Greening of alkene epoxidations via use of polymer-supported Mo(VI) catalysts in a continuous reactive distillation process

Lead Research Organisation: Loughborough University
Department Name: Chemical Engineering

Abstract

Alkenes are first generation fundamental organic chemical building blocks derived on a large scale from oil. These molecules are themselves converted into a wide range of second generation organic chemical building blocks which can be further chemically modified to provide a wealth of precursor organic molecules for the pharmaceutical and agrochemical, industries, and also for industries such as the household and personal products industries. One strategically important class of second generation organic chemical building blocks are the epoxides, and this proposal relates to a novel more environmentally friendly chemical technology for converting alkenes into epoxides. Currently this is carried out on both a small and large scale using soluble (homogeneous) metal catalysts e.g. molybenum complexes, with the oxygen required for the chemical reaction being provided by a specific oxidant, an alkyl hydroperoxide. The latter is converted to an alcohol molecule in the course of the reaction and this is easily recycled back to the hydroperoxide i.e. this part of the process is really quite environmentally friendly. Unfortunately however use of a soluble catalyst in the epoxidation reaction requires a complex chemical plant involving a large batch reactor, a substantial downstream product isolation and purification plant, and an additional process to recover any soluble catalyst that escapes from the reactor. This complex plant is costly to build and is very energy and materials (e.g. cooling water) inefficient i.e. it is by no means as environmental friendly as it might be.The present project aims to convert the usual soluble catalyst into an insoluble (heterogeneous) one by immobilising the catalyst inside the porous structure of small polymer (plastic) particles. This will allow the catalyst to be more easily handled and retained efficiently, ie. the catalyst recovery part of a conventional plant will be redundant. The particulate form of the catalyst will also allow it to be packed inside a hollow metal column, and the latter will be used as the reactor in which the chemical conversion of alkene to epoxide will take place. The simplicity of this is that the alkene and the oxidant can be flowed through the bed of insoluble catalyst in a continuous way without any leakage or loss of catalyst. In a further technology improvement the reactor column will also be utilised to separate the useful epoxide product from the by-product alcohol, and also from any traces unwanted sideproducts that are formed in the reaction, i.e. the downstream product isolation and purification plant will also be redundant. Overall therefore the project will give rise to a new integrated chemical technology, based on an insoluble catalyst, and eliminating a substantial part of the plant associated with the current process technology. The very simplicity of the new technology means that overall energy and materials demands will be reduced considerably, as well as the cost of any such a new process being much lower than that of a current process. The project will therefore make a substantial contribution to improving the environmental performance of alkene epoxidation processes.

Publications

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Ambroziak K (2009) Investigation of Batch Alkene Epoxidations Catalyzed by Polymer-Supported Mo(VI) Complexes in Industrial & Engineering Chemistry Research

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Ambroziak K (2010) Greener and Sustainable Method for Alkene Epoxidations by Polymer-Supported Mo(VI) Catalysts in International Journal of Chemical Reactor Engineering

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Ambroziak, K (2007) Exploitation of polymer-supported Mo(VI) alkene epoxidation catalysts under reactive distillation conditions in 1st International Congress on Green Process Engineering - GPE 2007

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Ambroziak, K. (2010) Greener and sustainable method for alkene epoxidations with novel polymer-supported Mo(VI) complexes in 5th International Conference on Ion Exchange (ICIE 2010)

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Ambroziak, K. (2009) Greener and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts in 2nd International Congress on Green Process Engineering - GPE 2009

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Ambroziak, K. (2011) Cleaner and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts in 3rd International Congress on Green Process Engineering - GPE 2011

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Ambroziak, K. (2007) Epoxidation of alkenes catalayzed by polymer-supported Mo(VI) complexes in 4th International Conference on Ion Exchange

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Ambroziak, K. (2007) Greener and sustainable approach for epoxidation of alkenes using polymer-supported Mo(VI) complexes in CHEMCON 2007 - Indian Chemical Engineering Congress, 60th Annual Session of the Indian Institute of Chemical Engineers

