Producing VCM from Ethane

Ethane is isolated from natural gas and is a by-product of petroleum refining. It is primary used to produce ethylene. The easiest route to produce VCM is through the chlorination of ethane. The cost of ethylene is a significant contribution to the final cost of VCM, ethane is one third of the cost of ethylene1,2 and therefore would make the most economical route, but his is not the case. This process route has been difficult to perform due to difficulty in controlling the temperature. The temperature tends to soar above 500oC, at these temperatures plant and catalyst corrosion is high and difficult to manage and therefore the process is neglected. Several companies have tried to produce VCM from ethane but few have been successful. European Vinyls Corporation(EVC) are one of the company s which is working towards ethane to VCM production. They have made a breakthrough. They have built a pilot plant in Wilhelmshaven to produce 1000t/yr it has run more than 2000 hours at reaction temperature and has shown no corrosion and the catalyst has been observed to be stable. EVC who have teamed up with BECHTEL have produced a method which keeps the temperature below 500o and therefore prolonging catalyst life and using a novel catalyst.1,2 VCM is produced by the catalytic oxychlorination ethane preferably at 450oC-470oC. Ethane oxygen and a chlorine source, which could be chlorine gas, HCl or a chlorinated hydrocarbon is reacted with a catalyst to produce 90% conversion from ethane to VCM and 99% oxygen conversion. Purity of VCM to be further increased to 92-95%. EVC have claimed this method of production reduces the production cost over the PVC chain by 20-30%. The catalyst used is a Cu/K/Ce C2 H6 + Cl + O2 C2H3Cl + by-products + H2O

By-Products By-products are inevitably produced which include saturates, unsaturates and combustion products. Saturates include ethyl chloride, 1,1 dichloroethylene, cis 1,2 dichloroethane and 1,1,2 trichlorethane. Combustion products include CO, CO2, carbon tetrachloride, chloroform and dichloromethane.

Unsaturates include 1,1 dichloroethylene, cis 1,2 dichloroethylene and trichloroethylene. It is possible to oxychlorinate the chlorohydrocarbons but only to a limited extent as unsaturated hydrocarbons would not react and also for the saturated hydrocarbons some would react to become unsaturated and therefore would not be able to be converted to VCM. A second reactor is added to hydrogenate the chlorohydrocarbons before it is fed back into the oxychlorination reactor.

Hydrogenation

Chlorohydrocarbons

Ethane Chlorine Oxychlorination Oxygen VCM Purification

Combustion Products

Feed The feedstock for this process include y y y y Ethane Oxygen Chlorine N2

Results have shown chlorine gas to produce better results than the usage of HCl. Using chlorine gas resulted in fewer combustion products and therefore a higher conversion of ethane to VCM

Ethane is fed into the system preferably in the ratio of 1:0.75 to 1:1 oxygen, Ethane to chlorine ratio 1:0.5 to 1:5

ethylene, HCl, and H2O. Here 7-25 mol% of ethane is converted to VCM, VCM then removed from the stream where the remaining products are reacted through oxychlorination to produce VCM.

The steps for producing VCM from ethane is:3

1. Reacting a gaseous stream containing ethane, chlorine and oxygen. The ratio of chlorine to ethane, 0.4:1 to 0.6:1. Oxygen to ethane, 0.1:1 to 0.4:1, these are mole ratios. A temperature within 700oC to below 100oC, for 0.1 to 10 seconds to obtain a gas stream of ethylene and hydrogen chloride 2. Passing ethylene and hydrogen chloride gas stream together with hydrogen chloride from step 3 and oxygen to produce ethylene dichloride 3. Recovering the ethylene dichloride and thermally cracking the ethylene dichloride to obtain vinyl chloride and hydrogen chloride which is recycled into step 2

In the oxyhdrochlorination process ethylene is reacted with oxygen and hydrogen chloride to form EDC

As Ethylene is produced from this method, the Ethylene can be used to complete the other process routes the direct chlorination and even the balanced route. Another route is to use the one step process which converts ethane directly into vcm using a Copper-containing ZSM-5 catalyst at 500oC the temperature is important as at this temperature there is high activity of the catalyst and good selectivity for the oxychlorination process It has been predicted the ethane route would take 20 years for this route to catch up as this was the time taken for the EDC route to take over the Acetylene process7

Dow Global Technologies Inc. Dow Global Technologies have produced there own method

Disadvantages y y y y y y y Not a mainstream process therefore experience in this process would be lacking. Uses Chlorine which is a toxic and hazardous gas Energy intensive High corrosion on plant and catalyst (depending on method) Patented, therefore fees may need to be paid to the patent holder to use technology, patent holders may not give permission altogether making this process not legally possible Raw materials are lost due combustion products producing mainly CO2 which is released into the atmosphere as waste CO2 released which is a green house gas which may contribute to global warming

Advantages y y y y y Cheaper Raw Materials High selectivity Simpler process configuration Minimal byproducts through EVC Can be a single step reaction

http://www.google.com/patents?id=aj4eAAAAEBAJ&pg=PA1&dq=ethane+to+vcm+ethylene&hl=en&ei=xLbATq_8JMKw8gPl3_2XBA&sa=X&oi=book_result&ct=result&resnum=2&ved= 0CDIQ6AEwAQ#v=onepage&q=ethane%20to%20vcm%20-ethylene&f=true http://www.freepatentsonline.com/3987119.html http://www.icis.com/Articles/1998/05/11/58734/evc-ethane-to-vcm-pilot-plant-onstream-inmay.html http://www.freepatentsonline.com/5763710.html http://www.patentgenius.com/patent/5663465.html http://www.freepatentsonline.com/6933417.html http://www.google.co.uk/patents?hl=en&lr=&vid=USPAT5210358&id=IDgdAAAAEBAJ&oi=fnd&dq=e thane+based+vcm&printsec=abstract#v=onepage&q=ethane%20based%20vcm&f=false http://www.google.co.uk/patents?hl=en&lr=&vid=USPAT5728905&id=31EbAAAAEBAJ&oi=fnd&dq= ethane+based+vcm&printsec=abstract#v=onepage&q=ethane%20based%20vcm&f=false

References

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Wilhelmshaven http://www.chemicals-technology.com/projects/wilhelmshaven/ hydrocarbon online new vcm plant will use ethane" http://www.hydrocarbononline.com/article.mvc/New-VCM-Plant-Will-Use-Ethane-0001 (September 9, 1999) free patents online production of vinyl chloride from ethane http://www.freepatentsonline.com/3987119.html VCM manufacturing: A new generation of plants by Faisal Khan and Farid Benyahia http://archivos.labcontrol.cl/wcce8/offline/techsched/manuscripts/6vpxrm.pdf oxychlorination of Ethane to Vinyl chloride over copper ZSM-5 Michael M. Olken, Daniel Hickmen, Mark Jones http://www.nacatsoc.org/20nam/abstracts/p-s2-01a.pdf Vinyls EDC/VCM Technology Benefits INEOS Technologies last accessed 10/11/11 http://www.ineostechnologies.com/68-edc_vcm_technology_benefits.htm VCM from ethane becomes profitable http://www.cheresources.com/vcm.shtml