PREPARATION OF ETHYL ACETATE

Abstract: Process for the preparation of ethyl acetate by hy­ drogenating acetic anhydride or a mixture of acetic anhyd­ ride and ethylidene diacetate using Raney nickel as a catalyst. An organic sulfonic acid may also be used for the reaction when a mixture of acetic anhydride and ethylidene diacetate is hydrogenated.

Description: PREPARATION OF ETHYL ACETATE This invention relates to a process for the preparation of ethyl acetate by hydrogenating acetic anhydride or mixtures of acetic anhdyride and ethylidene diacetate. The hydrogenation of acetic anhydride using a nickel catalyst in the presence of a strong acid, such as hydrochloric acid, hydrofluoric acid, or methane sulfonic acid, is disclosed in U.S. Patent 4,221,918. The products obtained are reported to be ethylidene diacetate, acetic acid and, when hydrochloric acid was the acid used, l-chloroethyl acetate. When ethyl acetate is the desired product, this prior art process is impractical. The process of this invention provides a very effective method of making ethyl acetate. In accordance with this invention acetic anhydride or a mixture of acetic anhydride and ethylidene diacetate is hydrogenated with Raney nickel as the hydrogenation catalyst to form ethyl acetate. The feed to the hydrogenation reactor can, if desired, contain, in addition to acetic anhydride and/or ethylidene diacetate, an inert solvent such as acetic acid. The acetic acid in the product from the reaction can be converted to methyl acetate and used in the production of acetic anhydride. Acetic anhydride containing little if any ethylidene diacetate, e.g., up to about 10 weight percent, can be readily hydrogenated to produce ethyl acetate in good product yields and space-time yields. However, the presence of larger amounts of ethylidene diacetate inhibits the conversion of acetic anhydride to products and thus, the use of more severe reaction conditions or an organic sulfonic acid is necessary to satisfactorily hydrogenate mixtures of acetic anhydride and ethylidene diacetate to form ethyl acetate. The concentration of the Raney nickel that is used is in the range of 0.1 to 10 weight percent, based on the acetic anhydride and, when present, ethylidene diacetate. Catalyst concentrations (same basis) of 0.5 to 2.5 weight percent will most often be used. The temperature for the reaction is in the range of 100 to 2500C., although at the higher temperatures ethyl acetate decomposition can be a problem. Pressures (total reaction pressure) in the range of 500 to 5000 psig (3550 to 34590 kPa) may be used, although the use of pressures in excess of 2500 psig (17340 kPa) normally is not advantageous. The preferred temperatures and pressures vary depending on whether the material being hydrogenated consists primarily of acetic anhydride or consists of a mixture of acetic anhydride and ethylidene diacetate, e.g. mixtures of acetic anhydride and ethylidene diacetate in weight ratios of about 4:1 to 1:4. When the material being hydrogenated consists primarily of acetic anhydride, the preferred temperatures and pressures are in the range of 130 to 2000C., especially 130 to 1500C., and 500 to 1500 psig (3550 to 10445 kPa). When the material is a mixture of acetic anhydride and ethylidene diacetate, preferred temperatures and pressures are 170 to 2500C., especially 200 to 2250C., and 2000 to 2500 psig (13895 to 17340 kPa). When a substantial amount of ethylidene diacetate is fed to the reaction with the acetic anhydride, for example 50:50 weight mixtures, the ethylidene diacetate resists hydrogenation and retards the hydrogenation of the acetic anhydride. Consequently, relatively severe reaction conditions are required to hydrogenate such mixtures to ethyl acetate when only Raney nickel is used in the reaction. Much milder reaction conditions can be used to hydrogenate such mixtures to ethyl acetate if an organic sulfonic acid is used in the reaction medium. The organic sulfonic acid enables the use of milder, more economical reaction conditions and it results in higher conversions of acetic anhydride and ethylidene diacetate to ethyl acetate. The amount of organic sulfonic acid that is used is within the range of 0.1 to 3 weight percent, based on the total weight of acetic anhydride and ethylidene diacetate. The preferred amount is 0.5 to 1.5 weight percent. Of the many organic sulfonic acids that can be used, the lower alkyl and aryl sulfonic acids are preferred. The most preferred