 
Description Collaboration with Professor David C. Sherrington FRS FRSE, University of Strathclyde 
Organisation University of Strathclyde
Country United Kingdom 
Sector Academic/University 
PI Contribution This was a very successful Chemistry (EP/C530969/1 - University of Strathclyde) and Chemical Engineering (EP/C530950/1 - formerly Loughborough University and then London South Bank University) collaboration through our project entitled, "Greening of alkene epoxidations via use of polymer-supported Mo(VI) catalysts in a continuous reactive distillation process." The contributions have been reported in the final project report. We have evaluated the polymer supported Mo(VI) catalysts in a batch liquid phase alkenes and terpenes epoxidation reaction. We have estimated of the techno-feasibility of this operation through a systematic procedure of residue curve maps (RCM). We have successfully constructed and commissioned a reactive distillation column (RDC). We have established an experimental methodology for the evaluation of reactive distillation strategies to optimise the process conditions and the column configurations using polymer-supported Mo (VI) catalysts for alkenes and terpenes epoxidation reactions. After successful completion of this project we were successful in securing a follow on fund (EP/H027653/1) on the development of a continuous clean alkene epoxidation process technology for the production of commercially important epoxide building blocks.
Collaborator Contribution Professor Sherrington and his group have successfully synthesised and characterised novel polymer-supported Mo(VI) complexes. They have evaluated the above complexes as heterogeneous catalysts in a batch liquid phase alkene epoxidation reaction. The have scaled up the production of polymer supported Mo(VI) complexes and supplied about ~100 g catalysts to us for evaluation in continuous a reactive distillation column (RDC). It was a very successful chemistry-chemical engineering collaboration. We have jointly publised a series of papers and filed a number of patents subsequently.
Impact Patents: Saha, B;, Ambroziak, K.; Sherrington, D.C.; Mbeleck, R., LIQUID PHASE EPOXIDATION PROCESS, US Patent Number US 8,759,552 B2 (Issued on: 24/06/2014), (filed by South Bank University Enterprises Ltd). Saha, B., Ambroziak, K., Sherrington, D.C, and Mbeleck, R., PROCESS, Indian Patent Application No. 192/KOLNP/2012 (Filing date: 05/10/2012), (filed by South Bank University Enterprises Ltd). Saha, B., Ambroziak, K., Sherrington, D.C, and Mbeleck, R., A CONTINUOUS PROCESS FOR THE LIQUID PHASE EPOXIDATION OF AN OLEFINIC COMPOUND WITH AN OXIDANT, Chinese Patent Application Number 201080044175.2 (Filing date: 18/07/2012), (filed by South Bank University Enterprises Ltd). Saha, B., Ambroziak, K., Sherrington, D.C, and Mbeleck, R., PROCESS (Publication number EP2459545), Europe Patent Application Number EP 10749674.7 (Filing date: 16/02/2012), (filed by South Bank University Enterprises Ltd). Saha, B., Ambroziak, K., Sherrington, D.C, and Mbeleck, R., PROCESS (Publication number WO/2011/012869), International Patent Application Number PCT/GB2010/001458, (Publication Date: 03.02.2011), (filed by South Bank University Enterprises Ltd). Journal articles: Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Greener and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts", International Journal of Chemical Reactor Engineering, 2010, 8 (A125), 1-13. Ambroziak, K., Mbeleck, R., He, Y., Saha, B. and Sherrington, D. C, "Investigations of batch alkenes epoxidation catalayzed by novel polymer-supported Mo(VI) complexes", Industrial and Engineering Chemistry Research, 2009, 48, 3293-3302. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C. "Epoxidation of limonene by tert-butyl hydroperoxide catalyzed by polybenzimidazole-supported Mo(VI) complex", Journal of Ion Exchange, 2007, 18 (4), 452-457. Mbeleck, R.; Ambroziak, K.; Saha, B.; Sherrington, D. C., "Stability and recycling of a polymer-supported Mo(VI) alkene epoxidation catalyst", Reactive and Functional Polymers, 2007, 67, 1448-1457. Mohammed, M. L.; Mbeleck, R.; Patel, D.; Sherrington, D. C.; Saha, B., "Greener route to 4-vinyl-1-cyclohexane 1,2-epoxide synthesis using batch and continuous reactors", Green Processing and Synthesis, 2014, manuscript accepted. Mohammed, M. L.; Patel, D.; Mbeleck, R.; Niyogi, D.; Sherrington, D. C.;, Saha, B., "Greener and efficient epoxidation of 4-vinyl-1-cyclohexene with polystyrene 2-(aminomethyl)pyridine supported Mo(VI) catalyst in batch and continuous reactors", Chemical Engineering Research and Design, 2014, in press, doi 10.1016/j.cherd.2014.08.001 Patel, D.; Kellici, S.; Saha, B., "Green process engineering as the key to future processes", Processes, 2014, 2, 311-332. Mohammed, M. L.; Patel, D.; Mbeleck, R.; Niyogi, D.; Sherrington, D. C.; Saha, B., "Optimisation of alkene epoxidation catalysed by polymer supported Mo(VI) complexes and application of artificial neural network for the prediction of catalytic performances", Applied Catalysis: A, 2013, 466, 142-152. Patel, D.; Kellici, S.; Saha, B., "Some novel aspects of green process engineering", Chimica Oggi - Chemistry Today, 2013, 31(3), 57-61. Conference papers: Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Cleaner and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts", 3rd International Congress on Green Process Engineering - GPE 2011, Kuala Lumpur, Malaysia, December 2011, [CD-ROM]. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Greener and sustainable method for alkene epoxidations with novel polymer-supported Mo(VI) complexes", 5th International Conference on Ion Exchange (ICIE 2010), Melbourne, Australia, July 2010, [CD-ROM]. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Greener alkene epoxidations via use of novel polymer-supported Mo(VI) catalysts in a continuous reactive distillation process", 8th World Congress of Chemical Engineering (WCCE8), Montreal, Canada, August 2009, 0860 [CD-ROM]. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Greener and sustainable method for alkene epoxidations by polymer-supported Mo(VI) catalysts", 2nd International Congress on Green Process Engineering - GPE 2009, Venice, Italy, June 2009, 63, [CD-ROM]. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Exploitation of polymer-supported Mo(VI) catalysts in epoxidation of selected terpenes and alkenes", Gordon Research Conference: Catalysis, New London, NH, USA, June 2008, 2. Mbeleck, R.; Sherrington, D. C.; Ambroziak, K.; Saha, B.;,"Stability and recycling of polymer-supported Mo (VI) alkene epoxidation catalysts", Gordon Research Conference: Catalysis, New London, NH, USA, June 2008, 1. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Greener and sustainable approach for epoxidation of alkenes using polymer-supported Mo(VI) complexes", CHEMCON 2007 - Indian Chemical Engineering Congress, 60th Annual Session of the Indian Institute of Chemical Engineers, Kolkata, India, 2007, F1240, pp 1-8 [CD-ROM]. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C. "Epoxidation of alkenes catalayzed by polymer-supported Mo(VI) complexes", 4th International Conference on Ion Exchange, Chiba, Japan, 2007, 22. Ambroziak, K.; Mbeleck, R.; Saha, B.; Sherrington, D. C., "Exploitation of polymer-supported Mo(VI) alkene epoxidation catalysts under reactive distillation conditions", 1st International Congress on Green Process Engineering - GPE 2007, Toulouse, France, 2007, No 94, pp 1-8 [CD-ROM]. Mohammed, M. L.; Patel, D.; Mbeleck, R.; Sherrington, D. C.; Saha, B., "A safer and scalable continuous alkene epoxidation process", 21st International Congress of Chemical and Process Engineering CHISA, Prague, August 2014, [CD-ROM]. Mohammed, M. L.; Patel, D.; Mbeleck, R.; Sherrington, D. C.; Saha, B., "Greener route to epoxides using batch and continuous reactors", 4th International Congress on Green Process Engineering, Seville, Spain, April 2014, Paper number 242, pp 1-7, [CD-ROM]. Mohammed, M. L.; Mbeleck, R.; Sherrington, D. C.; Saha, B., "An efficient and selective alkene epoxidation process", ChemEngDayUK 2014, Manchester, UK, April 2014. Mbeleck, R.; Mohammed, M. L.; Sherrington, D. C.; Saha, B. "Environmentally benign alkene epoxidation process," 9th World Congress of Chemical Engineering (WCCE9), Seoul, Korea, August, 2013, Paper number FrO-T104-3, Korean Institute of Chemical Engineers (KIChE): Seoul, Korea, 2013, [CD-ROM]. Mohammed, M. L.; Mbeleck, R.; Sherrington, D. C.; Saha, B. "Greener and efficient alkene epoxidation process", 9th European Congress of Chemical Engineering (ECCE9), April 2013, Hague, The Netherlands, Paper number 794, ECCE9-ECAB2 App, MCI-Eurocongress v.o.f.: Amsterdam, The Netherlands, 2013. Mohammed, M. L.; Mbeleck, R.; Patel, D.; Sherrington, D. C.; Saha, B., "A greener, inherently safer and scalable continuous alkene epoxidation process", ChemEngDayUK 2013, London, UK, March 2013, pp 86-87. Saha, B.; "Continuous clean alkene epoxidation process technology for the production of commercially important epoxide building blocks", 3rd International Conference of the Flow Chemistry Society, Munich, Germany, March 2013, [CD-ROM]. Mbeleck, R.; Mohammed, M. L.; Ambroziak, K.; Sherrington, D. C.; Saha, B. "Cleaner and efficient alkenes/terpenes epoxidation process catalysed by novel polymer-supported Mo(VI) complexes", IEX 2012, Cambridge, UK, 2012, [CD-ROM].
Start Year 2006
 
