Sustainable Manufacturing in Multiphase Continuous Reactors: Aerobic Oxidations

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

Abstract

While bulk chemicals are generally manufactured in efficient continuous processes, generating relatively little waste (E-factor <1-5), high value chemical products (fine chemicals, agrochemicals, pharmaceuticals) are usually manufactured in batch units, generating enormous waste (E-factor ca. 25-100). There is therefore a clear business advantage, if continuous manufacturing techniques could be adapted for use in these industries. Continuous processing can facilitate safe manipulation of potentially hazardous reagents that can nevertheless effect low-waste transformations, e.g. by efficient heat-transfer in very exothermic processes & minimising local inventory of hazardous material. Whilst most oxidations of bulk chemicals can be performed continuously using molecular oxygen in the gas phase, safety considerations (exotherm, formation of explosive mixtures) preclude its use in batch processes, particularly for thermally sensitive, involatile substrates found in fine chemical manufacture. This leads to two undesirable behaviours: a) adoption of costly, atom inefficient, waste-generating stoichiometric oxidants, with consequent negative environmental impact, and b) a tendency to avoid oxidative transformations by using inevitably less efficient 'workarounds'. It is therefore clear that oxidation is a potentially key enabling technology. The demonstration of cost-effective, safe, and efficient use of aerobic oxidation in an organic solvent would be transformative since a wide and increasing range of catalytic organic transformations would be considered seriously by industry, and not avoided due to safety concerns. The potential to drive further efficiency by 'telescoping' subsequent transformations would also be facilitated by continuous, work-up free oxidation. Thus, this project aims to instigate a step change in efficiency in the manufacture of many products by developing safe continuous oxidative transformations.

Planned Impact

Financial as well environmental factors drive the development of safer, cleaner, cheaper chemical processes. The chemicals industry is vital to the fiscal health of UK plc. It contributes about £5bn to the UK balance of payments (£50bn gross) and represents ca. 2% of GDP. It is the UK's number one manufacturing exporter, and contributes ca. 11% of manufacturing GVA. Further, about half of the products go to service downstream UK industries. The industry is under pressure from low cost manufacturing economies in Asia and South America, and hence innovation to retain IP and the associated revenue streams in the UK is both vital and timely. The chemical industry, in particular pharmaceuticals, fine chemicals, catalyst producers, will be main beneficiaries from this work, by accessing novel technology and catalysts for clean oxidation processes. The proposed approach will ultimately help reduce time and cost associated with scaling up from laboratory to production, due to information-rich experimentation that is proposed. These will give a significant competitive advantage to the chemicals industry, assisting it to remain at the forefront of innovation worldwide. The research will also benefit equipment manufacturers, by allowing them to introduce in the market innovative products. This can help place the UK as a leading supplier of flow chemistry equipment, where the UK currently has a strong position. Finally, more efficient, cleaner and cheaper process solutions, will benefit the society through the use of these technological advances for green and sustainable chemical manufacture.

Publications

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Brazier J (2017) Effects of Cl on the reduction of supported PdO in ethanol/water solvent mixtures in Catalysis, Structure & Reactivity

 
Description We have designed catalytic packed-bed membrane reactors that we used to carry out oxidations with pure oxygen. Two type of membranes were investigated, ceramic and polymer. Oxidation of benzyl alcohol to benzaldehyde using gold/palladium catalyst was demonstrated with excellent conversion and selectivity in both packed-bed membrane reactors without creation of gas liquid mixtures, hence providing enhanced safety. Catalysts for other oxidations were also investigated, but they their size or stability was not sufficient to be deployed in the membrane packed bed reactors. To address these challenges we have applied for an EPSRC grant with an expanded industrial consortium.
Exploitation Route The knowledge gained and the reactors developed can form the basis of cleaner, safer and cheaper chemical transformations. They can broaden the scope of synthetic transformations to other multiphase reactions of interest to pharmaceutical, agrochemical, flavors and fragrances production, avoiding environmentally unfriendly oxidation processes.
Sectors Chemicals,Manufacturing, including Industrial Biotechology,Pharmaceuticals and Medical Biotechnology

