Designer Catalysts for High Efficiency Biodiesel Production

Lead Research Organisation: University of Manchester
Department Name: Chem Eng and Analytical Science

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

Related Projects

Project Reference Relationship Related To Start End Award Value
EP/F063563/1 24/04/2009 01/07/2011 £87,008
EP/F063563/2 Transfer EP/F063563/1 23/01/2012 30/08/2013 £41,162
 
Description A comprehensive intrinsic kinetic and diffusion modelling framework to design transesterification reaction catalysts for biodiesel production has been established. The interlayer structure of the hydrotalcite and polystyrene beads with silica precursor, catalysts, enhanced diffusion and accessibility of species and hence the rates of triglyceride conversion and production of fatty acid methyl ester (biodiesel). Catalyst structural optimisation supported by simultaneous experimental investigation shows more than 98% molar conversion of triglycerides into high purity biodiesel production. Catalytic activity, surface area and porous sizes and structure were optimised by the predictive model to feed into the experimental design.
Exploitation Route 1. To optimise a biodiesel production process from waste cooking oil using heterogeneous catalyst
2. To optimise heterogeneous transesterification reaction system of triolein to produce biodiesel.
3. To scale-up pilot reactors into industrial system.
4. To determine kinetic parameters and estimate / optimise performance in an industrial scale reactor.
5. To develop heterogeneous model in order to estimate molecular diffusion, alongside reaction mechanisms.
6. To develop a solid base catalyst with improved activity for the transesterification of pure triacylglycerides and olive oil.
7. To convert a series of platform molecules such as levulinic acid, furans, fatty acids and polyols into a variety of fuel additives through catalytic transformations that include reduction, esterification, etherification, and acetalization reactions.
8. To obtain liquid hydrocarbon fuels by combining oxygen removal processes (e.g. dehydration, hydrogenolysis, hydrogenation, decarbonylation/descarboxylation etc.) with the adjustment of the molecular weight via C-C coupling reactions (e.g. aldol condensation, hydroxyalkylation, oligomerization, ketonization) of the reactive platform molecules
Sectors Chemicals,Energy,Environment,Manufacturing, including Industrial Biotechology,Transport

URL http://eu.wiley.com/WileyCDA/WileyTitle/productCd-1119990866.html
 
Description Research in biodiesel is currently focusing on more efficient ways of production, with the most promising avenue of research looking at the use of heterogeneous catalysis. When non-porous solid catalyst is used at a laboratory scale, the diffusion stages of the reaction can be neglected, leaving a simplified mechanism comprising the reaction and adsorption/desorption stages. Experimental investigations on concentration profiles with time thus allow developing insights into intrinsic kinetic (or site) mechanism of reactions. However, without the consideration of concentration gradient due to diffusive transport limitation, the interaction probabilities for all given active sites are identical. This is not true when nano-porous catalysts are used to help with the inter-particle transport for scaled up reactors. For scaling up processes, nano-porous solid catalysts such as hydrotalcite with layered double hydroxides and polystyrene beads with silica precursor have been investigated to provide high specific surface area, more access to active sites for reaction to occur and to reduce the amount of catalyst needed in a given volume. This porous nature however also makes the reaction process from nano-materials to process scale, more difficult to design, as diffusion through catalytic pores creates another step in the reaction sequence that must be accounted for in multi-scale design and simulation. This research demonstrates the effectiveness of the proposed multi-scale design framework combining experimental and computational approaches. The transesterification reactions with hydrotalcite catalysts; palmitic acid and methanol with polystyrene beads with silica precursor were optimised for high purity production. The main impact lies in predictive computer modelling to enable chemists, chemical engineers and catalyst designers to design hierarchical porous solid catalysts and multi-functional reactors for more efficient high purity production of desired product. A comprehensive intrinsic kinetic and diffusion modelling framework to design transesterification reaction catalysts for biodiesel production has been established. The interlayer structure of the hydrotalcite and polystyrene beads with silica precursor, catalysts, enhanced diffusion and accessibility of species and hence the rates of triglyceride conversion and production of fatty acid methyl ester (biodiesel). Catalyst structural optimisation supported by simultaneous experimental investigation shows more than 98% molar conversion of triglycerides into high purity biodiesel production. Catalytic activity, surface area and porous sizes and structure were optimised by the predictive model to feed into the experimental design. Beneficiaries: Catalyst designers in Cardiff. Contribution Method: The researcher on the grant spent time at Cardiff lab, to help with catalyst design and laboratory experimentation. At later stage, a number of joint collaborative publications with Profs Karen Wilson and Adam Lee are coming up. In addition to what has already been inputted in the publication, we are jointly presenting our collaborative work in Catalysis and Chemical Engineering Conference by IChemE on 4 June, 2013. The title is: Heterogeneously Catalysed Transesterification Reaction Kinetics and Diffusion Analyses for Optimal Synthesis, by Jhuma Sadhukhana, Adam F. Lee and Karen Wilson. The following combinations of hydrotalcites catalyst design parameters determined from predictive modelling gave rise to a triglyceride molar conversion >98% and almost pure biodiesel production on separation. 1. activity = 30 mmoles per gm; surface area = 500 m2 per gm; pore size (diameter) > 20 nanometer. 2. activity = 10 mmoles per gm; surface area = 160 m2 per gm; pore size > 15 nanometer. 3. activity = 6.8 mmoles per gm; surface area = 100 m2 per gm; pore size > 10 nanometer. 4. activity = 4.4 mmoles per gm; surface area = 50 cm2 per gm; pore size > 5 nanometer. Further, model validation is in progress with polystyrene beads catalysts. Further, journal papers (Chem Eng J.) will be submitted soon.
Sector Manufacturing/ including Industrial Biotechology
Impact Types Cultural

