# US 9,040,748 B2 · Hydrocarboxylation of aqueous formaldehyde using a dehydrating recycle stream to decrease water concentration > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,040,748 B2 - Document ID: US9040748B2 - Status: Granted - Kind: B2 - Application number: 13/491,954 - Filed: 2012-06-08 - Published: 2013-12-12 - Granted: 2015-05-26 - Earliest claimed: 2012-06-08 - Assignees: Eastman Chemical Company - Applicants: Mesfin Ejerssa Janka; Scott Donald Barnicki; Robert Thomas Hembre; Kelley Margaret Moran; Stephen Neal Falling - Inventors: Mesfin Ejerssa Janka; Scott Donald Barnicki; Robert Thomas Hembre; Kelley Margaret Moran; Stephen Neal Falling - Web page: https://patentgrep.com/patent/US9040748B2 ## CPC - C07C 51/12: on an oxygen-containing group in organic compounds, e.g. alcohols - C07C 29/149: with hydrogen or hydrogen-containing gases - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS ## Abstract Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of aqueous formaldehyde. The water in the hydrocarboxylation zone is reduced via reaction with the ester bonds in a recycle stream comprising glycolic acid oligomers and/or methyl glycolate oligomers. ## Claims ### Claim 1 A process for the preparation of glycolic acid, comprising (A) feeding carbon monoxide, aqueous formaldehyde, and a recycle dehydration stream to a hydrocarboxylation reaction zone to produce an effluent comprising glycolic acid, glycolic acid oligomers, and water; (B) dehydrating said effluent to produce a first dehydration stream having a higher degree of polymerization (Dp) than said effluent and a water stream; and (C) splitting said first dehydration stream into said recycle dehydration stream of step (A) and an intermediate stream, wherein said feeding of said recycle dehydration stream and said aqueous formaldehyde of step (A) occurs at a molar ratio of ester bond equivalents:water of from 0.2:1 to 4:1. ### Claim 2 (depends on 1) The process according to claim 1, wherein said first dehydration stream comprises glycolic acid and glycolic acid oligomers having said degree of polymerization (Dp) of from 1.1 to 4.0. ### Claim 3 (depends on 1) The process according to claim 1, wherein said first dehydration stream comprises glycolic acid and glycolic acid oligomers having said degree of polymerization (Dp) of from 1.5 to 3.0. ### Claim 4 (depends on 1) The process according to claim 1, wherein said feeding of said recycle dehydration stream and said aqueous formaldehyde of step (A) occurs at a molar ratio of ester bond equivalents:water of from 1.0:1 to 2.5:1. ### Claim 5 (depends on 1) The process according to claim 1, wherein said aqueous formaldehyde comprises 35 weight percent to 85 weight percent formaldehyde, based on the total weight of said aqueous formaldehyde, the molar ratio of carbon monoxide to formaldehyde ranges from 1:1 to 10:1, and said hydrocarboxylation reaction zone is operated at a pressure of from 35 bar gauge to 200 bar gauge and a temperature of from 80° C. to 220° C. ### Claim 6 (depends on 5) The process according to claim 5, wherein said hydrocarboxylation zone is operated at said temperature of from 160° C. to 210° C. ### Claim 7 (depends on 1) The process according to claim 1, wherein said aqueous formaldehyde and said recycle dehydration stream are contacted and allowed to react prior to said feeding of step (A). ### Claim 8 (depends on 1) The process according to claim 1, further comprising (D) reacting said intermediate stream with a first ethylene glycol while simultaneously removing water to produce an esterification effluent comprising EG glycolate ester oligomers and glycolic acid oligomers and an overhead stream comprising water; and (E) reacting hydrogen with said esterification effluent to produce a second ethylene glycol, separating said second ethylene glycol into a product ethylene glycol and said first ethylene glycol, and recycling said first ethylene glycol to step (D). ### Claim 9 A process for the preparation of glycolic acid, comprising (A) feeding carbon monoxide, aqueous formaldehyde, and a recycle dehydration stream to a hydrocarboxylation reaction zone to produce an effluent comprising glycolic acid, glycolic acid oligomers, methyl glycolate, methyl glycolate oligomers, and water; (B) dehydrating said effluent in the presence of methanol to produce a first dehydration stream having a degree of polymerization (Dp) higher than said effluent and an overhead stream comprising water and methanol; and (C) splitting said first dehydration stream into said recycle dehydration stream of step (A) and an intermediate stream, wherein said feeding of said recycle dehydration stream and said aqueous formaldehyde of step (A) occurs at a molar ratio of ester bond equivalents:water of from 0.2:1 to 4:1. ### Claim 10 (depends on 9) The process according to claim 9, wherein said first dehydration stream comprises glycolic acid, glycolic acid oligomers, methyl glycolate, and methyl glycolate oligomers having said degree of polymerization (Dp) of from 1.1 to 4.0. ### Claim 11 (depends on 9) The process according to claim 9, wherein said first dehydration stream comprises glycolic acid, glycolic acid oligomers, methyl glycolate, and methyl glycolate oligomers having said degree of polymerization (Dp) of from 1.5 to 3.0. ### Claim 12 (depends on 9) The process according to claim 9, wherein said feeding of said recycle dehydration stream and said aqueous formaldehyde of step (A) occurs at a molar ratio of ester bond equivalents:water of from 1.0:1 to 2.5:1. ### Claim 13 (depends on 9) The process according to claim 9, wherein said aqueous formaldehyde comprises 35 weight percent to 85 weight percent formaldehyde, based on the total weight of said aqueous formaldehyde, the molar ratio of carbon monoxide to formaldehyde ranges from 1:1 to 10:1, and said hydrocarboxylation reaction zone is operated at a pressure of from 35 bar gauge to 200 bar gauge and a temperature of from 80° C. to 220° C. ### Claim 14 (depends on 13) The process according to claim 13, wherein said hydrocarboxylation reaction zone is operated at said temperature of from 160° C. to 210° C. ### Claim 15 (depends on 9) The process according to claim 9, wherein said aqueous formaldehyde and said recycle dehydration stream are contacted and allowed to react prior to said feeding of step (A). ### Claim 16 (depends on 9) The process according to claim 9, further comprising (D) hydrogenating said intermediate stream to produce ethylene glycol. ### Claim 17 (depends on 9) The process according to claim 9, further comprising (D) reacting said intermediate stream with a first ethylene glycol while simultaneously removing water and methanol to produce an esterification effluent comprising EG glycolate ester oligomers and glycolic acid oligomers and an overhead stream comprising water and methanol; and (E) reacting hydrogen with said esterification effluent to produce a second ethylene glycol, separating said second ethylene glycol into a product ethylene glycol and said first ethylene glycol, and recycling said first ethylene glycol to step (D).