 
Description Aerobic Oxidation 
Organisation AstraZeneca
Country United Kingdom 
Sector Private 
PI Contribution Catalyst recipes were devised and carried out on a small scale and recipes were transferred to JM. Also commercial catalysts of interest were identified across the research team (IC, UCL, Leeds, Cardiff, Huddersfield) Catalysts were tested in a number of oxidation reactions. Fundamental understanding of the reaction (kinetics/ catalyst deactivation) was studied. Promising reactions were tested in a novel membrane reactor
Collaborator Contribution Partners at JM scaled up catalyst recipes supplied by Cardiff to provide sufficient material for testing at IC and UCL. They also provided samples of their own commercially available catalysts. All collaborators gave input into the types of reaction to study and provided useful input to the direction of the research Information on safety aspects was provided. All members want the collaboration to continue.
Impact The collaboration has led to successful Proof of Concept for the use of heterogeneous catalysts in membrane reactors for the safe oxidation of substrates using air or oxygen. Novel methods for studying the kinetics/catalyst deactivation were devised Novel membrane reactors were constructed. There have been a number of papers and presentations with further publications in progress
Start Year 2013
 
Description Aerobic Oxidation 
Organisation GlaxoSmithKline (GSK)
Country Global 
Sector Private 
PI Contribution Catalyst recipes were devised and carried out on a small scale and recipes were transferred to JM. Also commercial catalysts of interest were identified across the research team (IC, UCL, Leeds, Cardiff, Huddersfield) Catalysts were tested in a number of oxidation reactions. Fundamental understanding of the reaction (kinetics/ catalyst deactivation) was studied. Promising reactions were tested in a novel membrane reactor
Collaborator Contribution Partners at JM scaled up catalyst recipes supplied by Cardiff to provide sufficient material for testing at IC and UCL. They also provided samples of their own commercially available catalysts. All collaborators gave input into the types of reaction to study and provided useful input to the direction of the research Information on safety aspects was provided. All members want the collaboration to continue.
Impact The collaboration has led to successful Proof of Concept for the use of heterogeneous catalysts in membrane reactors for the safe oxidation of substrates using air or oxygen. Novel methods for studying the kinetics/catalyst deactivation were devised Novel membrane reactors were constructed. There have been a number of papers and presentations with further publications in progress
Start Year 2013
 
Description Aerobic Oxidation 
Organisation Johnson Matthey
Country United Kingdom 
Sector Private 
PI Contribution Catalyst recipes were devised and carried out on a small scale and recipes were transferred to JM. Also commercial catalysts of interest were identified across the research team (IC, UCL, Leeds, Cardiff, Huddersfield) Catalysts were tested in a number of oxidation reactions. Fundamental understanding of the reaction (kinetics/ catalyst deactivation) was studied. Promising reactions were tested in a novel membrane reactor
Collaborator Contribution Partners at JM scaled up catalyst recipes supplied by Cardiff to provide sufficient material for testing at IC and UCL. They also provided samples of their own commercially available catalysts. All collaborators gave input into the types of reaction to study and provided useful input to the direction of the research Information on safety aspects was provided. All members want the collaboration to continue.
Impact The collaboration has led to successful Proof of Concept for the use of heterogeneous catalysts in membrane reactors for the safe oxidation of substrates using air or oxygen. Novel methods for studying the kinetics/catalyst deactivation were devised Novel membrane reactors were constructed. There have been a number of papers and presentations with further publications in progress
Start Year 2013
 
Description Aerobic Oxidation 
Organisation Syngenta International AG
Department Syngenta Ltd (Bracknell)
Country United Kingdom 
Sector Private 
PI Contribution Catalyst recipes were devised and carried out on a small scale and recipes were transferred to JM. Also commercial catalysts of interest were identified across the research team (IC, UCL, Leeds, Cardiff, Huddersfield) Catalysts were tested in a number of oxidation reactions. Fundamental understanding of the reaction (kinetics/ catalyst deactivation) was studied. Promising reactions were tested in a novel membrane reactor
Collaborator Contribution Partners at JM scaled up catalyst recipes supplied by Cardiff to provide sufficient material for testing at IC and UCL. They also provided samples of their own commercially available catalysts. All collaborators gave input into the types of reaction to study and provided useful input to the direction of the research Information on safety aspects was provided. All members want the collaboration to continue.
Impact The collaboration has led to successful Proof of Concept for the use of heterogeneous catalysts in membrane reactors for the safe oxidation of substrates using air or oxygen. Novel methods for studying the kinetics/catalyst deactivation were devised Novel membrane reactors were constructed. There have been a number of papers and presentations with further publications in progress
Start Year 2013
 
