Catalytic Routes to Intermediates for Sustainable Processes

Lead Research Organisation: Imperial College London
Department Name: Department of Chemical Engineering

Abstract

Oil is the most important source of energy worldwide, accounting for 35% of primary energy consumption and the majority of chemical feedstocks. The quest for sustainable resources to meet demands of a constantly rising global population is one of the main challenges for mankind this century. To be truly viable such alternative feedstocks must be sustainable, that is "have the ability to meet 21st century energy needs without compromising those of future generations." Development of efficient routes to large-scale chemical intermediates and commodity chemicals from renewable feedstocks is essential to have a major impact on the economic and environmental sustainability of the chemical industry. While fine chemical and pharmaceutical processes have a diverse chemistry and a need to find green alternatives, the large scale production of petrochemical derived intermediates is surely a priority issue if improved overall sustainability in chemicals manufacture is to be achieved. For example, nylon accounts for 8.9% of all manmade fibre production globally and is currently sourced exclusively from petrochemicals. It is one of the largest scale chemical processes employed by the chemicals sector. Achieving a sustainable chemicals industry in the near future requires 'drop in' chemicals for direct replacement of crude oil feedstocks. The production of next-generation advanced materials from the sustainably-sourced intermediates is a second key challenge to be tackled if our reliance on petrochemicals is to end

The project will develop new heterogeneously catalysed processes to convert cellulose derivatives to high value platform and commodity chemicals. We specifically target sustainable production of intermediates for manufacture of polyamides and acrylates, thereby displacing petroleum feedstocks. Achieving the aims of the project requires novel multifunctional catalyst technology which optimises the acid-base properties, hydrogen transfer and deoxygenation capability. Using insights into catalyst design gleaned from our previous work, a directed high-throughput (HT) catalyst synthesis and discovery programme will seek multifunctional catalyst formulations for key biomass transformations. Target formulations will be scaled up and dispersed onto porous architectures for study in lab-scale industrial-style reactors. We will also seek to exploit multi-phase processes to improve selectivity and yield. This will be combined with multi-scale systems analysis to help prioritise promising pathways, work closely with industry to benchmark novel processes against established ones, develop performance measures (e.g. life cycle analysis (LCA)) to set targets for catalytic processes and explore optimal integration strategies with existing industrial value chains. Trade-offs between optimising single product selectivity versus allowing multiple reaction schemes and using effective separation technology in a "multiproduct" process will be explored. The potential utilization of by-products as fuels, sources of hydrogen, or as chemical feeds, will be evaluated by utilizing data from parallel programmes.

Planned Impact

The UK petrochemicals industry has been in decline for many years as access to cheap North Sea hydrocarbons has ceased. The UK has become heavily dependent on imported feedstocks and materials. New biomass based processes can facilitate a resurgence in the chemicals industry, improve security of supply, reduce the carbon footprint and hence the UKs contribution to global CO2 emissions, and open new and broader opportunities for the UK agricultural sector to supply a range of novel feedstocks. The sustainable chemical feedstocks programme also paves the way to waste valorisation, and is also in tune with the development of a knowledge based economy linked to manufacturing. The UK has world-leading contracting and catalyst industries, and technical consultancies which play an important role in maintaining the UK's international reputation for technology. These depend on access to cutting edge academic research and trained personnel such as provided by the proposed research. The Companies involved with project provide a direct outlet for the knowledge and technologies across the range of beneficiary sectors.

IP emerging from the project will be identified and protected by the relevant University organisations, with clear agreement and documentation of inventive steps allowing ready identification of IP ownership. IC, CU and UoL all have extensive experience in IP protection in multi-organisation research programmes of this type e.g. under the N4CF programme both Cardiff and Liverpool patented separate inventions with the industrial partner under the IP arrangements we envisage in this programme, which will be reflected in the Consortium Agreement to be drawn up by the Universities before project start.

