US2787636A - Process for the manufacture of lower aliphatic esters - Google Patents

Process for the manufacture of lower aliphatic esters Download PDF

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Publication number
US2787636A
US2787636A US479979A US47997955A US2787636A US 2787636 A US2787636 A US 2787636A US 479979 A US479979 A US 479979A US 47997955 A US47997955 A US 47997955A US 2787636 A US2787636 A US 2787636A
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bath
alcohol
ester
water
acid
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US479979A
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English (en)
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Alheritiere Louis
Mercier Jules
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Usines de Melle SA
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Usines de Melle SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/12—Acetic acid esters
    • C07C69/14—Acetic acid esters of monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
    • C07C69/04—Formic acid esters
    • C07C69/06—Formic acid esters of monohydroxylic compounds

Definitions

  • the invention relates to the process for the manufacture of lower aliphatic esters.
  • a conventional process of manufacture of such lower esters consists in continuously introducing the acid to be esterified and an amount of alcohol in excess of -40% over the theoretical proportion, into a reaction vessel containing an esterication catalyst such as sulphuric acid, and continuously distilling the reaction products in a distilling column surmounting the esterification vessel.
  • the ester and kwater resulting from the esterication reaction are withdrawn from the head of the column together with the excess alcohol, and the vapors of acid are prevented from rising to the top by reiiuxing part of the distillate.
  • An object of the present invention is to provide a simple, efficient process for the manufacture of such esters which will increase the productive capacity of a given esterification apparatus employing the conventional process mentioned, While reducing the heat expense as compared therewith.
  • Such process may be carried out by continuously introducing acid and alcohol to be esteriiied into a catalytic esterification bath containing at least 20% by weight of an auxiliary liquid which has a boiling temperature of at least 120 C., such boiling temperature being above that of the ester to be produced.
  • Theauxiliary liquid is one which is stable under the esterification conditions. It is miscible with the other constituents of the bath and does not cause displacement of water therefrom.
  • Such auxiliary liquid does not provide, with any of the other constituents of the bath, any azeotropic mixture which has a lower boiling point than that of the azeotropic mixture of Water with the ester produced.
  • the bath is maintained at the boiling. Continuous esterifcation occurs.
  • the ester is continuously recovered by distillation.
  • the auxiliary liquid remains behind and is not distilled from the body of the liquid where the esteriiication is occurring.
  • the auxiliary liquid is an organic compound or mixture of organic compounds taken from various classes, more particularly esters, ethers, ketones and hydrocarb ons.
  • esters constituting such auxiliary liquid there are preferably used those derived from the saine acid as that to be esteried and from an alcohol having a boiling point above that of the alcohol to be esteriiied.
  • ethers there may be used, for example, butyl oxides.
  • ketones for example, a dipropyl ketone may be employed.
  • hydrocarbons for example, one may use xylene.
  • the auxiliary liquid in the bath results in an increased boiling temperature, favoring removal by distillation ot 2,787,636 Patented Apr. 2, 1957 "ice the reaction water.
  • the so-lowered water content of the bath and the increased temperature result in increased reaction speed, allowing the excess amount of alcohol used to be considerably reduced, thus facilitating separation of water by decantation of the distillate withdrawn from the head of the column.
  • lower aliphatic alcohols which are soluble in water in any proportions, increase the mutual solubility of water and esters.
  • This invention applies more particularly to the manufacture of esters having no more than 6 carbon atoms in the molecule, from aliphatic acids and alcohols having no more than 4 carbon atoms.
  • the invention is especially suitable, though not restricted, to making esters of lower aliphatic alcohols, which alcohols are soluble in water in all proportions, such as methyl, ethyl, isopropyl and allyl alcohols. It is also applicable to other 4-carbon alcohols of lesser solubility in water.
  • Example 1 Manufactare of ethyl acetate An esterifcation vessel 4 is charged initially with butyl acetate as an auxiliary liquid, and sulphuric acid as an esterification catalyst.
  • the vessel in normal run contains 1200 kg. of reaction bath, the composition of which will be indicated herebelow.
  • This vessel is continuously fed with 256 kg. per hour of acetic acid from tank 2 and 263 kg. of ethyl alcohol from tank 3.which receives, on the one hand, pure ethyl alcoholof vol. percent strength from tank 1, and, on the other hand, recovered alcohol containing ethyl acetate, from column 22, as explained herebelow.
  • Constant liquid level isr maintained in tank 3 by means of a float-valve which automatically allows fresh alcohol to ow from tank 2.
  • Vessel 4 is heated by means of a coil 5 in such a manner that 330,000 calories are absorbed per hour by condenser 7 connected with distilling column 6 which is disposed above vessel 4.
  • the condensate from condenser 7 is mixed with water in a mixer 8 which preferably is a little tower filled with Raschig rings.
  • the added Water extracts the alcohol from the condensate.
  • the mixture is introduced into a decanter 9 where it separates into two layers.
