GB729305A - Improvements in or relating to process for the manufacture of esters - Google Patents

Improvements in or relating to process for the manufacture of esters

Info

Publication number
GB729305A
GB729305A GB23377/51A GB2337751A GB729305A GB 729305 A GB729305 A GB 729305A GB 23377/51 A GB23377/51 A GB 23377/51A GB 2337751 A GB2337751 A GB 2337751A GB 729305 A GB729305 A GB 729305A
Authority
GB
United Kingdom
Prior art keywords
acid
alcohol
water
ester
distillation column
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
GB23377/51A
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Standard Oil Development Co
Original Assignee
Standard Oil Development Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Standard Oil Development Co filed Critical Standard Oil Development Co
Publication of GB729305A publication Critical patent/GB729305A/en
Expired legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12Acetic acid esters
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/08Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Esters of aliphatic monocarboxylic acids and aliphatic monohydric alcohols, said esters boiling below the boiling-point of the acid utilized, are obtained by continuously feeding an aliphatic monocarboxylic acid and an aliphatic monohydric alcohol to a reaction zone containing a reacting mixture of the said acid and alcohol in the presence of an acid esterification catalyst, p feeding the vaporous reaction product containing ester, alcohol, carboxylic acid and water into an intermediate portion of a distillation column, withdrawing from the distillation column a bottoms liquid fraction consisting predominantly of the aliphatic monocarboxylic acid substantially free of the alcohol, recycling this bottoms fraction to the reaction zone and taking overhead from the distillation column a product containing ester, alcohol, and water substantially free of aliphatic monocarboxylic acid. Additional water is preferably <PICT:0729305/IV (b)/1> added to the distillation column to enable the formation of an ester, alcohol, water azeotrope therein. The aliphatic carboxylic acid may comprise any acid which boils above the corresponding ester or ester-water azeotrope. Specified acids are formic, acetic, propionic, butyric and valeric acids. The aliphatic alcohols may comprise, depending on the boiling-point of the ester and the acid used, alcohols such as methyl, ethyl, isopropyl, n-propyl, sec.-butyl, isobutyl, and isoamyl alcohols. The acid and alcohol used should preferably be as dry as possible and in starting the reaction it is preferred that the initial reacting mixture contains not more than three volumes of the acid per volume of the alcohol. The acid catalyst used may be sulphuric or hydrochloric acid or a sulphonic acid, e.g. benzene sulphonic acid. The description given with reference to the Figure utilizes secondary butyl alcohol and acetic acid with sulphuric acid as the esterification catalyst and the process is initiated in a reaction zone 1 containing a reacting mixture of the aliphatic acid and monohydric alcohol, the acid being preferably in excess. The subsequent continuous feed to the reaction zone preferably contains the acid and alcohol in approximately stoichio-metric proportions, and the reaction is carried out at 109-113 DEG C. The resulting vaporous mixture of exter, water, unreacted alcohol and acetic acid is fed at about 109 DEG C. by line 4 into an intermediate portion of distillation column 5, water being introduced through line 6 into line 4 in sufficient quantity to make the aqueous azeotrope compositions with the acetate and unreacted alcohol. The added water is preferably fed as liquid at about its boiling-point. The vaporous azeotropes are removed through line 7 at about 87 DEG C. and the mixture condensed in condenser 8 from which it flows into water separator 9 in which an upper ester layer and a bottom aqueous alcohol layer are formed. Part of each layer is sent as reflux through lines 10 and 11 respectively to the top of the distillation column, whilst the semi-finished ester product is withdrawn from separator 9 and purified by conventional means whilst part of the water layer and of the ester layer are sent as reflux through lines 10 and 11 to the top of the distillation column. The aqueous alcohol layer can also be returned through lines 16 and 12 in place of or supplementing fresh water entering through line 6 to the same plate as the feed in the distillation column. Acetic acid passes through line 13 to reboiler 14 which is maintained at about 115-120 DEG C. and recycled to the reactor either through the same line as the feed or through a different line, whereby the effective acid concentration in the reaction zone is considerably increased. Examples are given for the production of secondary butyl acetate from acetic acid and secondary butyl alcohol in the presence of sulphuric acid and the results obtained are tabulated and compared with those obtained by a prior art process in which excess acid is used and the esterification reactor is also the reboiler of a distillation column.ALSO:<PICT:0729305/III/1> Esters of aliphatic monocarboxylic acids and aliphatic monohydric alcohols, said esters boiling below the boiling point of the acid utilized, are obtained by continuously feeding an aliphatic monocarboxylic acid and an aliphatic monohydric alcohol to a reaction zone containing a reacting mixture of the said acid and alcohol in the presence of an acid esterification catalyst, and in the absence of extraneous water other than any small amounts that may be present in the acid and alcohol utilized; feeding the vaporous reaction product containing ester, alcohol, carboxylic acid and water into an intermediate portion of a distillation column, withdrawing from the distillation column a bottoms liquid fraction consisting predominantly of the aliphatic monocarboxylic acid substantially free of the alcohol, recycling this bottoms fraction to the reaction zone and taking overhead from the distillation column a product containing ester, alcohol and water substantially free of aliphatic monocarboxylic acid. Additional water is preferably added to the distillation column to enable the formation of an ester, alcohol, water azetrope therein. The aliphatic carboxylic acid may comprise any acid which boils above the corresponding ester or ester-water azeotrope. Specified acids are formic, acetic, proprionic, butyric and valeric acids. The aliphatic alcohols may comprise, depending on the boiling point of the ester and the acid used, alcohols such as methyl, ethyl, isopropyl, n-propyl, sec-butyl, isobutyl and isoamyl alcohols. The acid and alcohol used should preferably be as dry as possible and in starting the reaction it is preferred that the initial reacting mixture contains not more than three volumes of the acid per volume of the alcohol. The said catalyst may be sulphuric or hydrochloric acid or a sulphonic acid, e.g. benzene sulphonic acid. The description given with reference to the Figure utilizes secondary butyl alcohol and acetic acid with sulphuric acid as the esterification catalyst and the process is initiated in a reaction zone 1 containing a reacting mixture of the aliphatic acid and monohydric alcohol, the acid being preferably in excess. The subsequent continuous feed to the reaction zone preferably contains the acid and alcohol in approximately stoichiometric proportions and the reaction is carried out at 109-113 DEG C. The resulting vaporous mixture of ester, water, unreacted alcohol and acetic acid is fed at about 109 DEG C. by line 4 into an intermediate portion of distillation column 5, water being introduced through line 6 into line 4 in sufficient quantity to make the aqueous azeotrope compositions with the acetate and unreacted alcohol. The added water is preferably fed as liquid at about its boiling point. The vaporous azeotropes are removed through line 7 at about 87 DEG C. and the mixture condensed in condenser 8 from which it flows into water separator 9 in which an upper ester layer and a bottom aqueous alcohol layer are formed. Part of each layer is sent as reflux to the top of the distillation column whilst the semi-finished ester product is withdrawn from separator 9 and purified by conventional means. The aqueous alcohol layer can also be returned through lines 11 and 12 to the same plate as the feed in the distillation column. Acetic acid passes through line 13 to reboiler 14 which is maintained at about 115-120 DEG C. and is withdrawn through line 15 and recycled to the reactor either p through the same line as the feed or through a different line whereby the effective acid concentration in the reaction zone is considerably increased. Examples are given for the production of secondary butyl acetate from acetic acid and secondary butyl alcohol in the presence of sulphuric acid and the results obtained are tabulated and compared with those obtained by a prior art process in which excess acid is used and the esterification reactor is also the reboiler of a distillation column.
GB23377/51A 1951-05-16 1951-10-08 Improvements in or relating to process for the manufacture of esters Expired GB729305A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US729305XA 1951-05-16 1951-05-16

