Ester synthesis

Abstract

This invention relates to a process for the production of lower aliphatic esters by reacting a lower olefin with a saturated lower aliphatic mono-carboxylic acid in the vapor phase in the presence of a heteropolyacid catalyst characterized in that an amount of water in the range from 1-10 mole % based on the total of the olefin, aliphatic monocarboxylic acid and water is added to the reaction mixture during the reaction. The presence of water enhances the yield of the desired ester. The reaction mixture may optionally contain a di-ether to minimize the by-products. The process is particularly suitable for producing ethyl acetate from ethylene and acetic acid in the presence of water.

1. A process for the production of lower aliphatic esters said process comprising reacting a lower olefin and a di- ether  with a saturated lower aliphatic monocarboxylic acid in the vapour phase in the presence of a free acid silico-tungstic heteropolyacid catalyst supported on a siliceous support characterized in that an amount of water in the range from 1-10 mole % based on the total of the olefin, aliphatic mono-carboxylic acid and water is added to the reaction mixture during the reaction and the amount of di- ether is in the range from  1  to  6  mole  %  based on the total reaction mixture comprising the olefin, aliphatic carboxylic acid, water, and di - ether.    
     
     
       2. A process according to  claim 1  wherein the amount of water added is in the range from 1 to 7 mole % based on the total of the olefin, aliphatic monocarboxylic acid and water. 
     
     
       3. A process according to  claim 1  wherein the amount of water added is in the range from 1 to 5 mole % based on the total of the olefin, aliphatic monocarboxylic acid and water. 
     
     
       4. A process according to  claim 1  wherein the heteropolyacid catalyst is supported on a siliceous support which is in the form of extrudates or pellets, said siliceous support having an average pore radius of 30 to 100 Å. 
     
     
       5. A process according to  claim 4  wherein the siliceous support is derived from an amorphous, non-porous synthetic silica. 
     
     
       6. A process according to  claim 4  wherein the siliceous support is derived from fumed silica produced by flame hydrolysis of SiCl 4 . 
     
     
       7. A process according to  claim 4  wherein the silica support is in the form of pellets or beads or are globular in shape having an average particle diameter in the range from 2 to 10 mm, a pore volume in the range from 0.3-1.2 ml/g, a crush strength of at least 2 Kg force and a bulk density of at least 380 g/l. 
     
     
       8. A process according to  claim 4  wherein the siliceous support has at least 99% w/w purity. 
     
     
       9. A process according to  claim 4  wherein the siliceous support is a pelleted silica support which has an average bulk density of about 0.39 g/ml, an average pore volume of about 1.15 ml/g and an average particle size ranging from about 0.1-3.5 mm. 
     
     
       10. A process according to  claim 9  wherein the pelleted silica support is used as such or after crushing to an average particle size in the range from 0.5-2 mm to support the heteropolyacid catalyst. 
     
     
       11. A process according to  claim 1  wherein the heteropolyacids have a molecular weight e.g. in the range from 700-8500 and include dimeric complexes. 
     
     
       12. A process according to  claim 4  wherein the amount of heteropolyacid deposited/impregnated on the support for use in the esterification reaction is in the range from 10 to 60% by weight based on the total weight of the heteropolyacid and the support. 
     
     
       13. A process according to  claim 1  wherein the olefin reactant used is ethylene, propylene or mixtures thereof. 
     
     
       14. A process according to  claim 1  wherein the saturated, lower aliphatic mono-carboxylic acid reactant is a c1-C4 carboxylic acid. 
     
     
       15. A process according to  claim 1  wherein the aliphatic mono-carboxylic acid reactant is acetic acid. 
     
     
       16. A process according to  claim 1  wherein the reaction mixture has a molar excess of the olefin reactant with respect to the aliphatic mono-carboxylic acid reactant. 
     
     
       17. A process according to  claim 1  wherein the mole ratio of olefin to the lower carboxylic acid in the reaction mixture is in the range from 1:1 to 15:1. 
     
     
       18. A process according to  claim 1  wherein the mole ratio of olefin to the lower carboxylic acid in the reaction mixture is in the range from 10:1 to 14:1. 
     
     
       19. A process according to  claim 1  wherein the reaction is carried out in the vapour phase above the dew point of the reactor contents comprising the reactant acid, any alcohol formed in situ, the product ester and water. 
     
     
       20. A process according to  claim 1  wherein the supported heteropolyacid catalyst is used as a fixed bed which is in the form of a packed column. 
     
     
       21. A process according to  claim 1  wherein the heteropolyacid catalyst is further modified by the addition of phosphoric acid or other mineral acids thereto. 
     
     
       22. A process according to  claim 1  wherein the vapours of the reactant olefins and acids are passed over the catalyst at a GHSV in the range of 100 to 5000 per hour. 
     
     
       23. A process according to  claim 1  wherein the esterification reaction is carried out at a temperature in the range from 150°-200° C. using a reaction pressure which is at least 400 KPa. 
     
     
       24. A process according to  claim 1  wherein the reaction mixture is dosed with a  the di-ether which corresponds to the  comprises a by-product di-ether formed in situ during the reaction from the reactant olefin which  and the di-ether is recovered and recycled to the reaction mixture. 
     
     
       25. A process according to  claim 24  wherein the amount of di-ether recycled is in the range from 1 to 6 mole percent based on the total reaction mixture comprising the olefin, the aliphatic carboxylic acid, water and di-ether. 
     
     
       26. A process according  claim 24  wherein the di-ether is diethyl ether. 
     
     
       27. A process according to  claim 24  wherein the di-ether is an unsymmetrical ether.