  • the upper layer contains less water than does the distillate as withdrawn from column 6, and this feature permits removal of the distilled reaction water and Water initially contained in the starting alcohol;
  • the upper layer is drawn ofi through pipe 10' at a suitable rate. Part thereof is refluxed through pipe 11 to the top of column 6.
  • the remainder, amounting to 420 kg. per hour, is sent through pipe 12 to a washing tower 13, preferably illed with Raschig rings, which is fed with water through pipev 1 at a rate of 300 liters per hour.
  • the washing with water in tower 13 entirely removes the small amount of alcohol still contained in the raw ester constituting the upper layer from decanter 9.
  • the water issuing'from tower 13, which is .saturated with ethyl acetate and contains a little alcohol, is recycled by ⁇ pump to mixer .8 to be mixed .with the ⁇ distillate from column 6 as described above.
  • the lower layer from decanter 9 is fed to .column 22 together with that from decanter 20.
  • the condensate from condenser 2.4 connected with :column 22 contains, by weight, 18% of alcohol, 74% of ethyl acetate and 8% of water, Part of this .condensate is reuxed to the top of 4column 22 through pipe 25. The remainder, amounting ⁇ to 50kg. Aper jhour, is recycled through .valved pipe 2,6 to tank 3 which receives 213 kg. per hour .of fresh, 95 vol. percentalcohol, i. e. 197 kg. per hour of purealcohol, from -tank 2 which are automatically admitted by the oat-valve.
  • vessel 4 is ⁇ fed with a ,total amount ⁇ of 206 kg. per hour ,of pure alcohol, this representing .an excess .of 9 kg. over the theoretical amountrequired toesterify .the 2,56 kg. of acetic acid fed per hour, the .excess proportion of alcohol thus being 4.5% only.
  • the weight composition of the esteritication bath in vessel 4 is substantially as follows:
  • the boiling temperature of this bath is 110 C.
  • the steam expense -or expenditure per kg. of ester produced is of 1.7 kg. in vessel ⁇ 4 and 0.4 kg. in column 22, i. e. a total amount of 2.1 kg.
  • Ester produced-210 kg. per hour (instead of 375 kg).
  • isopropyl acetate The apparatus and process are the same as in Example l except for changes in operating conditions as indicated below.
  • the auxiliary liquid is beta-ethoxy-ethyl acetate, employed in such a quantity that the esterification bath contains by weight thereof.
  • the temperature of the bath is maintained at 110 C.
  • Acetic acid feed (from tank 1)-236 kg. -per hour.
  • Fresh isopropyl alcohol feed (from tank 2)-272 kg. per hour of water-isopropyl alcohol azeotropic mixture containing 87% by weight of isopropyl alcohol.
  • the auxiliary liquid is n-butyl oxide, employed -in such aquantity that the bath contains 70% "by weight thereof.
  • the bath is so heated that its operating temperature is C.
  • the operating conditions are as follows:
  • Anhydrous fresh propyl alcohol feed (from tank 2)- 300 kg. per hour.
  • the number of calories absorbed were-280,000.
  • Example 4.-Ma1mff!cture of isopropyl pmpionatc The apparatus and process are the same as in the preceding examples except for certain changes in the operating conditions as given below.
  • the auxiliary liquid is di-n-propyl ketone constituting 35% 'by weight of the bath. rIlhe bath is maintained at ya temperature of C.
  • the operating conditions are as follows:
  • a process for producing lower aliphatic esters containing 3 to 6 carbon atoms which comprises continuously introducing an alkanoic acid and -alcohol selected from the group consisting of an alkanol and an alltenol each containing from 1 to 4 carbon atoms into a boiling catalytic esterication bath, said alcohol being introduced in a quantity less than 20% excess of the theoretical amount required for producing the ester from said acid, said bath containing at least 20% by Weight of an auxiliary liquid which has a boiling temperature of at least 120 C.
  • a process for producing lower aliphatic esters con taining 3 to 6 carbon atoms which comprises continuously introducing an alkanoic acid and alcohol selected from the group consisting of an alkanol and an alkenol each containing from 1 to 4 carbon atoms into a boiling catalytic esteriication bath, said alcohol being introduced in a quantity less than 20% excess of the theoretical amount required for producing the ester from said acid, said bath containing at least 20% by vweight of an auxiliary liquid ester derived from the same acid as that to be esteriled and from an alcohol having a boiling point above that of the alcohol to be esterilied, said auxiliary ester having a yboiling temperature of at least C.
  • a process for producing lower aliphatic esters containing 3 to 6 carbon atoms which comprises continuously introducing an alkanoic acid land alcohol selected from the group consisting of an an alkanol and an alkenol each containing from 1 to 4 carbon atoms into a boiling catalytic esterication bath, said alcohol being introduced in a quantity less than 20% excess of the theoretical amount required for producing the ester from said acid, said bath containing at least 20% by weight of a butyl oxide and continuously distilling the ester formed.
  • a process for producing lower aliphatic esters containing 3 to 6 carbon atoms which comprises continuouslyr introducing an alkanoic acid and alcohol selected from the group consisting of an alkanol land an alkenol each containing from 1 to 4 carbon atoms into a boiling catalytic esteritication bath, said alcohol being introduced in a quantity less than 20% excess of the theoretical amount required for producing the ester from said acid, said bath containing at least 20% by weight of a dipropyl ketone amd continuously distilling the ester formed.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US479979A 1954-02-18 1955-01-05 Process for the manufacture of lower aliphatic esters Expired - Lifetime US2787636A (en)