Title PROCESS 
Description The present invention provides a continuous process for the epoxidation of an olefinic compound with an oxidant, which process comprises reaction of an olefinic compound with an oxidant in the presence of a catalyst in an apparatus that comprises a reactive distillation column, which column comprises (i) a reactive section, which comprises the catalyst (ii) a rectifying section situated above the reactive section and adapted to allow separation of reagents and/or by-products from products (ix) a stripping section situated below the reactive section and adapted to allow separation of product from reagents and/or by-products (x) a vessel situated below the stripping section and adapted to provide a source of heat for the column and in which initial vaporisation of one or more of the reagents can occur, wherein the temperature in the reactive section (i) is a temperature at which the reaction between the olefinic compound and the oxidant takes place and the temperature in the stripping section (iii) is higher than the temperature in the rectifying section (ii). 
IP Reference WO2011012869 
Protection Patent application published
Year Protection Granted 2011
Licensed No
Impact The smaller integrated plant design leads to lower capital cost of new plant, and very importantly to lower recurrent costs in terms of energy and materials (water, steam, solvent etc.) costs. Overall therefore this new process provides many advantages to potential users: feedstock flexibility, atom efficiency, flexibility of scale of production, energy efficiency, reduced unit costs and improved profitability. Importantly as well, the new process makes a big impact on the environmental acceptab
 