are methanesulfonic acid and p-toluenesulfonic acid because of their relatively low cost. When an organic sulfonic acid is used in the hydrogenation process, the reaction temperature can be in the range of 1300C. to 175 C., and the reaction pressure can be in the range of 500 to 3000 psig. (3550 to 20790 kPa). The process of the invention may be carried out as a batch operation or, more suitably, as a continuous process wherein acetic anhydride or mixtures of acetic anhydride and ethylidene diacetate are continuously fed to an autoclave and reaction mixture containing the desired products are continuously removed either as a liquid or as a vapor. Unreacted materials and co-product acetic acid may be removed from the reaction mixture after removal from the autoclave by distillation and recycled to the autoclave. The process of the invention is further illustrated by the following examples. EXAMPLES 1-18 Acetic anhydride (100 g.) and mixtures of acetic anhdyride (50 g.) and ethylidene diacetate (50 g.) were hydrogenated in the presence of varying amounts of Raney nickel using different temperatures and total autoclave pressures. The material hydrogenated in Examples 1-7 was acetic anhydride and in Examples 8-18 it was a 50-50 mixture of acetic anhydride and ethylidene diacetate. The acetic anhydride, ethylidene diacetate (when used) and Raney nickel catalyst were loaded into a 300 ml. stainless steel, rocking autoclave. The autoclave was purged with 100 psig (739 kPa) hydrogen gas pressure at room temperature and then the gas was vented. The internal pressure of the autoclave was increased to 10 psig (172 kPa) by adding hydrogen gas at room temperature. The autoclave was sealed and heated and rocked until reaction temperature was reached, at which time additional hydrogen gas was added to increase the autoclave internal pressure to the predetermined value. The time at which the autoclave internal pressure reached the predetermined value was taken as the start of the reaction time. A reaction time of 2 hours was used in Examples 1-16 and 1 hour in Examples 17 and 18. Reaction pressure was maintained at the preset value during the reaction by adding hydrogen gas at the same rate at which it was consumed by the reactants. When the predetermined reaction time was completed the autoclave was cooled by a stream of cold air. After the gas was vented from the autoclave the reaction product was analyzed by gas chromatographic methods. Table I shows the reaction temperature (or.) and pressure in psig and (kPa), the amount of catalyst (cat., g.) charged, the amount (in moles) of ethyl acetate (EA) produced, the percent of acetic anhydride (Ac2O) and ethylidene diacetate (EDA) consumed (cons.) and the product yield (PY, percent of theory) and space-time yields (STY, in grams/liter liquid-hour) for ethyl acetate. Table I Ac2O EDA EA EA Ex. Cat. Temp. Press. EA Cons. Cons. PY STY 1 1.5 170 1000 ( 7998) .42 97.8 - 87.5 185 2 2.5 140 500 ( 3550) .33 78.6 - 85.7 145 3 0.5 140 1500 (10445) .37 80.6 - 94.8 163 4 2.5 140 1500 (10445) .35 89.0 - 80.5 154 5 0.5 200 1500 (10445) .40 99.0 - 82.5 176 6 2.5 200 1500 (10445) .32 100.0 - 65.3 141 7 0.5 140 500 ( 3550) .21 46.9 - 65.3 141 8 1.5 190 1500 (10445) .20 77.6 32.4 66.6 88 9 2.5 170 750 ( 5275) .20 91.8 11.8 75.4 88 10 0.5 210 750 ( 5275) .13 36.7 55.9 46.4 57 11 0.5 170 2250 (15617) .12 46.9 8.8 82.7 53 12 2.5 210 750 ( 5275) .21 67.4 76.5 49.4 92 13 2.5 170 2250 (15617) .25 100.0 17.6 82.0 110 14 0.5 210 2250 (15617) .43 98.0 79.4 84.3 189 15 2.5 210 2250 (15617) .43 100.0 85.3 80.4 189 16 0.5 170 750 ( 5275) .09 26.5 50.0 38.4 40 17 2.0 200 2000 (13895) .35 100.0 55.0 80.8 308 18 2.0 200 2000 (13895) .22 96.3 21.8 69.4 194 EXAMPLE 19 Using the procedure described for the preceding examples, a mixture of 75 g. acetic anhydride and 75 g. ethylidene diacetate was hydrogenated for 1 hour at 2000C. and 2000 psig (13895 kPa) in the presence of 2.0 g. of Raney nickel. Six runs were carried out using the same catalyst. After each run the liquid product was pumped from the autoclave through a metal frit so as to leave the catalyst in the autoclave. Fresh acetic anhydride and ethylidene diacetate were then pumped into the autoclave and the next run was carried out. Table II shows the amount (moles) of ethyl acetate produced, the percent of the acetic anhydride and ethylidene diacetate consumed and the product yield and spacetime yield for ethyl acetate for each of the six runs. The overall average for