 
Description IAA: Bioresource knowledge & data system targeted for downstream conversions (Bio-TARG)
Amount £62,416 (GBP)
Funding ID Bioresource knowledge & data system targeted for downstream conversions (Bio-TARG) 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Academic/University
Country United Kingdom
Start 09/2014 
End 06/2015
 
Title Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling: Example of Biodiesel 
Description Biodiesel is fast becoming one of the key transport fuels as the world endeavors to reduce its carbon footprint and find viable alternatives to oil-derived fuels. Material pertaining to various aspects of the multiscale modeling of heterogeneously catalyzed reaction systems have been presented. Modeling of the intrinsic kinetics has been shown for Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Hattori mechanisms with assumptions of rate limiting steps. The UNIQUAC model for activity and concentration correlations for a non-ideal reaction system has been shown with calculations for transesterification reactions between triglyceride and methanol for fatty acid methyl ester (FAME) production. Analytical integration by Taylor's series first-order expansion has been done to estimate concentration versus time profiles of species. A simulation framework for implementation of a multiscale diffusion-reaction model has been provided. 
Type Of Material Computer model/algorithm 
Year Produced 2012 
Provided To Others? Yes  
Impact Computer models help to 1. Design hierarchical porous network of the catalyst to selectively aid diffusion of various sized molecules and surface adsorption; 2. Understand fundamental intrinsic kinetic and diffusion mechanism; 3. Control kinetic and diffusion mechanism by optimal hierarchical catalytic porous network design; 4. Control productivity and purity by controlling kinetic and diffusion mechanism; 5. Design optimal reactor configurations. 
URL http://onlinelibrary.wiley.com/doi/10.1002/9781118698129.ch18/summary
 