Title PROCESS 
Description The present invention provides a continuous process for the epoxidation of an olefinic compound with an oxidant, which process comprises reaction of an olefinic compound with an oxidant in the presence of a catalyst in an apparatus that comprises a reactive distillation column, which column comprises (i) a reactive section, which comprises the catalyst (ii) a rectifying section situated above the reactive section and adapted to allow separation of reagents and/or by-products from products (ix) a stripping section situated below the reactive section and adapted to allow separation of product from reagents and/or by-products (x) a vessel situated below the stripping section and adapted to provide a source of heat for the column and in which initial vaporisation of one or more of the reagents can occur, wherein the temperature in the reactive section (i) is a temperature at which the reaction between the olefinic compound and the oxidant takes place and the temperature in the stripping section (iii) is higher than the temperature in the rectifying section (ii). 
IP Reference US2012136165 
Protection Patent granted
Year Protection Granted 2012
Licensed No
Impact The smaller integrated plant design leads to lower capital cost of new plant, and very importantly to lower recurrent costs in terms of energy and materials (water, steam, solvent etc.) costs. Overall therefore this new process provides many advantages to potential users: feedstock flexibility, atom efficiency, flexibility of scale of production, energy efficiency, reduced unit costs and improved profitability. Importantly as well, the new process makes a big impact on the environmental acceptab