Development of fast pyrolysis based advanced biofuel technologies for biofuels

Lead Research Organisation: Cranfield University
Department Name: Sch of Aerospace, Transport & Manufact

Abstract

The use of biofuels, as a renewable source of energy has become increasingly important. More in particular, biofuels for transport have the potential to displace a substantial amount of petroleum around the world. The EU is aiming to achieve at least 10% of road fuel derived from plants by 2020. The Carbon Trust selected "Pyrolysis Challenge" as the first strand of Bioenergy Accelerator with £10m investment, highlighting the importance of pyrolysis-oil as the potential replacement for transport fuels with low system GHG (green house gases) emissions. While fast pyrolysis oils have the potential to be processed in existing petroleum refinery infrastructure to transportation fuels, our ability to process the oil requires improved understanding of how to control its chemical composition and improve its physical properties. Current fast-pyrolysis oils are inherently unstable due to their high oxygen content and acidity which leads to polymerisation of reactive components and subsequent viscosity increase via polymer formation which hinders direct refining. Catalytic processes are thus required capable of transforming fast pyrolysis oils such that their acidity and oxygen content is reduced under moderate conditions thereby improving oil stability and allowing direct refining. To minimise energy inputs, it would be desirable to catalytically treat pyrolysis oil vapours immediately after the pyrolyser using a close coupled catalytic reactor to facilitate deoxygenation, chain growth and/or aromatisation of molecules. Such an approach would minimise extra energy inputs but also reduce polymerisation routes into more intractable resins. To achieve these goals we propose to explore non-precious metal de-oxygenation cracking catalysts including doped zeolite materials and bifunctional Fe based catalysts for pre-treatment of pyrolysis oil vapours. By working in the vapour phase we should eliminate some of the problems currently associated with the use of such catalysts in liquid phase processes where leaching by acidic components and char deposition leads to deactivation. The impact of pre-treatment on overall final hydrodeoxygenation (HDO) of bio-oil will also be evaluated. These routes to refinery feedstocks will be compared technically and economically.

Planned Impact

The use of biofuels, as a renewable source of energy has become increasingly important. More in particular, biofuels for transport have the potential to displace a substantial amount of petroleum around the world. The EU is aiming to achieve at least 10% of road fuel derived from plants by 2020. The Carbon Trust selected "Pyrolysis Challenge" as the first strand of Bioenergy Accelerator with £10m investment, highlighting the importance of pyrolysis-oil as the potential replacement for transport fuels with low system GHG (green house gases) emissions. While fast pyrolysis oils have the potential to be processed in existing petroleum refinery infrastructure to transportation fuels, our ability to process the oil requires improved understanding of how to control its chemical composition and improve its physical properties. Current fast-pyrolysis oils are inherently unstable due to their high oxygen content and acidity which leads to polymerisation of reactive components and subsequent viscosity increase via polymer formation which hinders direct refining. Catalytic processes are thus required capable of transforming fast pyrolysis oils such that their acidity and oxygen content is reduced under moderate conditions thereby improving oil stability and allowing direct refining. To minimise energy inputs, it would be desirable to catalytically treat pyrolysis oil vapours immediately after the pyrolyser using a close coupled catalytic reactor to facilitate deoxygenation, chain growth and/or aromatisation of molecules. Such an approach would minimise extra energy inputs but also reduce polymerisation routes into more intractable resins. To achieve these goals we propose to explore non-precious metal de-oxygenation cracking catalysts including doped zeolite materials and bifunctional Fe based catalysts for pre-treatment of pyrolysis oil vapours. By working in the vapour phase we should eliminate some of the problems currently associated with the use of such catalysts in liquid phase processes where leaching by acidic components and char deposition leads to deactivation. The impact of pre-treatment on overall final hydrodeoxygenation (HDO) of bio-oil will also be evaluated. These routes to refinery feedstocks will be compared technically and economically.

Publications

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Gadkari S (2017) Numerical analysis of microwave assisted thermocatalytic decomposition of methane in International Journal of Hydrogen Energy

 
Description Zeolite based catalysts were tested for direct vapour cracking with significant coke deposition found for fixed bed reactors. A bi-functional catalyst was tested for deoxygenation reaction during the decomposition of anisole in a bench-scale fluidised bed reactor within the temperature range from 400 °C to 600 °C. Experimental results revealed that the increase in temperature and metal loading promoted the selectivity of BTX fraction.
Synthetic red mud was produced to establish the influence of components.
Circulating fluidised bed reactors for vapour cracking were designed and evaluated with CFD model. The lumped kinetic model for vapour cracking didn't give accurate prediction and more detailed molecular dynamic model needs to be carried out. CFD model is developed for catalytic upgrading of pyrolysis vapours in a pilot scale FCC riser
including hydrodynamics, residence time distribution (RTD) and chemical reactions.
Exploitation Route The model can be used for reactor design and validation by academic and industrial users.
Catalysts can be made commercially available by manufacturers.
Sectors Chemicals,Energy

