# US 5,703,252 A · Recovery of Tocopherols > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 5,703,252 A - Document ID: US5703252A - Status: Granted - Kind: A - Application number: 08/753,460 - Filed: 1996-11-25 - Granted: 1997-12-30 - Earliest claimed: 1996-11-25 - Assignees: Henkel Corporation - Inventors: Tracy K. Hunt; Joerg Schwarzer - Web page: https://patentgrep.com/patent/US5703252A ## CPC - C07D 311/72: 3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols - C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08) ## Abstract Starting from a mixture containing tocopherol, fats and/or fat derivatives, more particularly fatty acids, and optionally sterol and/or sterol derivatives, the free fatty acids present in the mixture are esterified with an alcohol and fatty glycerides are transesterified with an alcohol in the presence of a zinc oxide and/or zinc hydroxide catalyst. After the esterifications, the excess lower alcohol is distilled off from the reaction mixture. The transesterification catalyst and the glycerol present, if any, are removed and the fatty acid alkyl ester is distilled off from the mixture. Distillation of fatty acid alkyl esters can be accomplished with a packed column in sequence with a wiped film evaporator. The simultaneous recovery of tocopherol and sterol is possible. Tocopherols and sterols can be separated by the crystallization of sterols from a blend of organic solvents. ## Claims ### Claim 1 A process useful in the recovery of tocopherols from a tocopherol mixture comprised of fatty acids and tocopherols, said process comprising esterifying free fatty acids present in said tocopherol mixture and transesterifying fatty acid glyceride esters present in said tocopherol mixture by mixing said tocopherol mixture with a lower alcohol in the presence of a zinc catalyst selected from the group consisting of zinc oxide, zinc hydroxide, and mixtures thereof, to form a reaction mixture in a reaction vessel, the temperature of said reaction mixture being above the atmospheric boiling point of said alcohol and the pressure within said reaction vessel being sufficient to maintain at least a major proportion of said alcohol in a liquid phase. ### Claim 2 (depends on 1) The process of claim 1 wherein said lower alcohol is a member selected from the group consisting of primary and secondary mono-alkanols having less than five carbon atoms. ### Claim 3 (depends on 1) The process of claim 1 wherein the product of the process is dried and mixed with a lower alcohol in the presence of an alkoxide catalyst selected from the group consisting of alkali metal alkoxides of said alcohol, to form a reaction mixture in a reaction vessel, the temperature of said reaction mixture being above the atmospheric boiling point of said alcohol and the pressure within said reaction vessel being sufficient to maintain at least a major proportion of said alcohol in a liquid phase. ### Claim 4 (depends on 3) The process of claim 3 wherein the process further comprises distilling excess lower alcohol from the product of said process. ### Claim 5 (depends on 4) The process of claim 4 wherein said process further comprises washing the product of said process to remove glycerol produced by said transesterification. ### Claim 6 (depends on 5) The process of claim 5 wherein said washing comprises a first washing with an aqueous mineral acid followed by a washing with pure water. ### Claim 7 (depends on 1) The process of claim 1 wherein said lower alcohol is a C.sub.1 to C.sub.4 mono-hydric alkanol. ### Claim 8 (depends on 1) The process of claim 1 wherein said lower alcohol is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, n-butanol, and tert-butanol. ### Claim 9 (depends on 1) The process of claim 1 wherein the amount of said lower alcohol is equal in mass to from about 20% to about 80% with respect to the mass of original tocopherol containing starting material. ### Claim 10 The process of claim I wherein the amount of said lower alcohol is equal in mass to from about 50% to about 60% with respect to the mass of original tocopherol containing starting material. ### Claim 11 (depends on 1) The process of claim 1 wherein the amount of said zinc catalyst is from about 0.005% to about 5% by weight of the tocopherol mixture. ### Claim 12 (depends on 1) The process of claim 1 wherein the amount of said zinc catalyst is from about 0.01% to about 1% by weight of the tocopherol mixture. ### Claim 13 (depends on 1) The process of claim 1 wherein the amount of said zinc catalyst is from about 0.05% to about 0.2% by weight of the tocopherol mixture. ### Claim 14 (depends on 1) The process of claim 1 wherein said esterifying and transesterifying are conducted at a temperature between about 150.degree. C. and about 240.degree. C. ### Claim 15 (depends on 1) The process of claim 1 wherein said esterifying and transesterifying are conducted over a time of about 1 to about 3 hours. ### Claim 16 (depends on 1) The process of claim 1 wherein a major proportion of the fatty acids and fatty glyceride esters are esterified to produce alkyl fatty esters. ### Claim 17 (depends on 1) The process of claim 1 wherein more than about 50% by weight of the fatty acids and fatty glyceride esters are esterified to produce alkyl fatty esters. ### Claim 18 (depends on 1) The process of claim 1 wherein at least about 90% by weight of the fatty acids and fatty glyceride esters are esterified to produce alkyl fatty esters. ### Claim 19 (depends on 1) The process of claim 1 wherein the product is further transesterified in the presence of an alkoxide catalyst to effect essentially complete conversion of sterol esters to free sterols. ### Claim 20 (depends on 19) The process of claim 19 wherein the alkoxide catalyst is a lower alkoxide. ### Claim 21 (depends on 20) The process of claim 20 wherein said catalyst is sodium methoxide in methanol. ### Claim 22 A process useful in the recovery of tocopherols from a tocopherol mixture comprised of fatty acids and tocopherols, said process comprising esterifying free fatty acids present in said tocopherol mixture and transesterifying fatty acid glyceride esters present in said tocopherol mixture by mixing said tocopherol mixture with methanol in an amount of from about 20% to about 80% by weight of said tocopherol mixture, in the presence of a zinc catalyst selected from the group consisting of zinc oxide, zinc hydroxide, and mixtures thereof, in an amount of from about 0.005% to about 5% by weight of the tocopherol mixture, to form a reaction mixture in a reaction vessel, the temperature of said reaction mixture being above the atmospheric boiling point of methanol and the pressure within said reaction vessel being sufficient to maintain at least a major proportion of said alcohol in a liquid phase.