 Two Oceans Aquarium, Cape Town, South Africa Meeting of global centre leaders in Green Chemistry. EBRI was invited to join as a core member |
Year(s) Of Engagement Activity | 2014 |
Description | Talk on "Heterogeneous acid and base catalysts for biodiesel production", UK-China Workshop on Advanced Technologies for Energising Sustainable Urban Transport, 16-18 May 2016. |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Research presentation by Dr Jinesh Manayil at UK-China Workshop on Advanced Technologies for Energising Sustainable Urban Transport, 16-18 May 2016 for early career scientists. Stimulated discussion about the development of catalysts for biofuel synthesis with Chinese and UK scientists. |
Year(s) Of Engagement Activity | 2016 |
Description | Waste biomass: A key player in securing UK energy and chemical needs in the 21st century through biorefining |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | National |
Primary Audience | Policymakers/politicians |
Results and Impact | Panel Debate at Industry and Parliament Trust breakfast meeting with politicians as part of the Resilient Futures Programme. The PDF report was circulated throughout the UK and is available online |
Year(s) Of Engagement Activity | 2015 |
URL | http://www.ipt.org.uk/Portals/0/IPT%20News%20and%20Comment/Research%20Page/IPT%20Resilient%20Futures... |
Description | Waste not Want not interview |
Form Of Engagement Activity | A magazine, newsletter or online publication |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Interview with Prof Wilson by the Royal Society of Chemistry/Chemistry World focussed on the opportunities of using waste biomass as a feedstock for energy and chemicals, and how catalysis can help with facilitating such technology |
Year(s) Of Engagement Activity | 2015 |
URL | http://www.rsc.org/chemistryworld/2015/09/waste-not-want-not-karen-wilson-interview |