# US 11,440,863 B2 · Process for preparing an alcohol from hydrocarbons > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,440,863 B2 - Document ID: US11440863B2 - Status: Granted - Kind: B2 - Application number: 16/888,920 - Filed: 2020-06-01 - Published: 2020-12-17 - Granted: 2022-09-13 - Earliest claimed: 2019-06-12 - Assignees: Evonik Operations GmbH - Applicants: Evonik Operations GmbH - Inventors: Peter Kucmierczyk; Robert Franke; Dirk Fridag; Johannes Knossalla; Marc Schäpertöns; Frederik Gluth - Web page: https://patentgrep.com/patent/US11440863B2 ## CPC - C07C 29/149: with hydrogen or hydrogen-containing gases - B01J 31/2234: {Beta-dicarbonyl ligands, e.g. acetylacetonates} - C07C 29/132: by reduction of an oxygen containing functional group - C07C 29/76: by physical treatment - C07C 29/78: by condensation or crystallisation - C07C 29/80: by distillation - C07C 29/86: by liquid-liquid treatment - C07C 67/38: by addition to an unsaturated carbon-to-carbon bond - C07C 67/48: Separation; Purification; Stabilisation; Use of additives - B01J 2523/824: Palladium - B01J 2531/004: Ligands - C07C 67/03: by reacting an ester group with a hydroxy group - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS ## Abstract The invention provides a process for preparing an alcohol by hydrogenating an ester which is obtained by alkoxycarbonylating a C2 to C20 hydrocarbon having at least one multiple bond, preferably having at least one olefinic double bond, in which the homogeneous catalyst system used is separated from the product mixture by means of membrane separation. In a development of the present invention, the ester thus formed is converted to another ester by transesterification and then hydrogenated. ## Claims ### Claim 1 A process for preparing a target alcohol, wherein the process comprises the following steps: a) preparing an ester by carbonylating a C2 to C16 alkene or isoalkene with carbon monoxide and with an alcohol A, which is a mono- or polyalcohol (two or more OH groups) having from 1 to 50 carbon atoms or is a mixture of two or more mono- and/or poly alcohols and which is used in a molar ratio to the C2 to C16 alkene or isoalkene (alcohol:C2 to C16 alkene or isoalkene) of from 2 to 20, in the presence of a homogeneous catalyst system comprising at least one metal of groups 8 to 10 of the Periodic Table of the Elements or a compound thereof, a phosphorus-containing ligand and an acid, in a reaction zone to obtain a liquid product mixture, wherein the carbon monoxide is directly supplied or by a carbon monoxide-containing gas selected from the group consisting of synthesis gas, water gas, and generator gas; b) performing a membrane separation to separate the homogeneous catalyst system from the liquid product mixture, which enriches the homogeneous catalyst system and additionally unconverted hydrocarbon and/or unconverted alcohol A in the retentate and enriches the ester formed in step a) in the permeate, wherein the membrane material used is an organic solvent nanofiltration membrane material which is acid-stable, stable in the presence of the acid of the catalyst system for at least 300 h, and which has at least one separation-active layer, and wherein the retentate is returned to the reaction zone in step a) and the permeate is routed to the subsequent step c); c) separating the ester formed in step a) from the permeate in at least one separation process step selected from the group consisting of thermal separation, distillation, extraction, crystallization and membrane separation; d) hydrogenating the ester separated in step c) with hydrogen in the presence of the heterogeneous catalyst system in a hydrogenation zone to obtain an alcohol mixture comprising at least the target alcohol, the eliminated alcohol A and unconverted esters; and e) separating the target alcohol formed in step d) in at least one separation process step selected from thermal separation, distillation, extraction, crystallization, and membrane separation. ### Claim 2 (depends on 1) The process according to claim 1, wherein the separation-active layer is composed of a PAEK polymer. ### Claim 3 (depends on 2) The process according to claim 2, wherein the separation-active layer is composed of PEEK having a degree of sulfonation of less than 20%. ### Claim 4 (depends on 1) The process according to claim 1, wherein the alcohol A used in step a) is a mono- or polyalcohol (two or more OH groups) having from 1 to 15 carbon atoms, or a mixture of two or more mono- and/or poly alcohols. ### Claim 5 (depends on 4) The process according to claim 4, wherein the alcohol A used in step a) is selected from the group consisting of methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 2-propanol, tert-butanol, 3-pentanol, 2-propylheptanol, cyclohexanol, phenol and mixtures thereof. ### Claim 6 (depends on 1) The process according to claim 1, wherein the C2 to C16 hydrocarbon comprises at least one olefinic double bond. ### Claim 7 (depends on 1) The process according to claim 1, wherein the metal of groups 8 to 10 of the Periodic Table of the Elements or a compound thereof in the homogeneous catalyst system in step a) is palladium or a compound thereof. ### Claim 8 (depends on 1) The process according to claim 1, wherein the phosphorus-containing ligand in the homogeneous catalyst system has a bidentate structure. ### Claim 9 (depends on 1) The process according to claim 1, wherein the reaction in step a) is conducted at a pressure of from 5 to 60 bar. ### Claim 10 (depends on 1) The process according to claim 1, wherein the acid in the catalyst system in step a) is a Bronsted acid having a pKa≤5, or a Lewis acid having an LAU value of more than 25. ### Claim 11 (depends on 1) The process according to claim 1, wherein the acid in the catalyst system in step a) is a Bronsted acid or a Lewis acid, where the Bronsted acid is perchloric acid, sulfuric acid, phosphoric acid, methylphosphonic acid or a sulfonic acid, and where the Lewis acid is aluminium triflate, aluminium chloride, aluminium hydride, trimethylaluminium, tris(pentafluorophenyl)borane, boron trifluoride, boron trichloride or a mixture thereof. ### Claim 12 (depends on 1) The process according to claim 1, wherein the carbon monoxide-containing gas is the synthesis gas and is separated to obtain separated carbon monoxide and separated hydrogen upstream of the reaction zone and the carbon monoxide is routed to the reaction zone in step a) and the hydrogen separated to the hydrogenation zone in step d). ### Claim 13 (depends on 2) The process according to claim 2, wherein the separation-active layer is composed of PEEK. ### Claim 14 (depends on 2) The process according to claim 2, wherein the alcohol A used in step a) is a mono- or polyalcohol (two or more OH groups) having from 1 to 10 carbon atoms, or a mixture of two or more mono- and/or poly alcohols. ### Claim 15 (depends on 1) The process according to claim 1, wherein the acid in the catalyst system in step a) is a Bronsted acid having a pKa≤3, or a Lewis acid having an LAU value of more than 29. ### Claim 16 (depends on 2) The process according to claim 2, wherein the C2 to C16 hydrocarbon having at least one olefinic double bond which is used in step a) is an n- or isoalkene having from 2 to 16 carbon atoms.