Europaisches Patentamt ® p)) European Patent Otfice © & publication nmi: 0 000 847 Office européen des brevets Al ® EUROPEAN PATENT APPLICATION © Application number: 78300280.1 @ mci: © 07 C 21/06, C 07 C 17/34 ® dete offing: 14.08.78 © Prony: 1808.77 GB 94270777 © Avplicant: BP Chemicals Liited Britannic House Moor Lane London, EC2Y S868) © date of pubtication of appieton: 249279 Built 79/4 © invertor: Bure, Dork Arthur {BP Research Contre Chorney Road © Designated contracting state: Sunburcon-Thames Middlesex, TW16 TLN(GB) Be DE FR AL SE © tvertor: Bur, Edward John {P Resouch Contre Cheraey Road ‘Sunbury oo-Toumee Mdleses,TW18 7LN(GB) © tevertor: Capp, Cord Waa {b Mesonch Catre Chertsey oad Snbur-on Tames Midler, TW18 7LNGB) ]® Represonzive: Hany, John ota BP TRADING LIMITED Patents & Ucening Dion Corey Road Sunburron Thames WdslovexTW16 7LN(GB) © Viny! chloride monomer production. -:© This invention relates to « process for producing vinyl chloride monomer by pyrolysing a mixture of 12> ichloroethane and the isomer 1,1-lichloroethane. It hes ‘been found that mixtures containing between 0.1 and 10%¢by ! weight of the 1,1-isomer improves the yield of the monomer {otherwise obtainable by using the 1,-aomer alone. EP 0 000 847 A1 aan Pig Copan10 15 20 r 0000847 ‘VINYL CHLORIDE MONOMER PRODUCTION ‘The present invention relates to a process for the preparation of vinyl chloride by the dehydrochlorination of mixtures of isomeric dichloroethanes. It is known that vinyl chloride can be produced by the pyrolytic dehydrochlorination of 1,2-dichloroethane, The process involves the passing of 1,2-dichlorcethane through a small diameter reaction tube in which it is heated to elevated temperatures to bring about the dehydrochlorination thereof. In contrast to this, it has not hitherto been possible to convert the isoneric 1,1- @ichloroethane, which is a by-product of the pyrolysis of 1,2- @ichlorethane, into vinyl chloride 4n economic yields, Published data indicate that 1,1-dichloroethane pyrolyses very much more slowly than 1,2-dichloroethane and hence it has always been considered destrable to separate the two isomers prior to pyrolysis. Tt has now been found that mixtures of these isomers can be pyrolysed without impairing the quality or yield of vinyl chloride monomer produced by regulating the concentration of the two isomers in the mixture being pyrolysed. Aecordingly the present invention is @ process for producing vinyl chloride conprising pyrolysing at elevated temperature 1,2- dichloroethane mixed with between 0.2 end 10% by weight of 1,1- dichloroethane, The above reaction may be carried out in conventional. tubular reactors,as normally employed for the pyrolysis of 1,2-dichloro- ethane, The pyrolysis of mixtures of 1,1-dichlorcethane end 1,2-10 6 20 25 2 : 0000847 dichloroethane in the specified range of concentrations significantly increases the conversion of 1,1-dichloroethane from about 20% (for the pure some) to above 90% (when present in the isomeric mixtures), Both below and above this range the conversion of the 1,2-igomer is depressed relatively.’ The amount of the 1,1-dichloroethane in the isomeric mixture being pyrolysed is preferably between 1 and 8%, ‘The 1,l-isomer may be mixed with the pyrolysis feed prior to the introduction thereof into the reaction zone, Alternatively it may be incorporated in the pyrolysis feed in the reaction zone itself at ‘the time of pyrolysis. ‘The pyrolysis of the isomeric mixtures may be carried out in packed or unpacked tubular reactors, Where packed reactors are used ‘they may suitably be packed with ceramic spheres, ‘The pyrolysis of the isomeric mixture of dichloroethanes accerding to the present invention is suitably carried out at a