Designer Catalysts for High Efficiency Biodiesel Production

Lead Research Organisation: CARDIFF UNIVERSITY
Department Name: Chemistry

Abstract

Tackling the current world energy crisis is recognised as a top priority for both developed and developing nations. Alternative energy sources are therefore urgently sought in response to both diminishing world oil reserves and increasing environmental concerns over global climate change. To be truly viable such alternative energy sources must be sustainable, that is have the ability to meet 21st century energy needs without compromising those of future generations. While a number of sustainable technologies are currently receiving heavy investment, the most easily implemented and low cost solutions for transportation needs are those based upon biomass derived fuels. Spearheading such renewable fuels is biodiesel - a biodegradable, non toxic fuel synthesised from animal fats or plant oils extracted from cereal or non-food crops. We recently developed a range of first-generation solid acid and base catalysts that respectively remove undesired free fatty acid (FFA) impurities, and transform naturally occurring triglycerides found within plant oils into clean biodiesel. Here we propose to achieve a step-change in both catalyst, and overall process efficiency, through a combination of new synthetic materials chemistry and reactor technologies, in combination with computer-aided catalyst and process design. Our goal is the delivery of second-generation mesostructured solid acids and bases, optimised for efficient diffusion and reaction of bulky triglycerides and FFAs, and an intensified process allowing tandem esterification and transesterification of plant oil. Together these new green chemical technologies offer vastly streamlined biodiesel production, with associated annual energy savings of 5.5 billion kWh and a reduction in CO2 emissions by 2.4 million tonnes per annum at current production rates.

Publications

10 25 50
 
Description This research led to the development of catalytic materials possessing hierarchical pore networks that significantly enhance the diffusion of bulky triglycerides found in plant oils thereby enhancing their activity in biodiesel synthesis
Exploitation Route The details of the materials synthesis and surface derivatisation are all published and freely available for others to follow. These materials are expected to find application in many catalytic reactions where diffusion limitation and access of active sites are problematic, e.g in pyrolysis oil upgrading, biomass conversion, immobilisation of biocatalysts.
Sectors Chemicals

Energy

 
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 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 Optimising the nanoporous architecture of solid acid and base catalysts for biodiesel synthesis 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Type Of Presentation paper presentation
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact Talk stimulated discussions in the role of catalyst development in biofuels synthesis


.

After my talks requests for copies of published manuscripts increased
Year(s) Of Engagement Activity 2013
URL http://abstracts.acs.org/chem/245nm/program/view.php?obj_id=178819&terms=
 
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 Poster 210 - Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production - 248th American Chemical Society meeting Sanfrancisco Fall 2014 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Type Of Presentation poster presentation
Geographic Reach International
Primary Audience Postgraduate students
Results and Impact 2 210 - Alkali- and nitrate-free synthesis of highly active Mg-Al hydrotalcite-coated alumina for FAME production

A novel alkali- and nitrate-free impregnation route and subsequent calcination and hydrothermal treatment have been used for Mg-Al hydrotalcite (HT) coatings on alumina.1 The resulting Mg-HT/Al2O3 catalysts significantly outperform conventional2 and macroporous3 bulk hydrotalcites prepared via co-precipitation in the transesterification of C4-C18triglycerides for fatty acid methyl ester (FAME) production, with rate enhancements increasing with alkyl chain length. This work overcomes the mass transport limitations in biodiesel synthesis from viscous oils in bulk microporous hydrotalcites. XRD of the hydrotalcite-coated materials reveals a common set of reflections at 11.6°, 23.4°, 35°, 39.6°, 47.1°, and 61.1° characteristic of Mg-Al hydrotalcites, in good agreement with those observed for a conventional co-precipitated analogue (ConvHT). Surface areas of Mg-HT/Al2O3 are comparable to the alumina support for low Mg loadings, decreasing >9 wt% Mg but still remaining twice those of the Conv-HT. These HTs coatings possess significantly lower base site densities than the co-precipitated Conv-HT, but exhibit Turnover Frequencies (TOFs) for the transesterification of short and long chain TAGs far exceeding those achievable over conventional hydrotalcites, offering new possibilities for heterogeneously catalysed biodiesel production. This rate enhancement is attributed to improved accessibility of bulky triglycerides to active surface base sites over the higher area alumina support compared to conventional hydrotalcites (wherein many active sites are confined within the micropores). We have developed a simple, low cost route to depositing crystalline hydrotalcite coatings over high area alumina from benign precursors that affords highly active, reusable solid base catalysts for FAME production under mild conditions3.

Division: CATL: Division of Catalysis Science and Technology
Date/Time: Tuesday, August 12, 2014 - 06:00 PM
Session Info: CATL Poster Session (06:00 PM - 08:00 PM)
Location: Moscone Center, North Bldg.
Room: Hall D


increased visibility of published work
Year(s) Of Engagement Activity 2014
 
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 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