Designer Catalysts for High Efficiency Biodiesel Production

Lead Research Organisation: University of Surrey
Department Name: Centre for Environmental Strategy

Abstract

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Description Driven by the need to develop a wide variety of products with low environmental impact, biorefineries need to emerge as highly integrated facilities. This becomes effective when overall mass and energy integration through a centralised utility system design is undertaken. An approach combining process integration, energy and greenhouse gas (GHG) emission analyses is developed for non-food waste based biorefinery design, primarily producing biodiesel using oil-based heterogeneously catalysed transesterification or green diesel using hydrotreatment. The global warming potential from GHG emissions of the net energy produced (i.e. after covering energy requirements by the biorefinery systems) was 29 g CO2-eq per MJ output energy production, before accounting credits from displacement of fossil-based energy by bioenergy exported from the biorefineries. Using a systematic integration approach for utilisation of whole biorefinery, it is shown that global warming potential and fossil primary energy use can be reduced significantly if the integrated process schemes combined with optimised whole life cycle economic and environmental costs are adopted in waste-based biorefineries. The work provides multi-scale simulation tools as well as systems optimisation tools.

Important systems tools and observations include:

1. Differential economic and environmental impact analyses from units to systems.
2. Analysis across the scale linking process to system variables and design objectives.
3. Biorefinery Computer Aided Process Engineering (CAPE) tool in Excel-VBA platform http://biorefinerydesign.webs.com.
4. Cradle-to-grave environmental impact costs and credit values of streams are estimated.
5. Equivalent economic indicators are the cost of production and value on processing.
6. A novel economic value and environmental impact (EVEI) analysis methodology emerged from the combination of the value analysis method for maximisation of economic potential with environmental footprinting for impact minimisation.
7. Tighter policy directives can be in place if EVEI tool is employed.
8. The proposed tool is effective to target for stricter climate change mitigation policy.
9. A biofuel facility must be supplied with in-process generation of utilities.
10. Integrated biofuel with on-site raw material production is more sustainable.
For the multi-scale simulation, the following project goals were achieved.
We produced a framework for kinetic reaction and diffusive transport modelling of the heterogeneously catalysed transesterification of triglycerides into fatty acid methyl esters (FAMEs). In particular, the work makes recommendations on multicomponent diffusion calculations such as the diffusion coefficients and molar fluxes from infinite dilution diffusion coefficients using the Wilke and Chang correlation, intrinsic reaction kinetic studies using the Eley-Rideal kinetic mechanism with methanol adsorption as the rate determining steps and multi-scale reaction-diffusion process simulation between catalytic porous and bulk reactor scales.
An entire book chapter in the First Advanced Authored Textbook of its kind (Biorefineries and Chemical Processes: Design, Integration and Sustainability Analysis) on the subject has been devoted. This textbook is designed to bridge a gap between engineering design and sustainability assessment, for advanced students and practicing process designers and engineers. Chapter 18: Heterogeneously Catalyzed Reaction Kinetics and Diffusion Modeling: Example of Biodiesel:
"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. The chapter presents material pertaining to various aspects of the multiscale modeling of heterogeneously catalyzed reaction systems. 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 simulation framework for implementation of a multiscale diffusion-reaction model has been provided."
Exploitation Route Enabling biorefinery process design tools for advanced researchers, practicing process designers and engineers and policy makers.
All you need to learn about Sustainable biorefinery design.
A very comprehensive textbook on the subject can be found here:
http://as.wiley.com/WileyCDA/WileyTitle/productCd-1119990866.html#instructor
EVEI analysis tool can be found here:
http://biorefinerydesign.webs.com/eveianalysistool.htm
Biorefinery Computer Aided Process Engineering (CAPE) tool in Excel-VBA platform http://biorefinerydesign.webs.com.
A framework for heterogeneous catalytic reactor multiscale diffusion-reaction simulation can be found here: http://onlinelibrary.wiley.com/doi/10.1002/9781118698129.ch18/summary
Sectors Chemicals

Energy

Environment

Manufacturing

including Industrial Biotechology
URL http://onlinelibrary.wiley.com/doi/10.1002/9781118698129.ch18/summary
 
