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United States Patent (19) 11) 4,166,189 Wald Et Al

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United States Patent (19) 11) 4,166,189 Wald Et Al United States Patent (19) 11) 4,166,189 Wald et al. (45) Aug. 28, 1979 54 PRODUCTION OF METHYL ESTERS BY (56) References Cited CONTACTING METHANOL OR DIMETHYL. U.S. PATENT DOCUMENTS ETHER WITH CARBON MONOXDE AND ZANCODOE 1,562,480 1 1/1925 Wietzel et al. ....................... 560/232 FOREIGN PATENT DOCUMENTS 75) Inventors: Milton M. Wald; Leo Kim, both of Houston, Tex. 11671.16 10/1969 United Kingdom ................ 260/533A Primary Examiner-Vivian Garner (73) Assignee: Shell Oil Company, Houston, Tex. Attorney, Agent, or Firm-Howard W. Haworth; Ronald L. Clendenen 21 Appl. No.: 899,056 57 ABSTRACT Method for the production of branched chain esters (22) Filed: Apr. 24, 1978 comprising contacting methanol and/or dimethyl ether and carbon monoxide with zinc iodide at a temperature (51) Int. C.’....................... CO7C 67/36; CO7C 67/37 of from about 180° C. to 450° C. Improved selectivity to (52) U.S. C. ................................ 560/232; 260/652 R; methyl pivalate is obtained by incorporating ethylene, 560/233; 585/409; 585/733; 585/943 propylene and/or isobutylene into the reaction mixture. (58 Field of Search ................ 560/232, 233; 260/.532, 260/533 A; 562/517,519, 521 6 Claims, No Drawings 4,166,189 1. 2 invention. The purity of the methanol is not critical, PRODUCTION OF METHYLESTERs BY provided the impurities do not interfere with the reac CONTACTING METHANOL OR DIMETHYL tion. Thus, small amounts of water and ethanol, com ETHER WITH CARBON MONOXDE AND ZINC mon impurities in methanol, do not interfere. In general, ODDE dilute streams of methanol may be used, provided, as noted, the diluents do not interfere with the activity of BACKGROUND OF THE INVENTION the zinc iodide. The term "methanol', as used in the 1. Field of the Invention specification and claims, is intended to include the use This invention relates to a method of producing of such dilute streams containing methyl alcohol. More branched chain esters as for example methyl-2,2,3,3-tet 10 over, any material which will react to provide methanol ramethylbutyrate, from methanol and carbon monox in situ under the reaction conditions specified herein, ide. and which does not interfere with the reaction, and 2. Description of the Prior Art whose other reaction product or products, if any, do Previous efforts to convert methanol to higher car not interfere with the reaction, is within the scope of the bon number molecules have led to hydrocarbons rather 15 invention. For example, dimethyl ether may be used as than esters. Even this prior experimental work with a source of methanol, either as the total feed, or a por methanol conversion to hydrocarbons may be charac tion thereof. Under some conditions, disclosed herein, terized as largely academic or substantially uneconomic significant quantities of dimethyl ether may be formed. in present terms. For example, as early as 1878, LeBel This dimethyl ether may be separated and recycled, and Green (Compt. Rend. Vol. 87, p. 260) produced 20 thereby providing a highly efficient use of source mate alkyl hydrocarbons by contacting methanol with zinc rials. chloride at elevated temperatures. More recently, Grosse and Snyder describe and claim a process in U.S. The carbon monoxide utilized in this invention may Pat. No. 2,492,984 wherein a mixture consisting essen be pure or mixed with gases that are inert to the reaction tially of a specified metal halide and at least one com 25 conditions. Synthesis gas can provide an excellent pound selected from the group consisting of methanol source of carbon monoxide. Significant amounts of and dimethyl ether is subjected to conversion condi hydrogen do not interfere with the reaction. The car tions, including a temperature of 250 C. to 650 C., to bon monoxide partial pressure in the reaction mixture is form substantial amounts of recoverable hydrocarbons maintained at partial pressure greater than 100 psia, having at least four carbon atoms. The examples of the 30 preferably greater than 1000 psia. The molar ratio of patent employ a zinc chloride catalyst, and the specifi carbon monoxide to methanol or dimethyl ether must cation mentions that higher atomic weight halides of be kept relatively high to favor the formation of metals such as zinc, cadmium, thorium, and the like, branched chain esters. The ratio of carbon monoxide to may be used. methanol should be greater than 0.25 and preferably Normally, methanol conversion in zinc halides results 35 greater than 10. in alkanes and alkenes, even when conducted in the Lower carbon number olefins may be introduced into presence of olefins, e.g. see U.S. applications Ser. No. the