Title Continuous ceramic membrane reactor 
Description A novel continuous flow reactor using a ceramic membrane to keep the liquid and gaseous reactants apart excepting at the interface. This allows safe use of oxygen with flammable solvents 
Type Of Technology Physical Model/Kit 
Year Produced 2015 
Impact This technology has the potential to enable aerobic oxidations on scale - this will minimise waste and increase sustainability compared to standard methodology for oxidation reactions 
 
Description 2016 AIChE Annual Meeting San Francisco "Measurement of Oxygen Solubility in Toluene and Benzyl Alcohol Using a Tube-in-Tube Membrane Contactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Poster "Measurement of Oxygen Solubility in Toluene and Benzyl Alcohol Using a Tube-in-Tube Membrane Contactor"
Year(s) Of Engagement Activity 2016
URL https://www.aiche.org/conferences/aiche-annual-meeting/2016
 
Description Asia-Oceania Conference on Sustainable and Green Chemistry (AOC-SGC6), City University of Hong Kong (November 27-30, 2016 "Plenary Speaker _Flow Chemistry: Is It Green?" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Policymakers/politicians
Results and Impact Plenary Speaker _Flow Chemistry: Is It Green?
Year(s) Of Engagement Activity 2016
URL http://www.cityu.edu.hk/bch/aoc-sgc6/
 
Description CHEMREACTOR-22, "Continuous Flow Packed Bed Microreactors used for Deactivation Studies of Aerobic Alcohol Oxidation on Au-Pd/TiO2 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
G. Wu, G. L. Brett, E. Cao1, A. Constantinou1, P. Ellis, S. Kuhn, G. J. Hutchings, D. Bethell, A. Gavriilidis, "Continuous Flow Packed Bed Microreactors used for Deactivation Studies of Aerobic Alcohol Oxidation on Au-Pd/TiO2 Catalyst", 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 Catalytic Sustainability in the Future, Manchester 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Invited speaker - Mimi Hii
Year(s) Of Engagement Activity 2016
URL http://generic.wordpress.soton.ac.uk/dial-a-molecule/wp-content/blogs.dir/sites/50/2014/11/CSF-Meeti...
 
Description Dial-a-Molecule Annual Meeting exhibition 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Novel reactors developed during the project were displayed in an exhibition and also highlighted in flash presentations. Novel flow calorimeter was of particular interest to industry
Year(s) Of Engagement Activity 2015
 
Description Dial-a-Molecule Annual Meeting presentation 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Presentations given to 70+ audience members drawn from across the UK, academia and industry, highlighting progress with the project.
Year(s) Of Engagement Activity 2014,2015
URL http://generic.wordpress.soton.ac.uk/dial-a-molecule/chemical-synthesis-in-the-21st-century-annual-m...
 
Description ESCRE 2015, European Symposium on Chemical Reaction Engineering, Fürstenfeldbruck, Germany "Continuous Heterogeneous Oxidation of Benzyl Alcohol using a Packed Bed Ceramic Membrane 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 on "Continuous Heterogeneous Oxidation of Benzyl Alcohol using a Packed Bed Ceramic Membrane Reactor "
Year(s) Of Engagement Activity 2015
 
Description Euromembrane2015, Aachen, Germany, 2015 "Continuous Heterogeneous Oxidation of Benzyl Alcohol Using a Tube-in-Tube Membrane Microreactor: A Combined Experimental and Simulation Study" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Presentation on "Continuous Heterogeneous Oxidation of Benzyl Alcohol Using a Tube-in-Tube Membrane Microreactor: A Combined Experimental and Simulation Study"
Year(s) Of Engagement Activity 2015
 
Description Flow Chemistry Europe 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited speaker (Mimi Hii). Described work on catalyst deactivation and leaching, showing different mechanism from that described in the literature
Year(s) Of Engagement Activity 2016
URL https://selectbiosciences.com/conferences/biographies.aspx?speaker=1077202&conf=fce2016
 
Description Flow Chemistry Europe 2017, Cambridge, U.K. (February 7-8, 2017). "Keynote Speaker Interrogating Catalyst Deactivation and Leaching in Continuous Flow" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Keynote Speaker Interrogating Catalyst Deactivation and Leaching in Continuous Flow
Year(s) Of Engagement Activity 2017
URL https://selectbiosciences.com/conferences/index.aspx?conf=FCS2017
 
