EP 0 883 588 B1 European Patent Office Office européen des brevets Europaisches Patentamt (it) EP 0 883 588 B1 (12) EUROPEAN PATENT SPECIFICATION (45) Date of publication and mention of the grant ofthe patent: 19.09.2001 Bulletin 2001/38 (21) Application number; 96944988.3 (22) Date of fling: 17.12.1996 (61) Int ci7: CO7C 17/02, CO7C 17/25, C07C 21/06, CO7C 19/045, C258 1/26 (86) International application number: PcT/Uss6/20532 (87) International publication number. WO 97/24306 (10.07.1997 Gazette 1997/30) (64) PRODUCTION OF ETHYLENE DICHLORIDE BY DIRECT CHLORINATION AND PRODUCTION OF VINYL CHLORIDE MONOMER USING CHLORINE RECYCLE HERSTELLUNG VON ETHYLENDICHLORID DURCH DIREKTCHLORIERUNG UND. HERSTELLUNG VON VINYLCHLORID-MONOMER UND ZURUECKFUEHRUNG VON CHLOR PRODUCTION DE DICHLORURE D’ETHYLENE PAR CHLORATION DIRECTE ET PRODUCTION DUN MONOMERE DE CHLORURE DE VINYLE A L'AIDE DE CHLORE RECYCLE (84) Designated Contracting States: CH DEFRGBITLINL (80) Priority: 28.12.1995 US 9515 (43) Date of publication of application: 16.12.1998. Bulletin 1998/51 (73) Proprietor: El. DU PONT DE NEMOURS AND COMPANY Wilmington Delaware 19898 (US) (72) Inventors: * FREIRE, Francisco, Jose Wilmington, DE 19803-3938 (US) + KAISER, Bruce, Arthur ‘Wilmington, DE 19807-2200 (US) + MAH, Dennie, Turin Wilmington, DE 19810-2430 (US) + FELIX, Vinci, Martinez Kennett Square, PA 19348-1831 (US) + LAW, Clarence, Garlan, Jr. West Trenton, Nv 08628-2022 (US) + TRAINHAM, James, Arthur, II Newark, DE 19711-3444 (US) + NEWMAN, John, Scott Kensington, CA 94708 (US) + EAMES, Douglas, John ‘Chamblee, GA 30341 (US) (74) Representative: Beacham, Annabel Rose Frank B. Dehn & Co., European Patent Attorneys, 179 Queen Victoria Street London EC4V 4EL (GB) (86) References cited: EP-A- 0 260 650 Wo-A-95/14797 + HYDROCARBON PROCESSING, vol. 71, no. 8,1 ‘August 1992, pages 129-132, 134, XP000293720 WONG E W ET AL: "PRODUCE HIGH PURITY vem PRopucT* Note: Within nine months from the publication ofthe mention of the grant ofthe European patent, any person may give notice to the European Patent Office of opposition to the European patent granted, Notice of opposition shal be fled in ‘a writen reasoned slatement, it shall nt be deemed lo have been filed untl the oppostion fee has been paid. (Art 99(1) European Patent Convention), Pam Joom, 70% PRAISE)2% 2% EP 0 883 588 BI Description 1, Elold ofthe Invention [0001] The present invention relates to & process and a system for producing ethylene dichloride by direct chlorn ation, and for producing vinyl chloride monomer from this ethylene dichloride using chlorine recycle. 2, Deseription ofthe Related Ar [0002] Ethylene dichloride (EDC) has value as a chemical intermediate, See Riege!'s Handbook of Industrial Chem: sty, Seventh Edition, Van Nostrand Reinhold Company, pp. 783 - 785. Most of the EDC produced goes Into the manufacture of vinyl chloride monomer (VCM). Vinyl chide monomer, CHp=CHCI, by virtue of the wide range of ‘pplcations for its polymers in both flexible and rigid forms, is one ofthe largest commodity chemicals in the United States and is an important item of international commerce, See Kirk Othmer, Encyclopedia of Chemical Technology, ‘Thirdeition, Volume 23, pp. 865 - 866 (1983). For instance, vinyl chide monomeris used to makepoly(viny chloride). [0003] Hydrogen chloride (HC), in either anhydrous form or aqueous form (also referred to as hydrochloric acid), is 2 reaction by-product of many manufacturing processes which use chlorine. For example, chlorine is used to manu: facture polyvinyl chloride, isocyanates, andchlorinated hydrocarbonsiorinated hydrocarbons, with hydrogen chloride fas a by-product of these processes. Because supply so exceeds demand, hydrogen chloride, or hydrochloric acid, often cannot be sold or used, even after careful purification. Shipment overlong distances is not economically feasible. Discharge of the chloride ions or the acid into waste water streams is environmentally unsound, Recovery and feedback ofthe chlorine to the manufacturing process isthe most desirable route for handling the HCl by-product [0004] Direct chlorination isa known process for making VCM., However, this process does not recover and feed the chlorine back to the VCM manufacturing process, and therefor, Its not used commercially, Because of the environ: ‘mental considerations which make recovering and feeding chlorine back to a manufacturing process which uses chlo: rine particularly desirable, a balanced process using an oxychlorination process has been developed to make vinyl chloride from ethylene dichioride Ina typical plant producing vinyl chioride from ethylene cichloide, HCl is produced through pyrolysis of ethylene dichloride, and all the HC! produced inthis pyrolysis is normally