Patented Dec. 10, 1946 2,412,550 UNITED STATES PATENT OFFICE 2,412,550 PRE PARATION OF ETHYL HALDES Donald C. Bond, Northbrook, and Michael Savoy, Chicago, Ill., assignors to The Pure Oil Com pany, Chicago, Ill., a corporation of Ohio No Drawing. Application November 1, 1944, Serial No. 561,486 16 Claims. (C. 260-663) 2 This invention relates to the preparation of in the reactants and subsequently separated ethyl halides from ethylene or ethylene-contain from the reaction products and continuously re ing gases and hydrogen halides, and is more par cycled, ticularly concerned with a process in which the Another method of carrying out the process is reaction is catalyzed by means of zirconium salts. to Suspend or dissolve the catalyst in an inert An object of the invention is to provide a proc liquid, such as nitrobenzene, which does not boil ess for preparation of ethyl halides. under reaction conditions, and pass the reactants Another object of the invention is to provide through the body of liquid containing the sus a method for the preparation of ethyl chloride pended Catalyst. from hydrocarbon gases containing minor 0. When charging an ethylene-containing gas, in amounts of ethylene. Which the ethylene is present in minor propor Still another object of the invention is to pro tions, to the process, it may be desirable to mix vide a new catalyst in the Synthesis of ethyl therewith hydrogen halide in excess of the halides fom ethylene or ethylene-containing gases amount necessary to stoichiometrically react and hydrogen halides. 5 With the ethylene. By providing an excess of hy We have discovered that not only can high drogen halide a larger portion of the ethylene yields of ethyl halides be obtained by the reaction is caused to react than would react if the ratio of ethylene or ethylene-containing gases and hy of ethylene to hydrogen halide was stoichiometric. drogen halides in the presence of zirconium salts, Where dilute ethylenic gas is used as charging particularly zirconium tetrachloride and zir 20 material it is not desirable to recycle the ef conium oxychloride, but that the life of the cata fluent gas, as it only dilutes the fresh charging lyst is extremely long as compared to the life of stock. Therefore it is desirable to react as much Friedel-Crafts catalyst such as aluminum chlo as possible of the ethylene in the charging gas ride when used in the same type of synthesis. before discarding it. In accordance with our process ethylene or an 2 s Where the charging gas is substantially pure ethylene-containing gas, Such as the gases re ethylene it may be desirable to charge an excess Sulting from the cracking of hydrocarbon oils, in of ethylene over the amount stoichiometrically admixture with anhydrous hydrogen halide is neceSSary to react With hydrogen halide in order contacted With Zirconium Salt at a temperature to completely consume the hydrogen halide and of approximately 200-750 F., and preferably at 30 avoid recovery thereof from the effluent gas. The temperatures of approximately 350-500 F., and ethylene in the effluent gas can readily be sepa at atmospheric or superatmospheric pressure. rated from the reaction products and be recycled When operating under atmospheric pressure we to the process. prefer to operate within the limits of approxi In order to demonstrate the invention a cata mately 200-500 F. since attemperatures above 35 lyst Was prepared by dissolving in concentrated 500 F. at atmospheric pressure the ethyl halides hydrochloric acid, zirconium oxychloride, and dissociate to a marked extent. If the process is mixing the zirconium oxychloride solution with carried out under superatmospheric pressure, active charcoal in such amount that 20 grams of temperatures above 500 F. may be used with good Zirconium oxychloride (ZrOCl2.8H2O) were pres results, since the dissociation of ethyl halides is 40 ent per 100 cc. of active charcoal. The mixture Suppressed by superatmospheric pressure. Thus WaS evaporated to remove the water and was the higher the pressure the higher the tempera then dried at 400 F. A steel reactor having an ture at which the reaction may be carried out. inside diameter of approximately 1.5 inches and a Contact times ranging from a few seconds to length of approximately 14 inches, and a volume Several hours may be used. Where continuous 45 of 375 cc. was filled with the catalyst. Ethylene operation is practiced the contact times will be Was passed through the catalyst at the rate of relatively short particularly where unreacted ma 0.17 cubic foot per hour admixed with anhydrous terial is recycled. In batch Operations contact hydrogen chloride passed through the reactor at times will approach those necessary to establish the rate of 0.21 cubic foot per hour, both meas equilibrium conditions. 