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HOOK CR CHEMICALS S. PLASTICS CORP. NIAGARA Fus, N. . FORM 1076 a #1,54540 1-26-74 SMH Distribution: D. S. Rosenberg J. A. Cull W. L. Sutor V. J. Lloyd A. C. Schulz H* E, Buckholtz G. A. R. Trollope X Robots C, Woehr D. A. Scholes S. M. Hall M. -Brooks - Hicksville A U> aV November 26, 1974 To: From: G. C. Woehr S. M. Hall Monthly Report For November, 1974 Vinyl Chloride Abstract: Removal of vinyl chloride from stack gases via chemical reaction may be a feasible method of meeting the proposed Federal permissible exposure level of 1 ppm. A search of the Chemical Abstracts has uncovered eighty possible reactants of which four or five might be applicable. Benzene, chlorine, hydrogen chloride (with oxygen) and alkyl chlorocyclohexanes seem to react with vinyl chloride in reasonable times and at reasonable conditions (temperature, pressure) with high conversions (>907.). Study of the literature is not complete so no conclusions or recommendations are included. <^T /it. S. M. Hall Process Development /pjP I KEYWORDS: VINYL CHLORIDE POLLUTION REACTIONS OCC 1832 HOOKER CHEMICALS 4 PLASTICS CORP. NIAGARA FAULS, N. t. form of*a -2- I, Discussion The new Federal standards for vinyl chloride exposure call for a time averaged maximum of 1 ppm compared with the old standard of 500 ppm and the interim standard of 50 ppm. The new standards take effect January 1, 1975, however, it is understood that some manu facturers (particulary PVC producers) might take up to several years to meet the standards. Guidelines for air monitoring, medical examinations and respiratory equipment are applicable until the 0.5 ppm '`action level'' vinyl chloride standard is met. (See Federal Register 39:194 p, 53 (1974)). One possible method of removing vinyl chloride from stack gases is to chemically react the monomer to form a harmless or easily removable chemical. The Chemical Abstracts (Volumes 1 to date) have been searched for references to previous reaction studies. Eighty chemicals were found for which reactions with vinyl chloride have been documented (see Table 1). The vast majority of these are not applicable to the vinyl chloride pollution problem for reasons of pressure, temperature, conversion or product composition. Many of the reactions were run batchwise at high pressure for several days with the resulting vinyl chloride conversion very low (< 507.). The reactants that seem to offer the most promise are benzene, chlorine, hydrogen chloride and alkyl chlorocyclohexanes. Original articles and patents are on order which have not yet arrived so the evaluation of these reactions is at best incomplete. Even with all literature references in hand it will probably be most difficult to obtain more than an idea of possible vinyl chloride reaction schemes without laboratory work. 1. Benzene Two reactions are reported. The first, benzene + vinyl chloride 4aluminum chloride yields 1,1-diphenylethane; 9,10-dimethyldihydroanthracene; and a tar or resin. The reaction occurs at room temperature; yields and conversions are not given. Heating the reaction is said to increase tar formation. The other benzene reaction looks promising. Benzene + vinyl chloride + 947. H^SO^ (in a mole ratio of 4:1:2) react at 30*-60C. After two hours there remains 07. halo olefin and 07. initial starting material. This is from a Russian reference, not yet received. OCC 1833 MOOKfcft CHEMICALS & PLASTICS CORP, MIAGAfl* ALLS, N. Y. FORM IO?tA -3- 2. Chlorine At least a dozen references deal with the chlorination of vinyl chloride to form.dichloro- and trichloroethane. Catalytic, photochlorination batch and continuous experiments are described with yields and conversions as high as 997.. A basic problem of chlorination is that relatively toxic (10 to 350 ppm TLV) dichloro- and trichloroethane are produced and it is likely that liquefaction or scrubbing of these materials would be necessary to achieve satisfactory pollution control. Typical reactions: a. "Into a jacketed tube half-stuffed with Fe shavings just covered with CH^CCl^ was passed dry Cl mixed with Cl^CHCl <1:1.1 mols) atJ620 cc/min. while cooling the tube to 20-25 to give almost pure CH,CC1- (yield 99.27. of Cl).,, Japan 158669 b. '`Cl and vinyl chloride in a ratio of 1.02:1 (by volume) are passed into CICH.CHCl- (IX) contg. ,57. FeCl,. The TT is fed continuously into a reactor contg NaOH 1220 end H.O 11000 parts at 65-80, the CH-^CCl- distg. off. The reaction efficiency is 907.'* Brit 577876 c. ''Cl^CftCH-Cl (I) is prepd. by adding 1 mole Cl to a little more than 1 mole CH_=CHC1 (II) in at least 20 moles I in a packed tower, with the I flowing down and the mixt of Cl and II bubbled in near the middle or bottom at 20-50 in the dark. The yields are nearly theoretical.* Brit 627263. 3. Hydrogen Chloride Several references discuss HC1 addition to vinyl chloride. The product is dichloroethane; conversion is low and reaction time Is long. Oxychlorination (0, + HC1 + V.C.) achieves much better conversion, however, (as high as 937.). One patent (Neth appl. 6414743) describes a catalytic reaction in the gas phase of HC1, vinyl chloride and air (molar ratio 45:15:40) with a yield of 70.7% of 1,1,2-trichloroethane. What this means as far as conversion of vinyl chloride is concerned is uncertain. 4. Alkyl Chlorocyclohexanes 'Isomeric (B,B-dichloroethyl) methylcyclohexanes, b.80-4, were obtained in 957. yields from the condensation of CH =CHCl with a mixt. of isomeric chloromcthylcyclohexanes (I) iii the presence of purified anhydrous A1C1- when the reaction was carried out at -15 to -20 for 30-5 min. with 4-57. AICI3 based n I and a I-CH^CHCl molar ratio of 3:1." C.A. 64:15758c OCC 1834 MOOKcR CHEMICALS 4 PLASTICS CORP. NIAGARA FALLS. N. T . FORM I07AA -4- II. Future Work The literature will be studied to determine what scheme or schemes seem to offer the most hope for removing vinyl chloride from stack gases via chemical reaction. Particular attention will be paid to vinyl chloride conversion (especially when oxygen and nitrogen, eg air, are present) and to reaction product disposal (or use). Reaction mechanisms will be studied to determine if other compounds might offer an advantageous reation. 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