used as the feed for ‘oxychiorinaton. In this process, EDC production is about evenly split between direct chlorination and oxychlorination, {and there is no net production or consumption of HCI [0005} A plant, or system, employing a currently used balanced oxychlorination process for ethylene-based vinyl chloride production isilustrated in the block flow diagram of Fig 1. The plants shown generally at 10. Plant 10 includes {a direct chlorination reactor as shown at 12 in Fig, 1. A fist inlet feed line 14 as shown in Fig, 1 feeds ethylene (C,) to the direct chirination reactor. A second inlet feed ine 16 feeds chiorine (Cl) tothe dect chlorination reactor. The ethylene and the chiorine are reacted in the reactor to produce ethylene cichioride (EDC). The EDC is sent through a line 17 to an ethylene dichloride (EDC) purfcation uni 18 [0006] The EDC purtication unit pure the ethylene dichloride, and light and heavy ends, which are a by-product Of this purification, are released through a line 20 as shown in Fig. 1. Plant 10 also includes an ethylene dichloride (EDC) pyrolysis unit 22 as shown in Fig. 1. The purified EDC is delivered to the pyrolysis unit through a line 21. The pyrolysis unt pyrolyzes the ethylene dichloride to produce vinyl chloride monomer (VCM) and essentially anhydrous hydrogen chloride, which are both sent to a viny chioride monomer (VCM) purfcation unit 24 through a line 23 as shown in Fig. 1. The VGM purification unit separates the VCM and the essentially anhydrous hydrogen chloride. The \VCM is sent through a line 26 for further purification. A portion of the EDC is unreacted inthe pyrolysis unit, and may bbe recycled backto the EDC purification unit from the VCM purification unit through a line 28. The essentially anhydrous hhydrogen chloride is sent through a line 30 as shown in Fig. 1 to an oxychlorination reactor 32. Oxygen is added to the oxychlorination reactor through a line 34 as shown in Fig. 1. In addition, ethyiene (CgH,) from frst inlet feed line ‘4's addedto the oxychlorination unit through aline 36. Crude EDC, which has many impurties, and water are formed in the oxychlorination reactor, which are sent through a line 38 to an ethylene dichloride (EDC) dryer 40 as shown in Fig. 1. The EDC is dried in the EDC dryer, and the water resulting trom this drying is released from the EDC dryer through a line 42, The crude EDC from the EDC dryer is sent through @ line 44 back to the EDC purification unit [0007] Ethylene dichloride made from the oxychlorination process is generally less pure (~93 W.% yield) than EDC produced by direct chlorination and, thus, is usuelly washed with water and then with caustic solution to remove water extractable impurities. In contrast, direct chlorination generally produces EDC with a purity greater than 98.5 wt.% and, ‘excopt for removal of the catalyst used in the formation of ethylene dichloride, such as ferric chloride, litle further purification is necessary. Moreover, compared with direct chlorination, the oxychlorination process is characterized by higher capital investment and higher operating costs and less pure EOC product. However, the use of the oxychlorin ation process is dictated by the need to consume the HCI generated in EDC pyrolysis. [0008] Therefore, there exists @ need to develop a system and a process for producing EDC by direct chlorination,2% 2% EP 0 883 588 BI ‘Such a system and process could be used to make a wide variely of products from the EDC, including, in particular \VCM. The VCM manufacturing process produces anhydrous hydrogen chloride (AHCI), whichis dificult to dispose of, as noted above. Therefore, the need also exists to develop a system and a process for producing VCM which is able to use the AHC! from this process and recycle the chlorine from this AHCI back to the VCM manufacturing process. ‘SUMMARY OF THE INVENTION [0009] The present invention solves the problems of the prior art by providing a process and a system for manufac: turing EDC by direct chlorination. This EDC may be used in a process for making VOM which recycles chlorine to the VM manufacturing process and which eliminates the need for an oxychlorination unit or an EDC dryer. This results Inless capita investment and lower operating costs in producing EDC or VOM as compared to processes and systems ofthe prior art [0010] Moreover, since the process and the system of the present invention produce EDC by direct chlorination alone, and not by oxychilorination, the EDC produced by the present invention is much cleaner, L., thas much less light and heavy ends, than that produced by the prior at. This resulls in & much purer product (Le., purity greater than 99.5 wl.%, as opposed to aboul 93 wt.