CATALYTIC TRANSFORMATION OF BIO-DERIVED PLATFORM MOLECULES

Lead Research Organisation: University College London
Department Name: Chemical Engineering

Abstract

Humanity has enjoyed the benefits of the industrial revolution and has built a technologically sophisticated civilization based on oil. However, it is now waking up to the reality that the fossil fuels are not going to last forever. A paradigm shift, from reliance on fossil fuels to renewable resources, and a chemical industry transition to sustainable processes are needed to meet the challenges of resource depletion and climate disruption. Nature produces a vast amount of 170 billion metric tons of biomass per year by photosynthesis. Surprisingly, only a few percent is used by humans for food and non-food purposes. The size of this production is sufficient to supply virtually all of the raw materials now required for the chemical industry. Thus, biomass compounds are the most abundant renewable resources available, and they are currently viewed as a feedstock for the green chemistry of the future.

In direct analogy to a petroleum refinery, which produces fuels and chemicals from crude oil, a biorefinery is a facility that produces multiple products, including fuel, power, and bulk or fine chemicals, from biomass. Even though catalysis is regarded as a key enabling technology for biomass conversion, its deployment in biorefineries is still limited. More importantly, several of the catalysts used for biomass conversion are based on catalyst technology developed specifically for petroleum refining. Petroleum feedstocks are basically hydrophobic, in stark contrast to biomass hydrophilic, high oxygen content feedstocks. Hence, new catalytic processes are urgently needed with specifically tailored catalysts. This presents a unique opportunity which is yet to be exploited by the £12 Billion global catalyst market.

The complexity of the challenge cannot be met by single individuals, because innovation requires interdisciplinary research that integrates methods, skills and strengths of different disciplines. In line with this winning strategy, we intend to bring about sizable step change in catalytic process development methodology by building on the diverse expertise of the team members, which includes catalytic chemistry, synthetic organic chemistry, microreactor technology, systems engineering, in situ spectroscopy. This approach will ensure a level of understanding of biomass conversion processes that would enable the rapid evaluation of novel catalyst and catalytic processes. One unique feature of this research project is that we will develop rapid reaction profiling methodologies based on close interaction of experimental and theoretical investigations.

Planned Impact

Impact on economy.
The chemical, biorenewables and catalysis industry will be main beneficiaries from this work, by accessing novel technology and catalysts for biomass conversion processes. Such catalysts will be more robust and efficient. The proposed approach will ultimately help reduce time and cost associated with scaling up from laboratory to production, due to the information-rich experimentation that is proposed. This can result to shortening of the development time from laboratory to commercial production. All the above will give a significant competitive advantage to the above industries, assisting them to remain at the forefront of innovation worldwide. Biorefineries are still in their infancy, so cutting edge technology will play a key role in their development and give the edge to companies which are entering this potentially lucrative area. The research proposed can lead to technology which is applicable to other materials manufacturing companies ranging from absorbents to energy storage materials, thus benefiting in the longer term other manufacturing industries.

Impact on knowledge.
This work will assist research and development laboratories involved in catalysis research, both in industry and academia to better understand, predict and optimize catalytic processes. Catalysis is a complex phenomenon that, despite several experimental and theoretical developments, still has an element of an "art", so that no accurate theory can substitute empirical investigation. Micro-structured continuous flow reactors offer unequalled experimentation conditions to explore catalytic processes, since small scales facilitate excellent control of flow patterns, transport phenomena and kinetic pathways. Novel synthesis routes of high value molecules will be introduced to the armoury of organic/synthetic/catalytic chemists.

Impact on society.
The health and quality of life of the wider public will benefit through the provision of new, low carbon footprint, sustainable processes. The public is acutely aware of the challenges facing our environment, to the extent that many are prepared to pay a premium for products manufactured in environmentally friendlier fashion. Thus, more efficient, cleaner and cheaper process solutions, will benefit the society through the use of these technological advances for green and sustainable chemical manufacture. Finally, new technological capabilities will influence policy makers legislating the chemical and energy industries.

