Document 061gVboww23RKa9EnyL3GvkYV

Vinyl chloride ------B. F. GOODRICH CHEMICAL CO. Application! A process to produce vinyl chloride mon omer and ethylene dichlonde (EDC) from ethylene, chlorine and air. Descriptions Vinyl chloride monomer is produced by thermal cracking of EDO according to the following equation: A C1H4CI1 (EDC) -* HG1 + C,Hj a The feed EDC for this operation is supplied from two sources. In the first source, ethylene and chlorine are reacted in essentially stoichiometric proportions to pro duce EDC by direct addition thusly: Cl, + C3H4 - C,HCI, In the second source ethylene Is reacted with the HC1 produced from die thermal cracking operation to pro duce EDC by oxyhydrochlorination as follows: C,H* + 2 HC1 -+ 1/20, -* CjILCl, + H0 The oxyhydrochlorination reaction takes place in a fluid bed of copper chloride impregnated catalyst. Special reactor design and process conditions allow use of an all-carbon-steel reactor without risk of corrosion. The re action products are efficiently recovered by condensation in the primary recovery unit and absorption in the sec ondary recovery unit. Unreacted HCI is discharged with the water of reaction as a dilute (less than 1%) hydro chloric add stream which is easily neutralized and dis posed of. The heat of reaction is removed by the genera tion of steam. In the direct ehlorination unit, the heat of reaction is removed with cooling water. The resultant crude EDC is combined with the crude EDC from the OHCl unit and recycle EDC from the cracking unit The mixed stream is then fractionated to remove the small quan tities of low boiling and high boiling contaminants. The purified EDC is cracked in a furnace at elevated temperature and pressure. The hot effluent gases are rap idly quenched and distilled to remove first HCI and then VCJ1. Unconverted EDC is returned to the EDC purifica tion train to remove small quantities of contaminants which would otherwise build up in the system. Commercial Installations: The Badger Co., Inc., offers engineering design and construction services for plants using this combined process scheme. B.F. Goodrich Chemi cal Co. processes are in operation, or construction at Si locations throughout the world. Aggregate capacity of the plants exceeds 13 billion pounds per year of total EDC by oxyhydrochlorination and direct chlorination, and 11 billion pounds per year of vinyl chloride monomer. Reference: U-S. patent 2,724,006 F. Hoechst; U.S. Pat ent 3,488,396 B. F. Goodrich; Chemical Week, Aug. 29, 1964, pp. 101-108; U.S. and foreign patents applied for. 214 November 1975 Hydrocarbon Processing AP00022076 Vinyl chloride -- PPO INDUSTRIES, INC. A ipflcottant A process to produce vinyl chloride monor ler from ethylene, oxygen, chlorine and hydrogen d Loride. Description* The process as presented here is for a "balat :ed-integrated" vinyl chloride plant wherein vinyl chio rit e monomer (VCM) is the sole product, and all of the ty irogen chloride (HC1) produced from the cracking of et iyiene dichloride (EDO) is recycled to the oxyehlorinatic a unit and no externally produced hydrogen chloride is us :d as feed. Under other circumstances, die process can be arranged to produce either one or both EDC and HQ as co-products. The process also is well able to receive ex ernally produced hydrogen chloride as a feed. 'n the "balanced-integrated" arrangement, EDC is pr duced in both direct chlorination and oxychlorination ur ts. n the direct chlorination unit, chlorine Is combined tvi h ethylene in the liquid phase by the addition reaction to iroduee EDC. CaKfr + CL-eCiHftCli In the oxychlorination unit ethylene, oxygen and HC1 are re< ;ted in the vapor phase over a PPG-developed catalyst to jroduce EDC. CjH, + 2HCI + 1/2 O, -* C* H*C1* + HsO ' 'he heat of reaction is recovered as high pressure steam an<. used in other portions of the process. lue to the use of oxygen and the judicious choice of de gn and materials, the oxychlorination unit operates it i high onstream factor, under moderate pressure em ploying a simplified condensation system to provide high yields and essentially corrosion free operation. The crude EDC from the oxychlorination and direct chlorination units is combined with the EDC recycled from the cracking unit and purified by distillation. Vinyl