each of the results measured is shown at the bottom of the table. Table II Ac2O EDA EA EA Run EA Cons. Cons. PY Sty 100 36 2 .48 100 59 71 340 3 .29 100 37 53 210 4 .35 100 37 63 253 5 .24 100 38 42 170 6 .36 100 34 66 256 Avg. .33 100 40 56 208 EXAMPLES 20-36 A mixture of acetic anhydride (50 g.) and ethylidene diacetate (50 g.) was hydrogenated in the presence of varying amounts of Raney nickel (Examples 20-28) and Raney nickel promoted with p-toluenesulfonic acid (Examples 29-36) using different temperatures and total autoclave pressures. The reaction procedure and equipment were identical to Examples 1-18. The reaction time for Examples 20-28 was 2 hours and 1 hour for Examples 29-36. Table III shows the temperature (or.) and pressure in psig and (kPa), the amount of nickel catalyst (cat., g.) and p-toluenesulfonic acid (PTSA, g.) charged, the amount (in moles) of ethyl acetate (EA) produced, the percent of acetic anhydride (Ac2O) and ethylidene diacetate (EDA) consumed (cons.) and the product yield (PY, percent of theory) and space-time yields (STY, in grams/liter liquid-hour) for ethyl acetate. Table III Ac2O EDA EA EA Ex. Cat. PTSA Temp. Press. EA Cons. Cons. PY STY 20 1.5 - 190 1500 (10445) .20 77.6 32.4 66.6 88 21 2.5 - 170 750 (10445) .20 91.8 11.3 75.4 88 22 0.5 - 210 750 ( 5275) .13 36.7 55.9 46.7 57 23 0.5 - 170 2250 (15617) .12 46.9 8.8 82.7 53 24 2.5 - 210 750 ( 5275) .21 67.4 76.5 49.4 92 25 2.5 - 170 2250 (15617) .25 100.0 17.6 82.0 110 26 0.5 - 210 2250 (15617) .43 98.0 79.4 84.3 189 27 2.5 - 210 2250 (15617) .43 100.0 85.3 80.4 189 28 0.5 - 170 750 (15275) .09 26.5 50.0 38.4 40 29 2.0 1.5 110 1000 ( 7998) .08 58.2 2.4 52.5 70 30 2.0 0.5 110 2000 (13895) .11 81.6 7.1 49.1 97 31 2.0 0.5 150 1000 ( 7998) .31 99.6 63.8 67.1 273 32 2.0 1.5 110 2000 (13895) .10 69.4 0.3 55.6 84 33 2.0 1.5 150 1000 ( 7998) .39 99.8 97.4 67.0 345 34 2.0 0.5 150 2000 (13895) .11 81.6 7.1 49.1 97 35 2.0 1.5 150 2000 (13895) .43 100.0 100.0 74.2 382 36 2.0 0.5 110 1000 ( 7998) .09 62.9 3.5 51.8 76 Table III illustrates the advantages which result from the use of the organic sulfonic acid. In Example 14 almost all of the ethylidene diacetate was consumed whereas in Example 6, using significantly more severe conditions but in the absence of an organic sulfonic acid, only 17.6% of the ethylidene diacetate was consumed.

Claims: Claims: 1. The catalytic process for hydrogenating acetic anhydride or a mixture of acetic anhydride and ethylidene diacetate characterized by (a) using Raney nickel as a catalyst for the process and (b) ethyl acetate being a reaction product. 2. The process according to claim 1 wherein the reaction pressure is 500 to 5000 psig (3550 to 34590 kPa) and the reaction pressure is 1000 to 2500C. 3. The process according to claim 2 wherein the catalyst concentration is 0.1 to 10 percent, by weight, of acetic anhydride or a mixture of acetic anhydride and ethylidene diacetate. 4. The process according to claim 1 wherein acetic anhydride is hydrogenated at 1300C. to 1500C. using a catalyst concentration of 0.5 tb 2.5 percent, by weight, of acetic anhydride. 5. The process according to claim 1 wherein a mixture of acetic anhydride and ethylidene diacetate is hydrogenated at a pressure of 2000 to 2500 psig (13895 to 17340 kPa) and a temperature of 170 to 2500C. 6. The process according to claim 1 wherein a mixture of acetic anhydride and ethylidene diacetate is hydrogenated at a pressure of 500 to 3000 psig (3550 to 20790 kPa) and at a temperature of 1300C. to 175 0C. and an organic sulfonic acid is used with the Raney nickel in the hydrogenation reaction. 7. The process according to claim 6 wherein the concentration of Raney nickel is 0.1 to 10 percent, by weight, of acetic anhydride and ethylidene diacetate and the concentration of organic sulfonic acid is 0.1 to 3 percent, by weight, of acetic anhydride and ethylidene diacetate. 8. The process according to claim 7 wherein the organic sulfonic acid in methanesulfonic acid or p-toluenesulfonic acid. 9. The process according to claim 8 wherein the pressure is 500 to 1500 psig (3550 to 10445 kPa), the temperature is 1400C. to 1600C., the concentration of Raney nickel is 0.5 to 2.5 weight percent and the concentration of organic sulfonic acid is 0.5 to 1.5 weight percent.

Inventors: GLENN, THOMAS JACKSON, LARKINS, THOMAS HASSELL, JR., POND, DAVID MARTIN, TENNANT, BRENT ALAN
Applicants: EASTMAN KODAK COMPANY
Application year: 1982
Main classification: C07C69
IPC codes: C07C69