Impact on people.
The project will result in highly trained researchers with professional skills in a wide range of areas, including catalytic science and catalyst design, chemical reactor engineering, microreaction technology, flow processing. It will develop their ability to work independently and in a team, expose them to interdisciplinary research and facilitate acquiring transferable skills that will enhance their learning process and broaden their horizons. These will make them valuable assets to R&D departments of chemical companies. EPSRC requires to grow research capability and trained people in particular in Catalysis which is marked as a Grow area of the EPSRC portfolio. Thus employing 3 PDRAs will make a contribution in that respect.

To make our results available to beneficiaries we will:
- Disseminate them through publications in scientific and trade journals and presentations at international conferences. Communication will be enhanced by webinars though targeted websites.
- Involve chemical industry through the Cardiff Catalysis Institute and engage with UCL Business together with Cardiff RACD to evaluate the technology, foster knowledge transfer and explore potential exploitation routes.

Publications

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Al-Rifai N (2013) Microreaction technology aided catalytic process design in Current Opinion in Chemical Engineering

 
Description A multi-microchannel packed-bed reactor platform made by microfabrication techniques and mutliplexed with an inexpensive portable Raman spectrometer was developed and demonstrated for fast catalyst evaluation. The system requires a very small amount of catalyst and still provides useful information in terms of catalyst activity and deactivation Flow hydrodynamic studies revealed that there is a favourable gas-liquid flow regime in micropacked-bed reactors for maximizing the gas-liquid mass transfer for the catalytic oxidation of benzyl alcohol. Higher selectivity to benzaldehyde (~90%) can be achieved as compared to batch reactor (~70%) at same reaction conditions. This provides an appreciation of the best performance possible with the catalyst, which cannot be obtained using conventional batch laboratory reactors. Catalysts for bio-derived reactions were developed and their deactivation characteristics under continuous operation were studied. We also developed a model-based design of experiments approach (MBDoE), where experiments can be designed for both discriminating among competing models and for improving the estimation of kinetic parameters. This approach can lead to more information with fewer experiments. We further developed a reactor platform based on microchannel, microfabricated reactors, that utilizes very small amounts of catalyst for multistep catalytic processes, such as catalytic oxidation, gas liquid separation, coupling and catalytic hydrogenation all in continuous flow. The relative merits of these multistep transformations were compared with single, multi-functional catalysts utilized in batch reactors.
Exploitation Route The multi-microchannel packed-bed reactor platform can be applied for development for gas-liquid-solid multiphase reactions. The multistep reactor platforms developed can be used for cascade process development. The in situ Raman analysis platform can be utilized for studying catalyst deactivation kinetics. The model-based design of experiments methodology can be used to improve and accelerate catalyst kinetic studies. All these developments can be put to use by both academic and industrial researchers.
Sectors Chemicals,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

 
Description ECCE10, 'Liquid-solid mass transfer studies in micropacked bed reactor with gas-liquid flow' 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
Enhong Cao, Redza bin Hasanudin, Asterios Gavriilidis, "Liquid-solid Mass Transfer Studies in Micropacked-bed Reactor with Gas-liquid Flow", ECCE10, 10th European Conference of Chemical Engineering, Nice, France, 27 September - 1 October 2015.
Year(s) Of Engagement Activity 2015
URL http://www.ecce2015.eu/
 
Description 13th IMRET, "Hydrodynamic Effects on Au/Pd Catalysed Benzyl Alcohol Oxidation in a Micro-Packed Bed Reactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
N. Al-Rifai, E. Cao, G. Brett, G. Hutchings, A. Gavriilidis, "Hydrodynamic Effects on Au/Pd Catalysed Benzyl Alcohol Oxidation in a Micro-Packed Bed Reactor", 13th International Conference on Microreaction Technology, Budapest, Hungary, June 2014.
Year(s) Of Engagement Activity 2014
 