% for oxychlorination). In addition, less processing is necessary to achieve this, purer product. Furthermore, by producing much purer EDC, the process and system of the present invention reduce the formation of undesirable by-products and thus the cost of disposal of such by-products. [0011] _Inadaition, the oxychiorination process ef the prior art consumes oxygen, thus adding expense te the process, In contrast, the process and the system of the present invention produce hydrogen, a valuable commodity, thereby increasing the profitabilly of making EDC or VCM [0012] Thus, for all these reasons, the process and system of the present invention are more economical than proc: cesses and systems of the prior art for producing EDC or VOM. In addition, the process and system of the present Invention are more environmentally acceptable than prior art processes and systems for manufacturing VOM, since they minimize or eliminate the environmental problems associated with the disposal of undesirable by-products in the VM manufacturing process, such as anhydrous hydrogen chloride. [0013] To achiove the foregoing solutions, and in accordance with the purposes of the invention as embodied and broadly described herein, there is provided a system for producing ethylene dichloride from chlorine gas produced by the electrochemical conversion of anhydrous hydrogen chloride, comprising: a direct chlorination reactor; a first inlet supply line for supplying ethylene to the direct chlorination reactor; a second inlet supply line for supplying chlorine to the direct chlorination reactor, wherein the ethylene and the chlorine react in the direct chlorination reactor to produce ethylene dichloride: and an electrochemical cell including means for oxidizing he molecular anhydrous hydrogen chlo: Fide to produce dry chlorine gas and protons, an anode chamber disposed adjacent the oxidizing means, anode-side inlet means disposed in uid communication with the anode chamber for introducing the anhydrous hydrogen chloride tothe oxidizing means and anode-side outlet means also disposed In fluid communication withthe anode chamber for discharging the chlorine gas, cation-ransporting means for ransporting the protons therethrough, wherein the oxidizing ‘means is disposed in contact with one side of the cation-transporting means, means for reducing the transported protons, wherein the reducing means is disposed in contact with the other side of the cation-transporting means, a cathode chamiver disposed adjacent the reducing means, cathode-side inlet means disposed in luid communication with the cathode chamiver for introducing a fluid to the other side of the cation-transporting means and cathode-side outlet means also disposed in fluld communication with the cathode chamiber; a purification unit for liqualying the chlorine gas to liquid cry chlorine; and a recycie line connected to the outlet means al one end thereof and to the ‘second inlet supply line atthe other end thereat for recyeling the liquid dry chlorine to the direct chlorination reactor, [0014] Furtherin accordance withthe purposes of the invention, there is provided a system for producing vinyl chlo ride monomer from chiorine gas produced by the electrochemical conversion of anhydrous hydrogen chioride, com: prising: a direct chlorination reactor; a first inlet supply ine for supplying ethylene to the direct chlorination reactor; a ‘second inlet supply line for supplying chlorine to the direct chirination reactor, wherein the ethylene and the chlorine react in the direct chlorination reactor to produce ethylene aiehloride: a pyrolysis unit for pyrolyzing the ethylene dichlo: ride to produce vinyl chloride monomer; and an electrachemical cell including means for oxidizing the molecular an hydrous hydrogen chloride to produce dty chlorine gas and protons, an anode chamber disposed adjacent the axicizing ‘means, anode-side inlet means disposed in fluid communication with the anode chamber for introducing the anhydrous, hydrogen chloride to the oxidizing means and anode-side outlet means also disposed in fluid communication with the anode chamber for discharging the chlorine gas, cation-transporting means for iransporting the protons therethrough, whorein the oxidizing means is disposed in contact with one side ofthe cation-transporting means, moans for reducing tho transported protons, wherein the reducing moansis disposed in contact with the othorside ofthe cation-transporting ‘means, a cathode chamber disposed adjacent the reducing means, cathode-side inlet means disposed in fuld com: ‘munieation with the cathode chamber for introducing a fluid to the other side of the cation-transporting means and ccathode-sde outlet means also disposed in fluid communication with the cathode chamber; a purifier for lquetying the