Патент USA US2411236код для вставки
D Patented Nov. 19, 1946 ' ‘2,411,236 UNITED STATES PATENT OFFICE" 2,411,236‘ METHOD OF CONVERTING HYDROCARBONS INTO ORGANIC SULPHUR COMPOUNDS Carlisle M. Thacher, Highland Park, 111., assignm to The Pure Oil Company, Chicago, 111., a cor poration of Ohio No Drawing. Application March 30, 1940, Serial No. 326,963 7 Claims. (01. 23-206) 1 , This invention relates to a method of convert . 2 sures in?uence the reactions in the desired di ing hydrocarbons, particularly lowlboiling par rection. Typical reactions which may take place a?inic hydrocarbons, .to organic sulfur com - between a normally gaseous paraflinic hydrocar pounds, especially carbon-sulfur compounds. bon such as methane and sulfur are as follows: This application is a continuation in ,part of co-pending application Serial No. 177,411, filed December 1, 1937. " _ An object of this invention is to convert hydro carbons into organic sulfur compounds. Another object of this invention is to convert 10 low boiling para?inic hydrocarbons into carbon sulfur compounds. The amount of sulfur charged‘ with the hydro- ’ carbon may be varied between rather wide lim its depending upon a number of factors among which are time of residence of the reactants in . A further object of this invention is to cat alytically convert hydrocarbons into carbon-sul fur compounds at such temperatures as to afford 15 the reaction zone, particular products desired and . a minimum of corrosion to the apparatus in : reaction temperature and pressure. Where in which the process is conducted. termediate sulfur oxidation products are desired ' ‘ the sulfur should not be in excess of that nec Other objects of the invention will become essary to react with the'hydrocarbons to form apparent from the following description. It has been discovered that hydrocarbons can 20 mercaptans. In general the amount of sulfur charged with the gas is preferably not in excess be reacted with sulfur, selenium and sulfur or selenium yielding compounds at elevated tem‘ of that necessary to stoichiometrically react with peratures in the‘presence of a suitable catalyst I the hydrocarbon to form the desired organic sul- - fur compound. By controlling the proportion of bon-sulfur compounds and including alkyl sulfur 25 sulfur within this range, maximum yields of de compounds. As examples of such- compounds sirable reaction products may be obtained. The to form organic sulfur compounds such as car may be mentioned carbon disui?de and methyl, reactor as well as the remainder of the appara ethyl, propyl and butyl mercaptans. In carrying out the invention, substantially tus may be fabricated from ordinary iron, al though stainless steel, chromium steel, molyb 30 denum steel, silica, quartz or other materials which are resistant to sulfur corrosion or non ’ pure hydrocarbons such as methane, ethane, pro pane or butane or mixtures thereof or other hy resistant steel lined with a refractory lining drocarbons may be used as starting materials. such as silica or quartz are preferred. For example, when the starting material is a As shown by the foregoing equations, sulfur hydrocarbon gas such as'methane, the methane is heated and mixed with sulfur vapors and the 35 may react with hydrocarbon gas to form mer captans, thio-ethers and organic disul?des such mixture fed into a reactor where the mixed gas and sulfur vapor is contacted with appropriate as dimethyl disul?de and carbon disul?de. The catalyst. As catalysts suitable for effecting the reaction products are cooled and the organic conversion of hydrocarbons to organic sulfur sulfur compounds separated therefrom by frac compounds may-be mentioned oxides or sul?des 40 tionation, absorption in a suitable solvent such ‘as naphtha and subsequently separated therefrom of vanadium, manganese, copper, iron, cobalt, nickel, chromium and molybdenum. The sul by fractionation or by other suitable means. The . particular method of separation of reaction prod ?des of these metals are generally preferred. These compounds may be used alone or supported ucts from unreacted materials will depend large on materials such as silica gel,~ alumina gel, 45 ly upon the composition of the reaction products. Any hydrogen sul?de present may be separated pumice or charcoal, etc., which of themselves may possess catalytic activity. The reactants are pref from organic sulfur compounds by conventional erably contacted at temperatures of approximate- , methods such as by scrubbing with water or ly 400-700° C. and under pressures of approxi aqueous alkali under appropriate conditions of mately 1 to 125 atmospheres. While good yields 50 temperature and concentration and prior to sep , may be obtained under a relatively large number aration of the organic sulfur compounds from of satisfactory operating conditions of temper ature and pressure within the desired range, those conditions are preferred which maintain the reactants in the vapor phase. Elevated pres the remaining gases. Unreacted gases may be re " cycled for further reaction. Selenium may be substituted for sulfur when the reaction tempera 55 ture is sufficiently high to vaporize selenium. As 2,411,23o 4 sources of sulfur, compounds thereof which read ily yield free sulfur. may be used. The appara tus in which the process is carried out may be of any conventional type consisting of a heat ing means and reaction, chamber with cooling , . , was obtained. In all 0! the foregoing examples pressures slightly above atmospheric were em ployed. It is not intended that the invention shall be limited by the foregoing speci?c examples which ‘and fractionating and/or other separating means are presented for purpose of illustration, but that the invention shall be limited only by the connected to the reaction chamber. In a specific example methane was mixed with scope of the claims. What is claimed is: sulfur in a ratio of 0.58 mol of methane to one incl oi’ sulfur vapor. calculated as diatomic sul 10 1. The method of preparing carbon-sulfur compounds which comprises contacting paraf fur, and the mixture contacted with iron sulfide at a space velocity of 775 and at a temperature flnic hydrocarbon gases with sufficient sulfur , of 594° to 600° C. Space velocity may be de vapors to stoichiometrically‘ react with the gases ?ned as the ratio of the total volume of vapor to form mercaptans at a temperature of at least charged per hour to the total volume of-cata 15 400° 0., at which the sulfur and hydrocarbon lyst space. A liquid condensate was obtained, gases chemically react, in the presence of a the major portion of which was carbon disul?de catalyst selected from the group of preformed and which contained minor portions of inter metal sulfides. mediate suliur oxidation products. In another 2. Method in accordance with claim 1 in run using the same catalyst, 0.55 mols of 20 which the ‘temperature is between approximately methane was mixed with one moi of sulfur vapor, 400° and 700° C. calculated as diatomic sulfur, and the mixture 3. Method in accordance with claim 1 in contacted with the catalyst at a space velocity which the catalyst is supported on a carrier of ‘794 and a temperature of 594° C. to 598° C. selected from the group of silica gel, alumina A liquid condensate was obtained, the major por gel, pumice and charcoal. tion of which was carbon disul?de and which 4. Method in accordance with claim 1 contained- minor portions of intermediate sul which the catalyst is iron sul?de. fur oxidation products. In another run at a 5. Method in accordance with claim 1 temperature of 594° C. to 599° C. and using a which the catalyst is cobalt sul?de. proportion of 5.54 mols of methane to one mol 30 6. Method in accordance with claim 1 of sulfur vapor, calculated as diatomic sulfur, which the catalyst is nickel sul?de. the mixture was contacted at a space velocity of ‘7. Method in accordance with claim 806 with a catalyst consisting of manganese sul which the catalyst is a sul?de selected from the ?de deposited on Activated alumina in a ratio of group consisting of vanadium, manganese, cop 1 to 20. A liquid product consisting principally 35 per, iron, cobalt, nickel, chromium and molyb of carbon disul?de and containing minor por denum sul?des. tions of intermediate sulfur oxidation products, CARLISIE M. 'I'HACKER.