Enabling Oxidation Reactions on a Large Scale: Combining Electrochemistry with Flow
Lead Research Organisation:
Imperial College London
Department Name: Chemistry
Abstract
When a molecule is oxidised, it either loses electrons (increasing its 'oxidation state') or, more commonly in organic chemistry, it gains an oxygen atom from another molecule (the 'oxidant'). Oxygenated molecules are important intermediates for the preparation of complex molecules, including medicinally interesting compounds, and are thus important for phamaceutical production.However, oxidation reactions are often difficult to achieve on a large scale, due to the following reasons:(i) Many oxidants are either toxic, or are thermally unstable materials that are potentially explosive;(ii) Oxidation reactions are by nature exothermic and may involve induction periods - this makes a reaction inherently unsafe, as thermal runaway is unpredictable and thus difficult to control.(iii) Presence of oxidants in organic solvents may generate organic peroxides, which are explosive at a certain limit, and may also cause thermal runaway reactions;(iv) The reaction can be unselective, producing many products, which may be difficult and costly to separate.This project proposes to overcome these problems by designing a new equipment to perform these reactions safely and cleanly, using largely electricity and water to generate oxidants. As the oxidant is generated and consumed immediately, the effective concentration of the reactive oxidant is kept to a minimum during the process, thus eliminating explosive hazards and environmental exposure. We are interested in 'waste free' reactions that produces side products that are environmentally benign, such as water, or in a form that can be recovered and reused (recycled).
Publications
Bystron T
(2018)
2-Iodoxybenzoic Acid Synthesis by Oxidation of 2-Iodobenzoic Acid at a Boron-Doped Diamond Anode
in ChemElectroChem
Hellgardt K
(2018)
Advanced Green Chemistry - Part 1: Greener Organic Reactions and Processes
Zotova N
(2012)
Catalysis in flow: Au-catalysed alkylation of amines by alcohols
in Green Chem.
Brazier J
(2017)
Catalysis in flow: O 2 effect on the catalytic activity of Ru(OH) x /?-Al 2 O 3 during the aerobic oxidation of an alcohol
in Reaction Chemistry & Engineering
Zotova N
(2010)
Catalysis in flow: the practical and selective aerobic oxidation of alcohols to aldehydes and ketones
in Green Chemistry
Deadman B
(2022)
On-demand, in situ , generation of ammonium caroate (peroxymonosulfate) for the dihydroxylation of alkenes to vicinal diols
in Green Chemistry
Zhu J
(2016)
Toward a Green Generation of Oxidant on Demand: Practical Electrosynthesis of Ammonium Persulfate
in ACS Sustainable Chemistry & Engineering
Description | Two types of continuous flow reactors were investigated in this project. The first, a commerically avaialble fixed-bed reactor system, has been successfully utilised to carry out multiphase reactions, and to perform very efficient and safe oxidative reactions. The second electrochemical flow reactor has also been constructued, which can generate a synthetically useful level of oxidant in a single-pass. Preliminary results showed that this can be used for the catalysed oxidation of alcohols to acids very selectively. |
Exploitation Route | These reactors can potentially utilised by the chemical industy to perform oxidation reactions on a large-scale, in a safe and environmentally sustainable way. Commerical partners are being sort to bring forward an industrially-viable prototype of the electrochemical reactor. |
Sectors | Chemicals Pharmaceuticals and Medical Biotechnology |
Description | Patents have been filed and currently negotiating licensing terms. |
First Year Of Impact | 2016 |
Sector | Environment |
Impact Types | Economic |
Description | A flow reactor system for delivery of oxidants on-demand |
Amount | £52,792 (GBP) |
Funding ID | RSRP_P43480 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 03/2014 |
End | 10/2014 |
Description | Manufacturing in Flow: Controlled Multiphase Reactions on Demand (CoMRaDe) |
Amount | £662,057 (GBP) |
Funding ID | EP/L012278/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 03/2014 |
End | 03/2017 |
Description | Sustainable manufacturing in multiphase continuous reactors: Aerobic oxidations |
Amount | £999,981 (GBP) |
Funding ID | EP/L003279/1 |
Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
Sector | Public |
Country | United Kingdom |
Start | 09/2013 |
End | 04/2015 |
Title | Apparatus and method for production of oxidants |
Description | The inventors of the present invention have developed an apparatus and method which enables a user to manufacture a wide variety of different species of oxidants on-demand and in-situ. For example, the apparatus and method of the 5 present invention can be used in a laboratory or in a chemical plant, to deliver a desired oxidant type to a chemical process, at the time the oxidant is required and with user defined characteristics, for example, at a desired temperature, concentration and flow rate. The apparatus and method of the present invention thus avoids the need for oxidant storage in quantities which would be 10 of safety and quality concern and gives the option of delivering freshly prepared oxidant which can be used immediately and in-situ. |
IP Reference | GB1509769.4 |
Protection | Patent application published |
Year Protection Granted | 2015 |
Licensed | Commercial In Confidence |
Impact | Other patents applied (pending) |
Title | Electrochemical Cell |
Description | The invention relates to an electrochemical cell comprising a reservoir for storing reactants therein. The invention extends to uses of the cell, appliances and systems comprising the cell, and to methods of producing an oxidant. The apparatus allows an oxidant to be prepared in situ. This means that the oxidant can be prepared immediately prior to use, and there is therefore no need to store the oxidant. |
IP Reference | GB1710655.0 |
Protection | Patent application published |
Year Protection Granted | 2017 |
Licensed | Commercial In Confidence |
Impact | Further work is commissioned to produce a working prototype in anticipation of a product launch in 2019. |
Description | 6th Conference on Frontiers in Organic Synthesis Technology (FROST6): invited talk |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | led to collaborative opportunities |
Year(s) Of Engagement Activity | 2017 |
Description | A Youtube video |
Form Of Engagement Activity | Engagement focused website, blog or social media channel |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Public/other audiences |
Results and Impact | A video to explain the potential impacts of the technology developed in this research, particularly the device described in the patent (Oxi-Gen). 1,358 views recorded (2/2/2017) |
Year(s) Of Engagement Activity | 2015 |
URL | https://www.youtube.com/watch?v=8N-98QTRzU0 |
Description | Invited Speaker, Energy Dispersive X-ray Absorption Spectroscopy Workshop, Diamond Light Source, Harwell, March 10-11, 2016 |
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 | Workshop to discuss the use of X-ray absorption spectroscopy for catalysis research. |
Year(s) Of Engagement Activity | 2016 |
Description | Keynote Speaker (and co-chair), Flow Chemistry Europe 2017, Cambridge, UK, February 7-8, 2017 |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Keynote lecture at an international meeting |
Year(s) Of Engagement Activity | 2017 |
Description | Keynote Speaker at the 8th International Conference on Green and Sustainable Chemistry (GSC8), Melbourne, Australia, July 23-26, 2017. |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Professional Practitioners |
Results and Impact | Keynote presentation at an international meeting. |
Year(s) Of Engagement Activity | 2017 |
Description | Plenary Speaker, Asia-Oceania Conference on Sustainable and Green Chemistry (AOC-SGC6), City University of Hong Kong, November 27-30, 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 speaker at an international meeting |
Year(s) Of Engagement Activity | 2016 |
Description | Research seminar at University of Sydney, Australia |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Postgraduate students |
Results and Impact | Departmental research seminar attended by members of academic staff and research students |
Year(s) Of Engagement Activity | 2017 |