Description 2016 UKCC "Catalytic Benzyl Alcohol Oxidation in a Three Phase Micro-Packed Bed Reactor: Hydrodynamics, Mass Transfer and Deactivation" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Keynote presentation
N. Al-Rifai, G. Leivadarou, A. Venkatesh, E. Cao, S. Cattaneo, M. Sankar, G. J. Hutchings, A. Gavriilidis, "Catalytic Benzyl Alcohol Oxidation in a Three Phase Micro-Packed Bed Reactor: Hydrodynamics, Mass Transfer and Deactivation", Keynote Presentation, UK Catalysis Conference 2016, Loughborough, 6-8 January 2016.
Year(s) Of Engagement Activity 2016
 
Description 2016 UKCC "Multichannel Micropacked-Bed Reactor System Integrated with a Portable Raman Spectrometer for Catalyst Evaluation" 
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
Year(s) Of Engagement Activity 2016
 
Description 25th ESCAPE "Model-based design of experiments for the identification of kinetic models in microreactor platforms" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
F. Galvanin, E. Cao, N. Al-Rifai, A. Gavriilidis, V. Dua, "Model-based design of experiments for the identification of kinetic models in microreactor platforms", 25th European Symposium on Computer Aided Process Engineering, Copenhagen, Denmark, 31 May - 4 June 2015.
Year(s) Of Engagement Activity 2015
 
Description 26th ESCAPE 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Presentation
F. Galvanin, N. Al-Rifai, E. Cao, M. Sankar, G. Hutchings, A. Gavriilidis, V. Dua, "Merging Information from Batch and Continuous Flow Experiments for the Identification of Kinetic Models of Benzyl Alcohol Oxidation over Au-Pd Catalyst", 26th European Symposium on Computer Aided Process Engineering - ESCAPE 26, Portoro┼ż, Slovenia, 12-15 June 2016.
Year(s) Of Engagement Activity 2016
 
Description 2nd RSC/SCI Symposium "Catalytic Aerobic Oxidations of Alcohols in Continuous Flow Microreactors" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Poster presentation
E. Cao, N. Al-Rifai, G. Hutchings, A. Gavriilidis, "Catalytic Aerobic Oxidations of Alcohols in Continuous Flow Microreactors", 2nd RSC/SCI Symposium on Continuous Processing and Flow Chemistry, Novartis, Horsham, UK, September 2013.
Year(s) Of Engagement Activity 2013
 
Description AIChE 2016, "Heterogeneously Catalysed Benzyl Alcohol Oxidation in a Three-Phase Micro-Packed Bed Reactor: Influence of Hydrodynamics and Reactor Design on Reaction Performance and Catalyst Deactivation" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
N. Al-Rifai, G. Leivadarou, A. Venkatesh, E. Cao, S. Cattaneo, M. Sankar, G. J. Hutchings, A. Gavriilidis, "Heterogeneously Catalysed Benzyl Alcohol Oxidation in a Three-Phase Micro-Packed Bed Reactor: Influence of Hydrodynamics and Reactor Design on Reaction Performance and Catalyst Deactivation", AIChE Annual Meeting, San Francisco, November 2016.
Year(s) Of Engagement Activity 2016
 
Description Applied Catalysis and Reaction Engineering IChemE-RSC 2014 "Porous Silicon Supported Silver for Enhanced Catalytic Oxidation of Alcohols in Microstructured Reactors" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact A poster presentation
E. Cao, I. Zuburtikudis, N. Al-Rifai, A. Gavriilidis, "Porous Silicon Supported Silver for Enhanced Catalytic Oxidation of Alcohols in Microstructured Reactors", Applied Catalysis and Reaction Engineering IChemE-RSC Conference, Cambridge, September, 2014.
Year(s) Of Engagement Activity 2014
 
Description CAPE Forum 2015 "A model-based experimental design study for the development of kinetic models of methanol oxidation on silver catalyst". 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
F. Galvanin, N. Al-Rifai, E. Cao, A. Gavriilidis, V. Dua, "A model-based experimental design study for the development of kinetic models of methanol oxidation on silver catalyst", CAPE Forum 2015, Paderborn, Germany, April 2015.
Year(s) Of Engagement Activity 2015
 