To maximise the impact and benefit that can accrue from the research, we intend to disseminate the results as widely as possible to academic and industrial beneficiaries. We will: publish in high impact scientific journals over the full range of disciplines contributing to the project; present at international conferences associated with process systems, chemical engineering, catalysis and biomass conversion to chemicals and fuels; enhance the impact of the work by dissemination of results online by webinars and creating a website to advertise the technology; hold regular science exchange days with other consortia in the "Sustainable Feedstocks" programme; develop a demonstration for school visits and university open days to highlight the potential impact of science and engineering in the area of sustainable technology; organize a showcase workshop towards the end of the project, in which we will invite academics and industrial researchers by advertising in knowledge transfer and professional networks; propose a Royal Society Discussion Meeting and a Faraday Discussion on sustainable chemical processes.

The project will produce high quality researchers (RAs and associated PhD students) with a multidisciplinary perspective. This will make them highly valued in a range of economic spheres. In addition to the chemicals sector and catalyst industries, the UK has world-leading contracting and technical consultancies which depend on access to leading academic research and trained personnel with a whole system perspective such as provided by the proposed research.

Publications

10 25 50
 
Description The aim is to develop a sustainable route to nylon. This strategy is to convert glucose to the key intermediates for manufacture of nylon. Two catalytic routes have been explored: glucose to adipic acid by oxidation of glucose to glucaric acid and its selective hydrogenation to remove oxygen, and glucose to caprolactone via fructose and 5-HMF.
Catalysts for the oxidation of glucose to glucaric acid have shown good performance in comparison to recent patent claims. The kinetics of this reaction and the significance of leaching of catalytic metal have also been investigated. A methodology based on quantitative 2-d NMR has been developed to identify the products at all stages of the oxidation process. An important new finding is the quantification of the various lactones at all stages of the conversion, since conventional analytical approaches such as HPLC cannot differentiate these intermediates.
The understanding of the role of lactones has led to the development of a new process for production of pure, crystalline glucaric acid. This uses azeotropic distillation to remove water at temperatures too low for lactone formation. Crystalline glucaric acid is not currently available commercially and this new process opens potential application of glucaric acid in healthcare products and in pharmaceutical manufacture, in addition to a possible application as an intermediate for adipic acid manufacture. A techno-economic evaluation of conversion of biomass (corn stover) to crystalline glucaric acid has been completed and demonstrates the feasibility of such a process and its beneficial environmental impact based on CO2 emission reduction.
New zeolite-based catalysts have been developed for the efficient isomerisation of glucose to fructose, a key step in the route to 5-HMF an important bio-platform molecule. It has been shown that mild desilication of the zeolite is advantageous. Hydrogenation of 5-HMF has been explored in both batch and continuous processes using several types of new catalysts. Furfural and other related oxygenated compounds have been studied in order to understand the hydrogenation reaction pathway more fully. These studies have identified a number of promising catalysts for application in the selective hydrogenation of 5-HMF in a multistep process. In passing, a promising selective route to valuable cyclopentanone derivatives has been found.
A techno-economic evaluation and life cycle analysis of conversion of biomass (corn stover which is non-competitive with food) to caprolactone via fructose and 5-HMF has been completed. Caprolactone is a precursor for production of caprolactam.This early stage assessment demonstrates the potential of such a process to reduce environmental impact based on CO2 emission reduction and water consumption.
A techno-economic evaluation and life cycle analysis of conversion of biomass (corn stover) to high purity, crystalline glucaric acid via catalytic oxidation of glucose has been completed. Glucaric acid is a potential precursor for production of adipic acid. This early stage assessment demonstrates the potential of such a process to reduce environmental impact based on CO2 emission reduction and water consumption.
Exploitation Route The new process to produce crystalline glucaric acid has potentially wider application than the development of sustainable routes to nylon. Cardiff Catalyst Institute plan discussions with interested parties. A techno-economic and environmental impact assessment of this process has been published and will ensure a wide audience for this work.
Sectors Agriculture, Food and Drink,Chemicals,Energy,Environment,Healthcare,Pharmaceuticals and Medical Biotechnology