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CH (1) CH324436A (enrdf_load_stackoverflow)
FR (1) FR1099622A (enrdf_load_stackoverflow)
NL (1) NL90413C (enrdf_load_stackoverflow)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404175A (en) * 1964-04-06 1968-10-01 Melle Usines Sa Process for forming and separating ethers or esters by plural stage distillation with removal of water as an azeotrope
US3431181A (en) * 1966-06-22 1969-03-04 Melle Bezons Method of separating methanol from low boiling aliphatic esters and water by azeotropic distillation with a hydrocarbon
EP0060719A1 (en) * 1981-03-17 1982-09-22 BP Chemicals Limited Process for the production of methyl acetate by esterifying methanol with acetic acid
EP0060717A1 (en) * 1981-03-17 1982-09-22 BP Chemicals Limited Process for the production of methyl acetate by esterifying methanol with acetic acid
CN1039226C (zh) * 1995-04-17 1998-07-22 国营吴江香料厂 甲酸乙酯半连续生产工艺
WO2011117707A1 (fr) * 2010-03-25 2011-09-29 Rhodia Poliamida E Especialidades Ltda Procede d'obtention d'un ester d'acide carboxylique
WO2013143825A1 (en) 2012-03-30 2013-10-03 Exxonmobil Chemical Patents Inc. Esterification process
WO2013143824A1 (en) 2012-03-30 2013-10-03 Exxonmobil Chemical Patents Inc. Process for the production of terephthalate esters

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2147341A (en) * 1930-09-16 1939-02-14 Joseph F Harrington Process for the manufacture of esters
US2208769A (en) * 1935-11-15 1940-07-23 Du Pont Process for continuous esterification
US2575722A (en) * 1947-11-03 1951-11-20 Melle Usines Sa Process for production of lower aliphatic esters

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2147341A (en) * 1930-09-16 1939-02-14 Joseph F Harrington Process for the manufacture of esters
US2208769A (en) * 1935-11-15 1940-07-23 Du Pont Process for continuous esterification
US2575722A (en) * 1947-11-03 1951-11-20 Melle Usines Sa Process for production of lower aliphatic esters

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3404175A (en) * 1964-04-06 1968-10-01 Melle Usines Sa Process for forming and separating ethers or esters by plural stage distillation with removal of water as an azeotrope
US3431181A (en) * 1966-06-22 1969-03-04 Melle Bezons Method of separating methanol from low boiling aliphatic esters and water by azeotropic distillation with a hydrocarbon
EP0060719A1 (en) * 1981-03-17 1982-09-22 BP Chemicals Limited Process for the production of methyl acetate by esterifying methanol with acetic acid
EP0060717A1 (en) * 1981-03-17 1982-09-22 BP Chemicals Limited Process for the production of methyl acetate by esterifying methanol with acetic acid
CN1039226C (zh) * 1995-04-17 1998-07-22 国营吴江香料厂 甲酸乙酯半连续生产工艺
WO2011117707A1 (fr) * 2010-03-25 2011-09-29 Rhodia Poliamida E Especialidades Ltda Procede d'obtention d'un ester d'acide carboxylique
FR2957918A1 (fr) * 2010-03-25 2011-09-30 Rhodia Poliamida E Especialidades Ltda Procede d'obtention d'un ester d'acide carboxylique
CN102822135A (zh) * 2010-03-25 2012-12-12 罗狄亚聚酰胺特殊品有限公司 用于生成羧酸酯的方法
US20130131376A1 (en) * 2010-03-25 2013-05-23 Carlos Eduardo Marenco Method for producing a carboxylic acid ester
CN102822135B (zh) * 2010-03-25 2016-08-03 罗狄亚聚酰胺特殊品有限公司 用于生成羧酸酯的方法
WO2013143825A1 (en) 2012-03-30 2013-10-03 Exxonmobil Chemical Patents Inc. Esterification process
WO2013143824A1 (en) 2012-03-30 2013-10-03 Exxonmobil Chemical Patents Inc. Process for the production of terephthalate esters

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FR1099622A (fr) 1955-09-07
CH324436A (fr) 1957-09-30
NL90413C (enrdf_load_stackoverflow)

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