Description Biorefining rather than bioenergy implementation
Geographic Reach Multiple continents/international 
Policy Influence Type Influenced training of practitioners or researchers
Impact The main impact is in the design practices for sustainable biorefinery development, that should be done by cradle to grave impact analysis, alongside appropriately adapted process integration tools for enabling total site utility system design (energy and raw material recovery), polygeneration rather than cogeneration and resource use minimisation, governed by the fundamental principles of thermodynamics and mass, momentum and energy transfer. Our work jointly with ENERGY J.H. S.A. de C.V. to develop Jatropha biorefinery systems for Mexico demonstrates the following. Driven by the need to develop a wide variety of products with low environmental impact, biorefineries need to emerge as highly integrated facilities. This becomes effective when overall mass and energy integration through a centralised utility system design is undertaken. An approach combining process integration, energy and greenhouse gas (GHG) emission analyses is shown in this paper for Jatropha biorefinery design, primarily producing biodiesel using oil-based heterogeneously catalysed transesterification or green diesel using hydrotreatment. These processes are coupled with gasification of husk to produce syngas. Syngas is converted into end products, heat, power and methanol in the biodiesel case or hydrogen in the green diesel case. Anaerobic digestion of Jatropha by-products such as fruit shell, cake and/or glycerol has been considered to produce biogas for power generation. Combustion of fruit shell and cake is considered to provide heat. Heat recovery within biodiesel or green diesel production and the design of the utility (heat and power) system are also shown. The biorefinery systems wherein cake supplies heat for oil extraction and seed drying while fruit shells and glycerol provide power generation via anaerobic digestion into biogas achieve energy efficiency of 53 % in the biodiesel system and 57 % in the green diesel system. These values are based on high heating values (HHV) of Jatropha feedstocks, HHV of the corresponding products and excess power generated. Results showed that both systems exhibit an energy yield per unit of land of 83 GJ per ha. The global warming potential from GHG emissions of the net energy produced (i.e. after covering energy requirements by the biorefinery systems) was 29 g CO2-eq per MJ, before accounting credits from displacement of fossil-based energy by bioenergy exported from the biorefineries. Using a systematic integration approach for utilisation of whole Jatropha fruit, it is shown that global warming potential and fossil primary energy use can be reduced significantly if the integrated process schemes combined with optimised cultivation and process parameters are adopted in Jatropha-based biorefineries. We worked with ENERGY to take actions together with the Government, governmental organizations, universities, research centres and other companies.
 
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 Public
Country United Kingdom
Start 08/2014 
End 06/2015
 
Description Researcher Links Workshop in Mexico on Biorefinery research - promoting international collaboration for innovative and sustainable solutions
Amount £47,200 (GBP)
Organisation British Council 
Sector Charity/Non Profit
Country United Kingdom
Start 11/2014 
End 05/2015
 
Title Data Uncertainty and Multicriteria Analyses 
Description Multi-criteria methods are shown incorporation of techno-economics and socio-economics in the analysis. Biorefinery sustainability must be assessed using life cycle assessment (LCA), techno-economics and socio-economics. Data uncertainty analysis, sensitivity analysis and Monte Carlo simulations are essential to minimise errors in estimation, to find more important indicators, activity and inventory hotspots. The tools are shown with numerous practical problems for LCA, techno-economic and socio-economic analysis. 
Type Of Material Data analysis technique 
Year Produced 2012 
Provided To Others? Yes  
Impact The 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 Cádiz, 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. 
URL http://www.wiley.com/buy/9781119990864
 
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
 
Description IAA project with Bio-Sep Ltd. 
Organisation Bio-Sep
Country United Kingdom 
Sector Private 
PI Contribution Professor Richard Murphy leading and I am Co-I. Dr Mairi Black is working as the Research Fellow in the IAA grant. Contributions: Developing knowledge data system for agri-forest residues and wastes, with appropriate technical and economic parameter information necessary for downstream biorefining modelling (e.g. hemicellulose composition, recalcitrance indicators, geographic distribution and concentration of residue materials, residue prices and seasonality, etc.). The development and structuring of this knowledge and data is highly relevant to both academic and industrial research on biorefining and for policy and decision-making.
Collaborator Contribution expertise in ultrasonication for biomass fractionation into added value production.
Impact A robust Knowledge data system of waste biomass alongside detailed technical and market information. Academic and Industry
Start Year 2014
 
Description Jatropha biodiesel biorefining 
Organisation Energy J.H. S.A. de C.V.
Country Mexico 
Sector Private 
PI Contribution Full biorefining conceptualisation, design, techno-economics and environmental LCA.
Collaborator Contribution Agricultural systems yields, models and details on spatial and temporal disparity.
Impact Academic and industrial.
Start Year 2012
 
Title Economic Value and Environmental Impact Analysis 
Description A graphical analysis tool first time combined economic value and environmental impact assessment based on targeting for maximisation of economic value and minimisation of environmental impact assessment. 
Type Of Technology New/Improved Technique/Technology 
Year Produced 2013 
Impact Used to develop sustainable Jatropha biorefinery design, configurations in Mexico and bioethanol facility with in-process combined heat and power generation in UK. 
URL http://biorefinerydesign.webs.com
 
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 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