 
Description The societal impact have been addressed through the outreach activities of Cardiff Catalyst Institute and Imperial College Centre for Process Systems Engineering.
First Year Of Impact 2017
Sector Chemicals
Impact Types Societal

 
Title Data pertaining to quantitative determination of Pt- catalysed D-glucose oxidation products using 2D NMR 
Description This data set contains 1D and 2D NMR standard spectra for (i) equilibrium solutions of D-glucose in D2O and (ii) those C6 products identified in the published article - including equilibrated solutions of D-guluronic acid/ D-glucaric acid and their cyclic derivatives. All spectra were collected in D2O under standard conditions (298 K, 1 atm). Also included are the spectra pertaining to a high conversion D-glucose oxidation reaction (Table 2, Entry 17 of published article). 
Type Of Material Database/Collection of data 
Year Produced 2018 
Provided To Others? Yes  
 
Description Cardiff University 
Organisation Cardiff University
Country United Kingdom 
Sector Academic/University 
PI Contribution A techno-economic assessment of glucaric acid production has been completed. A joint publication is in preparation.
Collaborator Contribution Cardiff University have provided details of their process for purification of glucaric acid
Impact A joint publication is in preparation
Start Year 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 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 by Motaz Kawaji at TOCAT8: Effect of support morphology and catalyst preparation on the selective oxidation activity of 
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 by Motaz Khawaji at TOCAT8. An audience in excess of 100 attended the presentation. Several questions were asked concerning the oxidation of glucose. A more detailed study of glucose oxidation was undertaken as a result.
Year(s) Of Engagement Activity 2018
 
Description Oral presentation at 5th International Congress on Catalysis for Biorefineries by Prof D. Chadwick on glucose isomerisation 
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 at 5th International Congress on Catalysis for Biorefineries by Prof D. Chadwick on "glucose isomerisation over Mg-promoted Na-exchanged zeolites in water and alcohol solutions". A summary of the findings of our techno-economic study was also included in the talk. There was strong interest from the audience and the organisers. An invitation to contribute to the special issue publication has been received.
Year(s) Of Engagement Activity 2019
 
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 Oral presentation by Ines Graca at XXVI Ibero-ammerican Congress on Catalysis: Isomerisation of glucose to fructose using Na zeolites impregnated with Mg 
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 by Dr Ines Graca. Talk attended by more than 100 participants
Year(s) Of Engagement Activity 2018
 
Description Oral presentation by Motaz Khawaji at 258th ACS symposium: Catalytic conversion of bioderived oxygenates 
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 by Motaz Khawaji on selective oxidation of glucose using Au-Pd nanoparticles at 258th ACS symposium: Catalytic conversion of bioderived oxygenates. There was strong interest in the work and Motaz Khawaji received a follow up invitation to contribute an article to special issue.
Year(s) Of Engagement Activity 2019
 
Description Oral presentation by Motaz Khawaji at ACS Spring meeting on Catalysis, 2017, Highly active Au-Pd nanoparticles supported on titanate nanotubes 
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 in session on catalysts preparation by non-traditional methods. Impact is wider interest in the research and in research groups at Imperial College London
Year(s) Of Engagement Activity 2017
 
Description Oral presentation by Motaz Khawaji at EUROPACAT 2017, Selective oxidation of benzyl alcohol using Au-Pd/titanate nanotubes prepared by sol-immobilisation 
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. impact is wider dissemination of the research and more generally on the research on sustainable feedstocks; interest in the work of research groups at Imperial College.
Year(s) Of Engagement Activity 2017
 
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 XIII European Congress on Catalysis Dr Ruben Ramos 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Poster presetation titled "Selective conversion of 5-hydroxymethylfurfural to cyclopentanone derivatives over Cu-Al2O3 and Co-Al2O3 catalysts in water" to disemminate results and stimulate academic discussion,
Year(s) Of Engagement Activity 2017
 