temperature of between 450° and 550°C, preferably between 500° and 535°C. : ‘The pyrolysis of the isomeric mixture of dichloroethanes may be carried out at sub-atmospheric, atmospheric or super-atmospheric pressures, It is, however, preferred to use super-atmospheric pressure, preferably below 500 psig. The pyrolysis of the isomeric mixture of dichloroethanes may be carried out in a continuous manner, : The advantages of the present invention are illustrated with reference to the following Examples, EXAMPLES 7 ‘The apparatus, run at atmospheric pressure, consisted of feed reservoir, metering pump, vaporiser, cracker tube, coolers, organic product receiver, hydrogen chloride scrubbing colum, scrub liquor reservoir and wet gas meter, There was also a nitrogen diluent/ carrier feed applied to the vaporiser inlet, Feedstocks comprising pure 1,2-dichloroethane (1,2-EDC), 1,2. dichloroethane with up to 10 per cent by weight of 1,1-dichloro- ethane (1,1-DCE) and also pure (98.2% by weight) 1,1-DCE were pyrolysed at a peak temperature of 500°C and @ contact time of 4.510 15 20 3 2000847 seconds under conditions found to give a 50 per cent by weight conversion of pure 1,2-dichloroetiane, Analysis of feedstock, organic condensate, serub Liquor and vent gas were used to calculate the conversions tabulated below, Conversion (weir 2,230 | 1,1-208lL : 0000847 CLAIMS +: ‘A process for producing vinyl chloride comprising pyrolysing et elevated temperature 1,2-dichloroethane mixed with between 0.1 and 10% by weight. of 1,1-dichloroethane, A process according to claim 1 wherein the amount of 1,1-dichloroethane in the isomeric mixture being pyrolysed is between 1 and 6% by weight,. © ‘A process according to claim 1 or claim 2 wherein the pyrolysis of the isomeric mikture of SEE eae is carried out at a temperature between 450% C and 550% Cc. A process according to claim 3 wherein the pyrolysis of the isomeric mixture of dichloroethanes is carried out at a temperature between 500 and 535°C. A process accarding to any of the preceding claims wherein the pyrolysis of the isomeric mixture of dichloroethanes is carried out at superatmospheric pressures, A process according to claim 5 wherein the superatmospheric pressure is below 500 psig. A process according to any of the preceding claims wherein the pyrolysis of the isomeric mixture of dichloroethanes is carried out in a continuous manner. , A process for ‘producing vinyl chloride according to claim 1 as hereinbefore described with reference to the Examples. Vinyl chioride' whenever produced by @ process according to any of the preceding claims.European Paton: . » Ofe EUROPEAN SEARCH REPORT 5900847... EP 78 30 0280 DOCUMENTS CONSIDERED TO BE RELEVANT GASB EATON THE [siogay] Gabon of document wiv indication. whore appropri, of revert | erat passages team C 07 C 21/06 X | FR= A ~ 1 306 945 (WACKER CHEMIE) | 1-9 1 17/34 * Page 4, example 5; abstract 1 * X | US - A - 2 569 923 (H.A. CHENEY) 1-9 * Pages 8,9; example 4; claim 1 # ULLMANNS ENCYKIOPAEDIE DER TECHNI- | 1 SCHEN CHEMIE, 3.Auflage, Band 18, 1967, TECHNCAL FELD Urban & Schwarzenberg, SEARCHED (m.cl9 Miinchen-Berlin-Wien, . pages 91-93 © 07 C 21/06 © 07 C 17/34 * Page 91, paragraphs 4,6, 93, bottom * A | GB A ~ 1 265 245 (WACKER CHEMIE) | 1 . | * Page 3, example 4 * A | DE = B~ 4 075 592 (ETHYL CORP.) 1 # Pages 8,9; example 2 * W___| eATERORY OF ~ AED SoC Atenrs A | GB= A = 1 168 329 (MONSANTO) 1 fel cece taeere ‘technologie! background * Page 4, example 5 * 0: non-wrten cone P: intrmodite document _ 1 teary or elaine uncetying thelnvntion , : conticorgappleaion : docamentctaaintne seston L etatontor ater reasons Teor te ae plot ‘iy, 1g “Tne prsentsezehraport hasbeen dawn op for alcaine — bs ah TO Fomm TET OE