Description IChemE, Mixing Subject Interest Group, 2016, "High-content Data Extraction from Multiphase Flow Systems via Optical High-speed Imaging Methodology" 
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
A. N. Pallipurath Radhakrishnan, G. Valitov, L. Mazzei, A. Gavriilidis, "High-content Data Extraction from Multiphase Flow Systems via Optical High-speed Imaging Methodology", in Transport and Mixing in Micro-Scale Flow, IChemE, Mixing Subject Interest Group, UCL, 11th November, 2016.
Year(s) Of Engagement Activity 2016
 
Description ISCRE 24 2016, "Continuous Aerobic Oxidation of Benzyl Alcohol in a Catalytic Membrane 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
A. Constantinou, G. Wu, S. Kuhn, P. Ellis A. Gavriilidis, "Aerobic Oxidation of Benzyl Alcohol in a Catalytic Membrane Reactor", ISCRE24, 24th International Symposium in Chemical Reaction Engineering, Minneapolis, USA, 12-15 June 2016.
Year(s) Of Engagement Activity 2016
URL http://iscre.org/ISCRE24/
 
Description ISCRE25, 25th International Symposium in Chemical Reaction Engineering, 2018, "Development of a Flat Membrane Microchannel Packed Bed Reactor for Scalable Aerobic Oxidation of Benzyl Alcohol in 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
Wu G., Cao E., Ellis P., Kuhn S., Gavriilidis. "Development of a Flat Membrane Microchannel Packed Bed Reactor for Scalable Aerobic Oxidation of Benzyl Alcohol in Flow", ISCRE25, 25th International Symposium in Chemical Reaction Engineering, Florence, Italy, May 2018.
Year(s) Of Engagement Activity 2006,2018
 
Description Poster at International Symposium on Synthesis and Catalysis 
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 at a significant international symposium
Year(s) Of Engagement Activity 2015
 
Description Presentation at UKASF 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Industry/Business
Results and Impact Presentation on the outcomes of Dial-a-Molecule, including the Aerobic Oxidation project, to a group of industry representatives. Led to interest in involvement in a future project from one company
Year(s) Of Engagement Activity 2015
 
Description Project presentation to staff at the industry partners 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Industry/Business
Results and Impact Presentations to give update on project progress to staff at AZ, Syngenta and Johnson-Matthey. The audiences asked questions and gave input to the future direction of the project.
Year(s) Of Engagement Activity 2014,2015
 
Description UK Catalysis Conference 2015, Loughborough "Continuous Heterogeneous Oxidation of Benzyl Alcohol Using a Tube-in-Tube Reactor" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Presentation on "Continuous Heterogeneous Oxidation of Benzyl Alcohol Using a Tube-in-Tube Reactor"
Year(s) Of Engagement Activity 2015
 
Description UK Catalysis Conference 2016, Loughborough 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Plenary speaker - Mimi Hii
Year(s) Of Engagement Activity 2016
 
Description UK Catalysis Conference, Holywell Conference Centre, Loughborough (January 6-8, 2016). "Plenary Speaker - Catalysis in Flow" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Plenary Speaker - Catalysis in Flow
Year(s) Of Engagement Activity 2016
URL https://www.qub.ac.uk/sites/UKCC2016/
 
Description XXII International conference on chemical reactors, London, UK 2016 "CONTINUOUS FLOW PACKED BED MICROREACTORS USED FOR DEACTIVATION STUDIES OF AEROBIC ALCOHOL OXIDATION on AuPd/TiO2 CATALYST" 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact CONTINUOUS FLOW PACKED BED MICROREACTORS USED FOR DEACTIVATION STUDIES OF AEROBIC ALCOHOL OXIDATION on AuPd/TiO2 CATALYST
Year(s) Of Engagement Activity 2016
URL http://conf.nsc.ru/CR_22/en/invitation
 
Description XXIII International conference on Chemical Reactors, CHEMREACTOR23, 2018, "Aerobic Oxidation of Benzyl Alcohol in a Au-Pd/TiO2 Catalyst Slurry Reactor with Oxygen Delivery via a Tubular Membrane" 
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
B. Venezia, P. Ellis, A. Gavriilidis, "Aerobic Oxidation of Benzyl Alcohol in a Au-Pd/TiO2 Catalyst Slurry Reactor with Oxygen Delivery via a Tubular Membrane", XXIII International conference on Chemical Reactors, CHEMREACTOR23, Ghent, Belgium, November, 2018.
The presentation won a best presentation award
Year(s) Of Engagement Activity 2018