URL http://fast-pyrolysis.com/catalyticsystem/home.html
 
Description The research is making positive impact to the community for biomass fast pyrolysis. We have presented our research plan and results in national and international conferences in particular UK SUPERGEN Bioenergy meetings and EU bioenergy conferences. We are applying this technology for waste to energy process with an industrial partner to develop pyrolysis based technology. The technology was demonstrated in UK National Recycling Awards 2014 and won a number of awards. We worked with industrial partners to test the quality of pyrolysis oils with engines. The test results lead to a number of journal publications. We are also exploring joint projects with industrial and academic partners on economic ways for upgrading pyrolysis oils including co-processing at existing petroleum refinery. We also start to look at the integration of the whole process from waste to energy and chemicals using pyrolysis, upgrading and fuel cells technologies to reduce the costs and wastes. We have been approached by various companies in Asia, Africa and South America to help them develop pyrolysis based technologies for waste treatment, plastic recycling, energy generation, transport fuels or chemicals. We continue to pursue opportunities for wider dissemination of our research.
First Year Of Impact 2020
Sector Chemicals,Energy,Environment
Impact Types Economic

 
Description Catalytic thermal conversion mechanism to produce aromatic compounds from lignin
Amount ¥200,000 (CNY)
Organisation National Natural Science Foundation of China 
Sector Public
Country China
Start 09/2016 
End 09/2018
 
Description Combined Energy Recovery & CO2 Removal Project
Amount £147,622 (GBP)
Funding ID EP/N508615/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 09/2015 
End 09/2016
 
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 Shanghai Jiaotong University 
Organisation Shanghai Jiao Tong University
Country China 
Sector Academic/University 
PI Contribution To provide CFD modelling and optimisation of their designed fast pyrolysis reactors at different scales
Collaborator Contribution To carry out the fast pyrolysis for different feedstock available in China with data for product yields
Impact Organised workshop and seminars in China for bioenergy research
Start Year 2014
 
Description Collaboration with South East University 
Organisation Southeast University China
Country China 
Sector Academic/University 
PI Contribution To share our multiscale modelling expertise
Collaborator Contribution To provide large scale experimental facility
Impact A number of visits were made between the partners.
Start Year 2014
 
Description Collaboration with Southeast University of China 
Organisation Southeast University China
Country China 
Sector Academic/University 
PI Contribution Collaborating with Southeast University of China on bio-oil upgrading and fundamental kinetic study
Collaborator Contribution Our researcher visited Southeast University and carried out experimental work. The collaboration leads to joint publication and supervision of PhD researchers.
Impact This is leading to journal publications which are listed in the publication record.
Start Year 2015
 
Description Partnership with Peterborough City Council 
Organisation Peterborough City Council
Country United Kingdom 
Sector Public 
PI Contribution We provide technical support to the city council on development of clean tech sector including staff training, research and technology development
Collaborator Contribution The city council provided sponsorship for an academic post and also facilities for a clean energy centre.
Impact We support Peterborough's bid for the UK future city and Peterborough was awarded £3m from TSB.
Start Year 2013
 
Description AIChE Annual Meeting San Francisco 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact We host a Reception to promote our research in this largest chemical engineering conference.
Year(s) Of Engagement Activity 2016
 
Description International Conference on New Horizons in Biotechnology 2015, Trivandrum, November 22-25, 2015, India 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Give presentation on "CFD Modelling of Biomass Fast Pyrolysis in fluidized bed reactors with focusing different kinetic schemes"
Year(s) Of Engagement Activity 2015
 
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 Participate 4th International conference on thermochemical conversion of biomass, TCBiomass2015 , Chicago, November 2-5, 2015, USA 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact Give presentation "CFD simulation of catalytic upgrading of pyrolysis vapour in FCC riser" to audience over 200
Year(s) Of Engagement Activity 2015
URL http://eventegg.com/tcbiomass-2015/
 
Description Participate International Symposium on Analytical and Applied Pyrolysis-PYRO 2014 Birmingham, May 19-23, UK 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Industry/Business
Results and Impact Give presentation "CFD Modelling of an Ebullated bed reactor for the upgradation of Bio-oil derived from Lignocellulose Biomass" in this large conference with over 300 participants.
Year(s) Of Engagement Activity 2014
URL http://10times.com/pyro
 
Description Participate SUPERGEN Bioenergy Hub Annual Assembly, Rothamsted Research, 19th November 2015 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Industry/Business
Results and Impact Poster presentation on particle size effects of Fe3O4 in catalytic ketonisation of acetic acid
Year(s) Of Engagement Activity 2015
 
Description Participate SUPERGEN Bioenergy Hub Researchers Day, University of Bath, 2015 
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 Oral and Poster presentation on Development of fast pyrolysis based on bioenergy technologies, SUPERGEN Bioenergy Hub Researchers Day, 21st May, University of Bath
Year(s) Of Engagement Activity 2015
 
Description Participate VN-UK Bioenergy Meeting, Da Nang, Vietnam, 6th - 7th July 2015 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral Presentation on UK Bioenergy Research and Designer Catalysts for Biodiesel Synthesis
Year(s) Of Engagement Activity 2015
 
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 Poster presentation at Thermochemical lignocellulose conversion technologies (CASCATBEL workshop) 18-20 May 2016 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Poster presentation at workshop on Thermochemical lignocellulose conversion technologies - 18-20 May 2016 which was attended by a wide range of academics and industrialists with interest in biomass conversion technologies.

Title of presentation: Influence of alkyl chain length on sulfated zirconia catalysed batch & continuous esterification of carboxylic acids by light alcohols.

Poster led to discussions with potetial EU collaborators
Year(s) Of Engagement Activity 2016
 
Description Presentation "Catalysts from Waste: Red Mud as a Heterogeneous Catalyst for Bio-oil Upgrading" at UK Catalysis Conference Loughborough University, 8th - 9th January 2015 
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 Over 100 researchers from academia and industry attended the conference.
Year(s) Of Engagement Activity 2015
 
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 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