Title Life Cycle Assessment 
Description Computer models are generated for life cycle assessment (LCA) of biorefinery systems for analyzing interactions between engineering systems and the environment through assessments of resource depletion and pollutant emissions. The goal and scope definition involved in identification of LCA: i. Functional unit; ii. System definition; iii. System boundaries. The inventory analysis included the following steps, detailed definition of the system, data collection, allocation and quantification of the environmental burdens. The impact assessment were carried out using the following steps: i. Classification; ii. Characterization; iii. Normalization; iv. Valuation. Interpretation of an LCA study included identification of major burdens, impacts, hot spots; identification of areas with a scope for improvement; sensitivity analysis; robustness of results; evaluation and recommendations. A number of LCIA methods were included to predict impact under various categories. The LCIA methods also included combinations of primary as well as mid- or end-point impacts. 
Type Of Material Computer model/algorithm 
Year Produced 2010 
Provided To Others? Yes  
Impact The LCA tools developed are taught as part of the LCA course in Surrey, attended by regular Masters students and EngDs. As a result, the tools have been adopted by dedicated teams in organisations, National Physical Laboratory, Nestle, TWI Ltd., Recycling Technologies, Universidad de C?diz, Universities of Birmingham and Reading and by various EU funded consortia. The tools help to demonstrate emission cuts achievable by appropriate technologies to policy makers, and graphically explain other multi-criteria benefits. In addition, there are various outputs from the work done: 1. Sadhukhan J., Ng K.S., Martinez-Hernandez E. 2014. 'Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis.' Wiley. . (625 pages paperback + Web based problem solutions, 3 additional Chapters and 4 Life Cycle Assessment case studies). ISBN-10: 1119990866 | ISBN-13: 978-1119990864. This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers. 1. Sadhukhan J., Ng K.S. and Martinez-Hernandez, E. 2015. Process Systems Engineering Tools for Biomass Polygeneration Systems with Carbon Capture and Reuse. A Chapter in the Edited Book: Process Design Strategies for Biomass Conversion Systems, in press, John Wiley & Sons, Inc. 2. Sadhukhan, J. 2013. 'Life Cycle Assessment of Biorefinery' Book chapter in Future Design of Biorefineris. Springer. In Press. 3. Hosseini, S.A. Patel, M. Sadhukhan, J. Cecelja, F. and Shah, N. 2013. Multi-scale process and supply chain modelling of Biorefinery: from feedstock to process and products' Book chapter in Future Design of Biorefineris. Springer. In Press. Refereed Journal Articles published (my role as the main Supervisor when last authored) 1. J Sadhukhan. 2014. Distributed and micro-generation from biogas and agricultural application of sewage sludge: Comparative environmental performance analysis using life cycle approaches. Applied Energy. 122, 196-206. 2. Martinez-Hernandez, E., Campbell, G. M., & Sadhukhan, J. 2014. Economic and environmental impact marginal analysis of biorefinery products for policy targets. Journal of Cleaner Production, 74, 74-85. 3. Martinez-Hernandez, E., Martinez-Herrera, J., Campbell, G. M., & Sadhukhan, J. (2014). Process integration, energy and GHG emission analyses of Jatropha-based biorefinery systems. Biomass Conversion and Biorefinery, 4(2), 105-124. 4. E Martinez-Hernandez, GM Campbell, J Sadhukhan. 2013. Economic Value and Environmental Impact (EVEI) analysis of biorefinery systems. Chemical Engineering Research Design. 8(91), 1418-1426. 5. E Martinez-Hernandez, MH Ibrahim, M Leach, P Sinclair, GM Campbell, J Sadhukhan. 2013. Environmental sustainability analysis of UK whole-wheat bioethanol and CHP systems. Biomass and Bioenergy, 50, 52-64. 
URL http://onlinelibrary.wiley.com/doi/10.1002/9781118698129.ch4/summary
 
Description Aston and Newcastle 
Organisation Aston University
Country United Kingdom 
Sector Academic/University 
PI Contribution Understanding of fundamental kinetic mechanism of transesetrification reactions and the effect of catalyst structure and hierarchical pore sizes on the kinetic mechanism and thereby influence on kinetic and diffusion model to design optimal reactors
Collaborator Contribution Experimental data for validation and observations from experiments.
Impact Advanced Engineering Text Book 1. Sadhukhan J., Ng K.S., Martinez-Hernandez E. 2014. 'Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis.' Wiley. . (625 pages paperback + Another ~400 pages of Web based problem solutions, 3 additional Chapters and 4 Life Cycle Assessment case studies). ISBN-10: 1119990866 | ISBN-13: 978-1119990864. This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers. Refereed Journal Articles published (my role as the main Supervisor when last authored) 1. TJ Davison, C Okoli, K Wilson, AF Lee, A Harvey, J Woodford, J Sadhukhan. 2013. Multiscale modelling of heterogeneously catalysed transesterification reaction process: an overview. RSC Advances, 3, 6226-6240. 2. Kapil A., Lee A.F., Wilson K. and Sadhukhan J. 2011. Kinetic modelling studies of heterogeneously catalyzed biodiesel synthesis reactions. Industrial & Engineering Chemistry Research, Special Issue, 50(9), 4818-4830.
Start Year 2008
 
