US2740800A - Process for producing aliphatic esters - Google Patents

Process for producing aliphatic esters Download PDF

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Publication number
US2740800A
US2740800A US355724A US35572453A US2740800A US 2740800 A US2740800 A US 2740800A US 355724 A US355724 A US 355724A US 35572453 A US35572453 A US 35572453A US 2740800 A US2740800 A US 2740800A
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United States
Prior art keywords
bath
propylene
isopropyl
per hour
acid
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US355724A
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English (en)
Inventor
Mention Maurice
Godet Pierre
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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
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety
    • C07C69/24—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety esterified with monohydroxylic compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
    • 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
    • C07C69/22—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen having three or more carbon atoms in the acid moiety

Definitions

  • acetic acid can react with propylene in the presence of sulfuric acid. Many modes of carrying out such reaction have been described, to produce a mixture comprising sulfuric acid, mono-isopropyl sulfate, acetic acid and isopropyl acetate, but containing in addition propylene polymers and decomposition products.
  • the reaction mixture obtained is then treated for recovery therefrom of the ester formed, the treatment generally consisting in diluting the mixture with water to isolate a mixture of acid, ester and water by decantetion and/or distillation, the acid-ester-water mixture being then separated into its components by known means.
  • the recovered sulfuric acid thus, is in dilute form-"and must be concentrated before reuse.
  • a process of the batch type has: been proposed which involves the production of the ester in'a reactor, removal of the reacted mixture and distillation of same by bubbling an olefine therethrough to remove some'of the' ester. Thereafter the remainder of the mixture-is re turned to the reactor for further processing.
  • the principal object of the present invention accordingly is to produce a simple and efiicient process for the production of aliphatic esters which shall overcome in part at least some of the disadvantages of the prior processes.
  • the invention accordingly comprises the novel processes and steps of processes, specific embodiments of' which are described hereinafter by way of example and in accordance with which we now prefer to practice the invention.
  • Percent Sulfuric acid 20-30 Aliphatic acid 5-30 isopropyl ester 5-10 Water 0.5- isopropyl hydrogen sulfate 69.5-20
  • bath may be initially formed by any suitable means. In operation, the bath is fed with acetic acid and propylene under conditions hereinbelow set forth.
  • the working temperature is maintained substantially constant at a value in the range 60-80 C.
  • the preferred temperature is between 65 and 70 C. because at such temperatures polymer formation is very low while the bath is still capable of absorbing enough pro-.
  • ACETIC ACID FEED Acetic acid is continuously fed to the bath at a rate such that the acetic acidity in the bath remains substantially constant at the chosen value.
  • acetic acidity is in the range of 5-30%. However, the preferred range is 10-20% because below 10% the quickness of absorption of propylene is relatively low, whereas above 20% more acetic acid is carried 01f by the nonabsorbed propylene, and, as a result, recovery of isopropyl acetate in a pure state is more costly.
  • PROPYLENE FEED For maintaining in equilibrium the composition of the bath and removing the isopropyl acetate as it is formed, it is necessary that the gaseous feed rate be maintained between certain limits.
  • the propylene feed rate to the bath should be of 2-5 cubic meters per hour per kg. of bath, preferably 2.5-4 cubic meters per hour per kg. of bath. Under such conditions the Whole of the isopropyl acetate formed is carried off as Vapors by the excess gas, together with a quantity of acetic acid and small amounts of isopropyl alcohol and isopropyl oxide.
  • the resulting gaseous mixture is freed from the vapors it contains, preferably by cooling then, if need be, washing with'acetic acid or another liquid capable of dissolving isopropylacetate but from which isopropyl acetate can be readily separated, for example through distillation.
  • the gas freed from the products carried 0a is recycled to the reaction bath.
  • absorbable gases introduced are not possible to discard only the non-absorbable gases, so that the discard always contains an amount of propylene.
  • the discarding is controlled so as to maintain sufficient richness of propylene in the cycle.
  • the propylene richness may be as low as 30% of propylene by volume but in order that the absorption capacity per hour of the bath be high, it is recommended to maintain said richness above 50% by volume, for example between 50% and 90% by volume.
  • 1 is the reaction vessel or reactor which preferably is a tower into the bottom part of which propylene is introduced through a porous plate 2 or any other means for distributing a gas throughout a liquid.
  • the required temperature is obtained and maintained by means of a heating device 3 which may be a steam jacket, an electrical winding or any other conventional device.
  • Aliphatic acid such as acetic acid from tank 4 is fed to reactor 1 through pipe 5 fitted with a control valve 6.
  • Sulfuric acid is fed through pipe 1A.
  • the mixture of gases and vapors leaving reactor 1 through pipe 7 are introduced into a condenser 8, then, if need be, into a scrubbing column 9 to wash them.
  • Column 9 is fed at its upper part with a suitable washing liquid, more particularly aliphatic acid from tank 4, fed through pipe 10 fitted with a control valve 11.
  • the gases leaving from the top of column 9 are recycled to reactor 1 through pump 12.
  • Residual mixture of propylene and inert gas if any is discarded through pipe 13.
  • Fresh propylene or proplyene-containing gas is fed through pipe 14. Regulation of the throughput is effected by means of valve inserted in pipe 13.
  • the bath may be effected through a pipe 16 which, for the sake of illustration, has been placed at the bottom of reactor 1 in the drawing.
  • Column 9 may be removed from the apparatus if either condenser 8 is cooled very strongly so that the ester content of the escaping gases is very low, or the non-condensed ester is allow to remain the gas recycle but such a feature results in diminution of production capacity of the bath.
  • an important characteristic of our invention consists in the continuous removal from the bath of the isopropyl ester as it is formed therein. This is done by the propylene containing gas of which only a part reacts while the remainder carries off the ester. This feature makes it possible to operate at a temperature substantially below the boiling point of the reaction mixture and to perform the production and separation of the ester in a one-phase, continuous process.
  • Example 1 Composition of the bath: Sulfuric acid, 3.2 kg. Acetic acid, 5.2 kg. Isopropyl acetate, 1.3 kg. Water, 1 kg. Isopropyl hydrogen sulfate, 9.3 kg. Feed:
  • Example 2 Composition of the bath: Sulfuric acid, 4.6 kg. Acetic acid, 1.6 kg. Isopropyl acetate, 1.1 kg. Water, 1.75 kg. Isopropyl hydrogen sulfate, 7.7 kg. Feed:
  • Our invention is particularly suitable for producing isopropyl acetate but is not limited to such production.
  • we may react propylene with aliphatic acids other than acetic, such for example as propionic, butyric and isobutyric acids and the homologues of such acids having 5 to 8 carbon atoms.
  • aliphatic acids other than acetic such for example as propionic, butyric and isobutyric acids and the homologues of such acids having 5 to 8 carbon atoms.
  • Formic acid cannot be employed.
  • the conditions of sulfuric acidity, amount of aliphatic acid, temperature, rate of passage of gas, should be adjusted according to the aliphatic acid in use, but should be kept within the limits hereinabove set forth.
  • the rate of feed of said aliphatic acid being sufficient to maintain the aliphatic acid content of the bath within the range mentioned above, the rate of feed of propylene being about 2-5 cubic meters per hour per kg. of said bath, and removing the isopropyl ester from the bath by gas containing propylene at substantially the rate at which the isopropyl ester is formed in the bath.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US355724A 1952-12-05 1953-05-18 Process for producing aliphatic esters Expired - Lifetime US2740800A (en)