Publications (1)

Publication Number Publication Date
GB729305A true GB729305A (en) 1955-05-04

Family

ID=22110622

Family Applications (1)

Application Number Title Priority Date Filing Date
GB23377/51A Expired GB729305A (en) 1951-05-16 1951-10-08 Improvements in or relating to process for the manufacture of esters

Country Status (1)

Country Link
GB (1) GB729305A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066059A1 (en) * 1981-05-29 1982-12-08 Hüls Aktiengesellschaft Esterification process of acetic acid by C2 to C5 alcohols
WO2009033381A1 (en) 2007-09-14 2009-03-19 Hunan Zhongchuang Chemical Co., Ltd A process of removing heavier hydrocarbons from the reaction products of producing sec-butyl acetate
CN112299993A (en) * 2020-10-30 2021-02-02 河北金谷再生资源开发有限公司 Device and method for producing tributyrin

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0066059A1 (en) * 1981-05-29 1982-12-08 Hüls Aktiengesellschaft Esterification process of acetic acid by C2 to C5 alcohols
WO2009033381A1 (en) 2007-09-14 2009-03-19 Hunan Zhongchuang Chemical Co., Ltd A process of removing heavier hydrocarbons from the reaction products of producing sec-butyl acetate
EP2192104A1 (en) * 2007-09-14 2010-06-02 Hunan Zhongchuang Chemical Co., Ltd A process of removing heavier hydrocarbons from the reaction products of producing sec-butyl acetate
EP2192104A4 (en) * 2007-09-14 2011-02-16 Hunan Zhongchuang Chemical Co Ltd A process of removing heavier hydrocarbons from the reaction products of producing sec-butyl acetate
CN112299993A (en) * 2020-10-30 2021-02-02 河北金谷再生资源开发有限公司 Device and method for producing tributyrin
CN112299993B (en) * 2020-10-30 2023-06-16 河北金谷再生资源开发有限公司 Device and method for producing tributyrin

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