Description CHEMREACTOR-22, "Catalytic Benzyl Alcohol Oxidation in a Three Phase Micro-Packed Bed Reactor: Hydrodynamics, Mass Transfer and Deactivation" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
N. Al-Rifai, G. Leivadarou, A. Venkatesh, E. Cao, S. Cattaneo, M. Sankar, G. J. Hutchings, A. Gavriilidis, "Catalytic Benzyl Alcohol Oxidation in a Three Phase Micro-Packed Bed Reactor: Hydrodynamics, Mass Transfer and Deactivation", XXII International Conference on Chemical Reactors, CHEMREACTOR-22, UCL, London, 19-23 September 2016.
Year(s) Of Engagement Activity 2016
URL http://conf.nsc.ru/CR_22/en
 
Description IMRET 14, ""Liquid-Solid Mass Transfer Studies during Gas-Liquid Flow Through a Micropacked-Bed Reactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Presentation
E. Cao, R. bin Hasanudin, C. Waldron, A. Gavriilidis, "Liquid-Solid Mass Transfer Studies during Gas-Liquid Flow Through a Micropacked-Bed Reactor", 14th International Conference on Microreaction Technology, Beijing, China, 11-14 September 2016.
This presentation got an award.
Year(s) Of Engagement Activity 2016
 
Description ISCRE23, "Heterogeneous Catalysis with Continuous Flow Microreactors: Hydrodynamic Effects on Benzyl Alcohol Oxidation" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
N. Al-Rifai, E. Cao1, G. Brett, G. J Hutchings, A. Gavriilidis, "Heterogeneous Catalysis with Continuous Flow Microreactors: Hydrodynamic Effects on Benzyl Alcohol Oxidation", ISCRE23, 23rd International Symposium in Chemical Reaction Engineering, Bangkok, Thailand, Sept 2014.
Year(s) Of Engagement Activity 2014
 
Description MNF2014, "A Hydrodynamic Study of Benzyl Alcohol Oxidation in a Micro-Packed Bed Reactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Oral presentation
N. Al-Rifai, M. Morad, G. Leivadarou, E. Cao, G. Brett, G.J. Hutchings, A. Gavriilidis, "A Hydrodynamic Study of Benzyl Alcohol Oxidation in a Micro-Packed Bed Reactor", MNF2014, 4th Micro and Nano Flows Conference, London, UK, September 2014.
Year(s) Of Engagement Activity 2014
 
Description Operando V, "Application of Raman Analysis in a Multichannel Micropacked-Bed Three Phase Reactor System for Catalyst Evaluation" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Poster presentation
E. Cao, S. Barrass, G. Brett, P. J. Miedziak, J. M. Douthwaite, P. F. McMillan, G. J. Hutchings, A. Gavriilidis, "Application of Raman Analysis in a Multichannel Micropacked-Bed Reactor System for Catalyst Evaluation and Reaction Optimization", 5th International Conference on Operando Spectroscopy Deauville, France, May 2015.
Year(s) Of Engagement Activity 2015
URL http://10times.com/operando-spectroscopy
 
Description UK ChemEng Day 2013 "Deactivation Studies of Supported Gold Palladium Nanoalloy Catalysts during the Selective Oxidation of Alcohols in a Micro-packed Bed Reactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Poster presentation
N. Al-Rifai, E. Cao, M. Morad, M. Sankar, P. Miedziak, D. Knight, G. Hutchings, A. Gavriilidis, "Deactivation Studies of Supported Gold Palladium Nanoalloy Catalysts during the Selective Oxidation of Alcohols in a Micro-packed Bed Reactor", UK ChemEng Day, London, March 2013
Year(s) Of Engagement Activity 2013
 
Description UKCC 2015 "A Model-Based Design of Experiments Approach for the Identification of Kinetic Models of Methanol Oxidation on Silver Catalyst" 
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
F. Galvanin, N. Al-Rifai, E. Cao, A. Gavriilidis, V. Dua, "A Model-Based Design of Experiments Approach for the Identification of Kinetic Models of Methanol Oxidation on Silver Catalyst", UK Catalysis Conference 2015, Loughborough, UK, January 2015.
Year(s) Of Engagement Activity 2015