# US 4,391,753 A · Process for the manufacture of carboxylic peracids > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 4,391,753 A - Document ID: US4391753A - Status: Granted - Kind: A - Application number: 06/225,189 - Filed: 1981-01-15 - Granted: 1983-07-05 - Earliest claimed: 1978-03-28 - Assignees: Propylox - Inventors: Nicolas Hardy; Luc Lerot; Rene Walraevens - Web page: https://patentgrep.com/patent/US4391753A ## CPC - C07D 301/14: with organic peracids, or salts, anhydrides or esters thereof - C07C 407/00: Preparation of peroxy compounds - C07C 407/003: {Separation; Purification; Stabilisation; Use of additives} - C07C 409/24: the —O—O— group being bound between a >C=O group and hydrogen, i.e. peroxy acids - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract A continuous process for the manufacture of carboxylic peracids by reacting the corresponding carboxylic acid with hydrogen peroxide in the presence of a catalyst and in the presence of an inert organic liquid which is a solvent for the peracid and is capable of forming a heterogeneous azeotrope with water, removing the water present in the reaction mixture by distillation of the water/organic liquid azeotrope, and keeping sufficient water in the reaction mixture to allow the formation of an aqueous phase which is separate from an organic phase containing the organic liquid. ## Claims ### Claim 1 In a continuous process for the manufacture of an olefin oxide from an olefin by reaction of the olefin with a carboxylic peracid comprising: (a) preparing the carboxylic peracid by reaction, in a reaction mixture, of the corresponding carboxylic acid with hydrogen peroxide in the presence of a catalyst and in the presence of an inert organic liquid which is contained in an organic phase and is a solvent for the peracid and is capable of forming a heterogeneous azeotrope with water, said organic liquid having a higher boiling point that that of the olefin and the olefin oxide, does not form an azeotrope with the olefin and the olefin oxide, and of which the possible azeotropes with the carboxylic acid and the carboxylic peracid have a higher boiling point than that of the olefin and the olefin oxide, removing water present in the reaction mixture by distillation of the water/organic liquid azeotrope, and maintaining a sufficient amount of water in the reaction mixture to allow the formation of an aqueous phase which is separate from the organic phase which contains the organic liquid and the carboxylic peracid; (b) withdrawing part of the reaction mixture of step (a), and then separating the aqueous phase from the organic phase, by decantation, of the part of the reaction mixture which has been withdrawn; (c) introducing the separated aqueous phase of step (b) into the reaction mixture of step (a); (d) reacting an olefin with the carboxylic peracid in the separated organic phase obtained in step (b) to form a reaction mixture containing unreacted olefin, olefin oxide, carboxylic acid and organic liquid; (e) subjecting the reaction mixture of step (d) to a separation to obtain unreacted olefin and an organic solution containing organic liquid, olefin oxide, and carboxylic acid; (f) distilling the organic solution obtained in step (e) to separate the olefin oxide from the carboxylic acid and organic liquid; and (g) feeding the separated carboxylic acid and organic liquid of step (f) to step (a). ### Claim 2 (depends on 1) Process according to claim 1, wherein the weight ratio of the aqueous phase to the organic phase, in the reaction mixture of step (a), is more than 0.1 and less than 10. ### Claim 3 (depends on 1, 2) Process according to claim 1 or 2, wherein the unreacted olefin obtained in step (e) is absorbed in gaseous form in the separated organic phase obtained in step (b) before the separated organic phase is fed to step (d). ### Claim 4 (depends on 1, 2) Process according to claim 1 or 2, wherein the unreacted olefin obtained in step (e) is fed into step (d). ### Claim 5 (depends on 1, 2) Process according to claim 1 or 2, wherein the organic liquid is chosen from among 1,2-dichloropropane, 1,2 dichloroethane, 1,1,2,2-tetra-chloroethane and mixtures thereof. ### Claim 6 (depends on 1, 2) Process according to claim 1 or 2, wherein the olefin in step (d) is propylene, and a temperature of 20 to 100.degree. C. and a pressure of 0.8 to 30 kg/cm.sup.2 are employed in the reaction of step (d). ### Claim 7 (depends on 1, 2) Process according to claim 1 or 2, wherein the olefin in step (d) is allyl chloride or allyl alcohol, and a temperature of 20 to 150.degree. C. and a pressure of 0.1 to 10 kg/cm.sup.2 are employed in the reaction step (d). ### Claim 8 (depends on 1, 2) Process according to claim 1 or 2, wherein the catalyst of step (a) is sulfuric acid. ### Claim 9 (depends on 1, 2) Process according to claim 1 or 2, wherein the organic liquid has a composition such that the solubility of water in the organic phase of step (a) is less than the proportion of water in the water/organic liquid azeotrope. ### Claim 10 (depends on 1, 2) Process according to claim 1 or 2, wherein the amount of catalyst present in the reaction mixture of step (a) is between 0.1 and 30 times the total weight of carboxylic acid and carboxylic peracid. ### Claim 11 (depends on 1, 2) Process according to claim 1 or 2, wherein the organic liquid is chosen from among carboxylic acid esters, ethers, halogenohydrocarbons, unsubstituted hydrocarbons, hydrocarbons substituted by nitro groups, and non-acidic esters of nitric, phosphoric and carbonic acids. ### Claim 12 (depends on 1, 2) Process according to claim 1 or 2, wherein the carboxylic acid is propionic acid or acetic acid. ### Claim 13 (depends on 1, 2) Process according to claim 1 or 2, wherein the catalyst is chosen from among sulphuric acid, alkyl-, aryl-, arylaklyl- and alkylaryl-sulphonic acids, phosphoric acid, alkyl, aryl, alkylaryl and arylaklyl acid phosphates, trifluoroacetic acid, acetyl-sulphoacetic acid and sulphonated ion exchange resins. ### Claim 14 (depends on 1, 2) Process according to claim 1 or 2, wherein the organic liquid is chosen from among 1,2-dichloropropane and 1,2-dichloroethane, the carboxylic acid is propionic acid and the catalyst is sulphuric acid. ### Claim 15 (depends on 1) Process according to claim 1, wherein the weight ratio of the aqueous phase to the organic phase in the reaction mixture of step (a) is more than 0.05.