50 ured at standard temperature and pressure. The The process may be carried out by passing the catalyst was maintained at a temperature of reactants through a bed of the catalyst, prefer 370 F. During the first hour of the run no ethyl ably in the form of a Solid porous carrier impreg chloride was produced. In the next interval of 2.2 nated with the zirconium salt, or the catalyst in hours, 9.2 grams of ethyl chloride Was produced, finely divided or powder form may be suspended 55 corresponding to a conversion of 30.4% on the 2,412,550 3 basis of the ethylene, and 24.7% on the basis of It will be seen, therefore, that we have de the hydrogen chloride. veloped a process for synthesizing ethyl halides, In the next interval of 3 hours the rate of particularly ethyl chloride, in the presence of flow of ethylene was 0.18 cubic foot per hour and catalysts which have a high activity and which anhydrous hydrogen chloride was 0.17 cubic foot do not rapidly become Spent during use. per hour, measured at standard temperature and It is claimed: pressure. During this 3 hour period 21.6 grams . . The method of preparing ethyl halides Com of ethyl chloride was produced corresponding to prising contacting a mixture of an ethylene-con a conversion of 49.3% based on the ethylene taining gas and hydrogen halide with a Zirconium charged and 42.1% based on the hydorgen chlo O Salt at a temperature at which the ethylene and ride charged. hydrogen halide combine. Under approximately the same conditions 2. Method in accordance with claim 1 in which above stated using active charcoal alone as cata the temperature is approximately 200-750 F. lyst, a conversion of about 5% based on both the and the reaction is carried out under Superat ethylene and hydrogen chloride was obtained. 5 mospheric pressure. As another example of our process a catalyst 3. Method in accordance with claim in which was prepared by impregnating silica gel with Zir the temperature is approximately 350-500 F. conium oxychloride in the manner above de 4. Method in accordance with claim 1 in which scribed in connection with the impregnation of the zirconium salt is zirconium oxychloride. active charcoal, so that the catalyst contained 20 5. Method in accordance with claim 1 in which grams of zirconium oxychloride per 100 cc. of sil the zirconium Salt is zirconium tetrachloride. ica gel. Using the silica gel impregnated with 6. The method of preparing ethyl chloride zirconium oxychloride as catalyst in the same re comprising contacting a mixture of ethylene actor as above described at a temperature of 385 containing gas and anhydrous hydrogen chlo F. and with a hydrogen chloride to ethylene ratio 25 ride with a catalyst comprising a zirconium Salt of approximately 1, and contact time of approx at a temperature of approximately 200-750 F. imately 2 minutes, a conversion of 66% to ethyl and the reaction is carried out under Superat chloride based on the ethylene charged and 64% mospheric pressure. on the hydrogen chloride charged over a period 7. Method in accordance with claim 6 in which of 120 hours was obtained, as against a 34% con 30 the salt is zirconium tetrachloride. version for active charcoal impregnated with zir 8. Method in accordance with claim 6 in which conium oxychloride under the same conditions, the salt is zirconium. Oxychloride. thus demonstrating the unusual catalytic effect 9. Method in accordance with claim 6 in which obtained by using silica gel as the support for the the catalyst is a solid porous carrier impregnated zirconium salts. During the first 12 hours of with a zirconium Salt. the run the conversion to ethyl chloride was 66% 10. Method in accordance with claim 6 in which and 67%, respectively, and during the last 6 the catalyst is active charcoal impregnated with hours of the run the conversion to ethyl chloride. a Zirconium Salt. was 67% and 64%, respectively, thus showing 11. Method in accordance with claim 6 in which that the activity of the catalyst remained sub the catalyst is silica gel impregnated with zir stantially constant during the entire run. conium Oxychloride. As another example of our process 35 grams 12. Method in accordance With claim 6 in which of zirconium tetrachloride was mixed with 350 the catalyst is silica gel impregnated with zir cc. of nitrobenzene. Ethylene and anhydrous conium tetrachloride. hydrogen chloride were passed through this solu 13. The method of preparing ethyl chloride tion maintained at a temperature of 266 F. at a comprising Contacting a mixture of ethylene rate of 0.16 cubic foot per hour of ethylene and containing gas and anhydrous hydrogen chlo 0.15 cubic foot per hour of anhydrous hydro ride at a temperature of approximately 350-500 gen chloride, both measured at standard ten F. with a catalyst prepared by impregnating a perature and pressure. At the end of 3.5 hours : solid porous carrier with a solution of zirconium 37% of ethyl chloride on the basis of the ethyl oxychloride in hydrochloric acid and drying the ene charge, and 39.7% of ethyl chloride on the resulting mixture. m basis of the hydrogen chloride charge WaS pro 14. Method in accordance with claim 3 in duced. The yield of ethyl chloride was increas which the carrier is Silica ge. ing as the experiment proceeded. 5 5 15. The method of preparing ethyl chloride Although we prefer the halides and oxyhalides comprising contacting a mixture of ethylene of zirconium as catalysts, other salts of zirconium, containing gas and anhydrous hydrogen chloride such as the sulfates, nitrates and phosphates, may at a temperature of approximately 350-500 F. be used with good results. with a catalyst prepared by impregnating a solid In continuous operations contact times of ap 60 porous carrier with zirconium oxychloride. proximately 1 to 10 minutes give good yields. In 16. Method in accordance with claim 15 in batch operations longer contact times may be which the carrier is Silica gel. resorted to in order to reach equilibrium condi DONATD. C. BOND. tons. MICHAE, SAVOY,