Description Poster presentation by Ines Graca at EUROPACAT 2017, Magnesium-promoted Na-zeolites as catalysts for the glucose isomerisation into fructose 
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. Impact is wider dissemination of the work and more generally on the research on sustainable feedstocks, and interest in the research groups at Imperial College London.
Year(s) Of Engagement Activity 2017
 
Description Poster presentation by Ines Graca at NAM25, USA, Glucose isomerisation into fructose over magnesium-promoted NaY zeolite catalysts 
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. Impact is wider dissemination of the research work and more generally on the research on sustainable feedstocks, and interest of capability of research groups at Imperial College London
Year(s) Of Engagement Activity 2017
 
Description Poster presentation by Vaishali Thaore at International Bioenergy Conference, Manchester, UK, 2017, The techno-economic analysis for renewable production of Caprolactam 
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. Outcome is wider dissemination of the research and more generally on the research on sustainable feedstocks, and interest in work of research groups at Imperial College London.
Year(s) Of Engagement Activity 2017
 
Description RSC/SCI Flow Chemistry III - Cambridge - 14-16th March 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact RSC/SCI Flow Chemistry III - Cambridge - 14-16th March 2016

Poster and Flash presentation - "Effect of reaction conditions and reactor type on biomass valorisation reactions - Selectivity control in Pt catalysed Cinnamaldehyde hydrogenation"

Poster presentation and Flash presentation Dr Lee Durndell
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 Talk at XII European Congress on Catalysis- Noemie Perret: Selectivity in the liquid-phase hydrogenation of 5-hydroxymethyl furfural over Ni-Al catalysts 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Dissemination and discussion of results
Year(s) Of Engagement Activity 2015
 
Description The Gold Rush : Summer Science Exhibition Royal Soc 2014 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Schools
Results and Impact Research on gold catalysis was exhibited
Year(s) Of Engagement Activity 2014
URL http://sse.royalsociety.org/2014
 
Description The Inaugural UK Catalysis Conference, Loughborough - 8-9th January 2015 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Tunable Platinum Nanocatalysts for the Aerobic Selective Oxidation of Cinnamyl Alcohol - Poster Presentation by Dr Lee Durndell
Year(s) Of Engagement Activity 2015
 
Description UK-Mexico Research Links Biofuels Workshop - "Biorefinery research - promoting international collaboration for innovative and sustainable solutions" 
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 UK-Mexico Research Links Biofuels Workshop - "Biorefinery research - promoting international collaboration for innovative and sustainable solutions" - 18-22nd May 2015

Oral Presentation Dr Lee Durndell - "Effect of reaction conditions and reactor type on biomass valorisation reactions - Selectivity control in Pt catalysed Cinnamaldehyde hydrogenation"
Year(s) Of Engagement Activity 2015
 
Description Waste biomass: A key player in securing UK energy and chemical needs in the 21st century through biorefining 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Policymakers/politicians
Results and Impact Panel Debate at Industry and Parliament Trust breakfast meeting with politicians as part of the Resilient Futures Programme. The PDF report was circulated throughout the UK and is available online
Year(s) Of Engagement Activity 2015
URL http://www.ipt.org.uk/Portals/0/IPT%20News%20and%20Comment/Research%20Page/IPT%20Resilient%20Futures...
 
Description Waste not Want not interview 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Interview with Prof Wilson by the Royal Society of Chemistry/Chemistry World focussed on the opportunities of using waste biomass as a feedstock for energy and chemicals, and how catalysis can help with facilitating such technology
Year(s) Of Engagement Activity 2015
URL http://www.rsc.org/chemistryworld/2015/09/waste-not-want-not-karen-wilson-interview
 
Description poster presentation at Farady Discussions by Vaishali Thaore, Ines Graca, Renewable production routes for Nylon-6 precursor: techno-econmic analysis for caprolactam 
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. Impact is wider dissemination of the research work and the TEA approach to sustainable process develoment. Increased interest of capability of research groups at Imperial College London
Year(s) Of Engagement Activity 2017