Description Aston and Newcastle 
Organisation Newcastle University
Country United Kingdom 
Sector Academic/University 
PI Contribution Understanding of fundamental kinetic mechanism of transesetrification reactions and the effect of catalyst structure and hierarchical pore sizes on the kinetic mechanism and thereby influence on kinetic and diffusion model to design optimal reactors
Collaborator Contribution Experimental data for validation and observations from experiments.
Impact Advanced Engineering Text Book 1. Sadhukhan J., Ng K.S., Martinez-Hernandez E. 2014. 'Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis.' Wiley. . (625 pages paperback + Another ~400 pages of Web based problem solutions, 3 additional Chapters and 4 Life Cycle Assessment case studies). ISBN-10: 1119990866 | ISBN-13: 978-1119990864. This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers. Refereed Journal Articles published (my role as the main Supervisor when last authored) 1. TJ Davison, C Okoli, K Wilson, AF Lee, A Harvey, J Woodford, J Sadhukhan. 2013. Multiscale modelling of heterogeneously catalysed transesterification reaction process: an overview. RSC Advances, 3, 6226-6240. 2. Kapil A., Lee A.F., Wilson K. and Sadhukhan J. 2011. Kinetic modelling studies of heterogeneously catalyzed biodiesel synthesis reactions. Industrial & Engineering Chemistry Research, Special Issue, 50(9), 4818-4830.
Start Year 2008
 
Title Multi-scale kinetic diffusion model 
Description Modeling of the intrinsic kinetics has been shown for Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW) and Hattori mechanisms with assumptions of rate limiting steps. The UNIQUAC model for activity and concentration correlations for a non-ideal reaction system has been shown with calculations for transesterification reactions between triglyceride and methanol for fatty acid methyl ester (FAME) production. Analytical integration by Taylor's series first-order expansion can be done to estimate concentration versus time profiles of species. A unified simulation framework for implementation of a multiscale diffusion-reaction model has been provided. 
Type Of Technology New/Improved Technique/Technology 
Year Produced 2013 
Impact A spreadsheet-VBA based software for kinetic and diffusion modelling of heterogeneously catalysed transesterification reaction systems. 
URL http://onlinelibrary.wiley.com/doi/10.1002/9781118698129.ch18/summary
 
Description Invited speaker in Workshop on EPSRC Polygeneration Platform Grant in University of Surrey 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact My talk was on Techno-economic analysis of biofuel systems. This showed economic parameters and findings to industrial participants (e.g. Vireol). I showed them how the whole-wheat integrated system, wherein the combined heat and power from the excess straw grown in the same season and from the same land utilised in the wheat bioethanol plant, can be demonstrated for potential sustainability improvement, achieving 85% emission reduction and 97% fossil resource saving. The economics also looked attractive. Vireol representative took the numbers for applying to their industrial site and said "If it were in China or even USA, they could have proceeded with these findings. But here validation after validation has to be done before anything could start of the ground."

Vireol representative noted all the calculations of environmental sustainability and economic analysis and got my presentation for applying to their bioethanol plant.
Year(s) Of Engagement Activity 2010
 
Description Invited speech in 2. ACI's 4th Annual Lignofuels Summit, London, UK on 25-26 September 2013. "Wood biorefineries: Design, integration and sustainability analysis". 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Collaborative proposals for Horizon 2020 with VITO (VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK N.V.)

Working with VITO on a number of project proposals and research visits.
Year(s) Of Engagement Activity 2013
URL http://www.wplgroup.com/aci/conferences/eu-eef4.asp
 
Description Invited speech in Second Indo-Norwegian Conference, Indian Institute of Petroleum (IIP), Dehradun, India 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact My talk was on Process Integration tools for biorefinery systems. They sparked loads of questions and discussions afterwards. I and IIP exchanged loads of papers afterwards and we have a strong working relationship.

The Director of IIP, Dr MO Garg, visited my research lab afterwards.
Year(s) Of Engagement Activity 2010