chloride monomer is produced by thermally cracking the purified EDC at high temperature. CiHCIt -V C.K.Q + HC1 The cracker effluent is quenched and the HC1 sepa rated and recycled to the oxychlorination unit. High purity polymer grade VCM is separated from the un reacted EDC. The unreacted EDC is recycled to the puri fication unit. The process has been designed and automated for safe, low manpower, high yield and high stream factor opera tion over a broad range of turndown. In addition to pro ducing high purity polymerization grade VCM, the process enjoys essentially corrosion free operation, low catalyst cost, infrequent decoking and low maintenance cost. Commercial Installations* PPG bolds more than 400 domestic and foreign patents on the subjects of oxychlor ination and vinyl chloride. PPG's oxychlorination and VCM technology was developed in the early 1950s and commercialized in the early 1960s. Polymer grade VCM and EDC axe produced by the PPG process in plants in the United States, Japan and Europe. The combined capacity of the plants now in operation and under con struction is more than 3.8 billion pounds per year of EDC and 2 billion pounds per year of VCM. I AP6o622077 Application! A process to produce vinyl chloride monomer from ethylene, chlorine and air. Anhydrous hydrochloric acid may be either consumed or produced as well as EDO. EDO is then carefully purified and thertnically cracked in a pyrolysis furnace: CjH-jCl* C*H,Q + HC1 (VCM) The products are separated, HC1 is fed back to the oxychlorination section and VCM is purified and stored. Description! Ethylene dichloride (EDC) is produced in two ways: Direct chlorination in which chlorine is reacted with ethylene in liquid EDC according to: C2H* + Cl* -*0*11*01, * Oxychlorination in which hydrochloric acid recycled from the cracking unit reacts with air and ethylene according to; CaH, + 2HC1 + /a O, -* CjH.CI, + HaO A very efficient fluidized bed catalytic system has been developed. Features: High yield due to a selective oxychlorination catalyst High reliability due to a carefully purified EDC and pyrolysis conditions (no boilers or furnace clogging, de coking cycle: more than 12 months) No pollution: waste waters suitable for biological treatment, chlorinated wastes destroyed in Rhone-Poulenc incineration process (HC1 recycled to oxychlorination). Commercial operations Rhone-Poulenc plant at La* vera, France: 350 to 500,000 tons/year MVC. < 216 1Q7^ LX' TV- . -....... AP00022078 I Vinyl chloride (Monsanto Co.) SCIENTIFIC DESIGN CO., INC. Application* Processes for die manufacture of vinyl ch! iride monomer (VCM) from ethylene, chlorine, air or ox) gen. Externally produced hydrogen chloride may also be :ed, De criptiom The flowsheet presented represents a "bal* an< >d" vinyl chloride plant, wherein all hydrogen chloride pr< duced as a coproduct of the cracking of ethylene dichloride (EDO) to monovinyl chloride (VCM) is re* eye id to the oxychlorination reactor. The latter may also rec< ive externally produced hydrogen chloride as a feed. Ret ctions) C ,H, + Cl, CjH.CI, (Direct Chlorination) >H4 + 2HCI+1/2 O, C,H*C1, + H,0 (Oxychlor- mat on) C tHCIa CH, = CHCI + HCI (Cracking) T ie oxychlorination process Is a vapor-phase reaction carr ed out in a carbon steel reactor operating at moder ate ] ressures. In direct chlorination, ethylene and chlorine gases are charged to a reactor system containing liquid EDC as reaction mwriting and coolant The EDO pro duced in the reaction system is then treated for removal of chlorine and HCL The crude EDC is purified by distillation and fed to pyrolysis furnaces where it is cracked to yield vinyl chlor ide and HCL The anhydrous hydrogen chloride Is recycled to the oxychlorination reactor. Vinyl chloride is refined to product meeting the highest industrial specifications. Commercial Installations! Monsanto Co., Texas City, Texas; Electrochemical Industries (Frutarom) Ltd, Haifa, Israel; Mitsubishi Chemical Industries, Ltd, Mizushima, Japan; Mitsubishi Monsanto, Yokkaichi, Japan; Petroleos Mesdeanos, Pajaritos, Vera Crux; Mex ico; Chinese Petroleum Carp., Kaohsiung, Formosa. References Ozero, B. J. and Schaffel, G. S., "The Mon santo-Scientific Design Vinyl Chloride Process" AIChE, Houston, March 1971. AP00022079