reaction mixture to provide an increase in methyl 850,872 and 850,874 both filed on Nov. 14, 1977, as well pivalate production. Preferred olefins are ethylene, as U.S. Pat. No. 4,059,647 issued Nov. 22, 1977. The propylene and isobutylene, with isobutylene being par particular advantage of this invention is that carboxylic ticularly preferred. acid esters are also produced. The highly branched The zinc iodide need not be pure, but may contain ester products of the invention find use as solvents and impurities which do not interfere with the reaction. chemical intermediates. Commercial grade zinc iodide is acceptable in the pro cess of the invention. SUMMARY OF THE INVENTION 45 Temperatures employed in the reaction range from Accordingly, the invention provides a method for the about 180° C. to about 450 C., preferably from about production of branched chain esters by reacting metha 190° C. to about 350° C. and most preferably from about nol, dimethyl ether or mixtures thereof with carbon 200' C. to about 280 C. monoxide at a ratio of carbon monoxide to methanol of The ratio of olefin when utilized to methanol is greater than 0.25 in the presence of zinc iodide, at a 50 widely variable, and those skilled in the art may vary temperature of from about 180° C. to about 450° C. The the proportions as desired. Thus, a ratio of 0.1 mols to use of zinc bromide does not give the same beneficial 25 mols of methanol permol of olefin may be employed, results. The invention produces methyl esters of with a ratio of from 0.3 mols to 10 mols of methanol per branched acids having carbon numbers from about five mol of olefin being preferred. At the same time, how to about eight. The invention particularly produces 55 ever, the appropriate ratio of methanol to Zn2, i.e., in methyl pivalate ((CH3)3CCOOCH3) and methyl an amount sufficient to initiate and sustain the reaction, 2,2,3,3-tetramethylbutyrate must be employed. Those skilled in the art may readily ((CH3)3CC(CH3)2COOCH3) in major amounts. Addi determine appropriate amounts, keeping in mind that tion of ethylene, propylene, isobutylene and mixtures excessively high ratios of reactants, especially methanol thereof to the reaction mixture results in an increase in 60 to Zn2, or mixtures thereof, may not be used. For ex methyl pivalate production. ample, ratios of from about 0.01 mol of methanol per mol of Zn2 to about 24 mols of methanol per mol of DESCRIPTION OF THE PREFERRED Zn2 may be used, while ratios of from about 0.1 mol of EMBODIMENT methanol per mol of Zn2 to about 10 mols of methanol The source of the methanol employed is a matter of 65 per mol of Zn2 are preferred. Where dimethyl ether is choice. For example, methanol derived from synthesis used as a feed, the ratio offeed to Zn2 would be similar, gas produced from coal, and methanol produced from and where dimethyl ether is used as a portion of the natural gas are eminently suited to the practice of the feed, adjustment of the feed ratio may be made readily. 4,166,189 3 4. The process may be conducted batch-wise or in a Analysis (GLC and mass spectrographic) of the gaseous continuous fashion. Whichever procedure is employed, and liquid products indicated the following product good mixing or contact of the Zn2 and the reactants is yields, stated as grams of products per 100 grams of important for good results. Any reaction system which methanol feed: provides a high degree of mixing or contact of reactants CH4: 0.2 may be employed. For example, fixed bed systems, i-C4H10: 5.3 slurry reactors, and trickle bed reactors may be used. i-C5H12; 1.2 Contact times are not critical, and those skilled in the art may vary the contact times to provide sufficient contact 2,2,3-trimethylbutane: 18.7 time to produce optimum results, depending on, e.g., 10 Other C7 & C3 hydrocarbons: 2.0 - volume of reactants, reactor design, temperature, etc. C9-C13 hydrocarbons: 8.4 For example, utilizing a fixed bed reactor design, and Hexamethylbenzene: 4.7 continuous flow of reactants, contact times on the order CHI: 25.0 of from about 0.5 minute (245 C.) to about 120 minutes, CO2: 2.9 or 180 minutes (200' C), or even longer, may be used. 15 Methyl pivalate: 7.7 Where batch procedures are employed, contact times Methyl ester of C5H11COOH: 3.9 may be considerably longer. In both batch and continu Methyl ester of C6H13COOH: 2.8 ous procedures, it is not necessary that 100 percent Methyl 2,2,3,3-tetramethylbutyrate: 24.0 conversion of the methanol be obtained before recover ing the product, the methanol being easily separable and 20 EXAMPLE 2 recyclable. Example 1 was repeated using 200g of ZnBr2 instead The process of this invention is described by the of the Zn2. The temperature of the reactor was lined following illustrative embodiments which are provided out at 235 C.
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