Enabling Oxidation Reactions on a Large Scale: Combining Electrochemistry with Flow

Lead Research Organisation: Imperial College London
Department Name: Dept of 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).
 
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 Academic/University
Country United Kingdom
Start 04/2014 
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 Academic/University
Country United Kingdom
Start 04/2014 
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 Academic/University
Country United Kingdom
Start 10/2013 
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