Applications Claiming Priority (1)

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FR1068204T 1952-12-05

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US2740800A true US2740800A (en) 1956-04-03

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US355724A Expired - Lifetime US2740800A (en) 1952-12-05 1953-05-18 Process for producing aliphatic esters

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US (1) US2740800A (pm)
BE (1) BE524866A (pm)
DE (1) DE949823C (pm)
FR (1) FR1068204A (pm)
GB (1) GB743463A (pm)
NL (1) NL87452C (pm)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5384426A (en) * 1992-12-08 1995-01-24 Daicel Chemical Industries, Ltd. Process for the preparation of isopropyl acetate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2079652A (en) * 1934-03-09 1937-05-11 Socony Vacuum Oil Co Inc Manufacture of esters from olefines

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2079652A (en) * 1934-03-09 1937-05-11 Socony Vacuum Oil Co Inc Manufacture of esters from olefines

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5384426A (en) * 1992-12-08 1995-01-24 Daicel Chemical Industries, Ltd. Process for the preparation of isopropyl acetate

Also Published As

Publication number Publication date
NL87452C (pm) 1958-02-15
FR1068204A (fr) 1954-06-23
DE949823C (de) 1956-09-27
GB743463A (en) 1956-01-18
BE524866A (fr) 1954-06-05

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