# US 2018/0023031 A1 · Recovery of tocopherols/tocotrienols, carotenoids, glycerols, sterols and fatty acid esters from crude vegetable oil and the process thereof > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0023031 A1 - Document ID: US20180023031A1 - Status: Published application - Kind: A1 - Application number: 15/543,125 - Filed: 2015-05-07 - Published: 2018-01-25 - Earliest claimed: 2015-01-12 - Inventors: DAVID SUE SAN HO - Web page: https://patentgrep.com/patent/US20180023031A1 ## CPC - C11B 3/12: by distillation - C11B 3/02: by chemical reaction {(C11B3/003 takes precedence)} - C11B 7/0008: {by differences of solubilities, e.g. by extraction, by separation from a solution by means of anti-solvents (addition of a minor amount of solvent intended to lower the melting point C11B7/0083, C11B7/0091)} - C11C 3/003: {by esterification of fatty acids with alcohols (C11C3/02 takes precedence)} - C11B: PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES (drying-oils C09F) - C11C: FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM ## Abstract A process for recovering tocotrienols/tocopherols, carotenoids and sterols from crude vegetable oil, characterised in that prior to the recovery steps, the amount of the free fatty acids in the oil is reduced to 3.50% by weight by distillation or neutralization. ## Claims ### Claim at position 1 -70. (canceled) ### Claim 71 A process for recovering tocotrienols, tocopherols, carotenoids and sterols from crude vegetable oil, wherein prior to a recovery step, an amount of free fatty acids in the crude vegetable oil is reduced to less than 3.50% by weight of a total crude vegetable oil composition, comprising the steps of: distilling the crude vegetable oil or fractions thereof using two distillation columns, in a sequential arrangement, each column operating under a pressure and at a temperature suitable for separating tocotrienols, tocopherols, carotenoids or sterols from the fractions. ### Claim 72 (depends on 71) The process according to claim 71, wherein the amount of the free fatty acids in the crude vegetable oil is reduced by distillation or neutralization. ### Claim 73 A process for recovering tocotrienols, tocopherols, carotenoids and sterols from crude vegetable oil, wherein prior to the recovery steps, comprising the steps of: distilling an amount of free fatty acids in the crude vegetable oil so that the fatty free acids are reduced to 3.50% by weight, wherein the distilling step is performed using two distillation columns, a first column operating at a temperature of 90 to 200° C. and a pressure ranging from 10 to 100 kPa and a second column operating at a temperature of at 120 to 250° C. and a pressure ranging from 0.10 to 10 kPa. ### Claim 74 (depends on 73) The process according to claim 73, wherein the distilling step is performed to produce a first fraction enriched with carotenoids and a second fraction enriched with tocotrienols or tocopherols. ### Claim 75 (depends on 74) The process according to claim 74, further comprising the steps of: transesterifying the first fraction in the presence of an alcohol and a basic catalyst to convert any glycerides therein to fatty acid esters and glycerine, forming a transesterified mixture comprising glycerine, fatty acid esters and carotenoids, followed by distilling the transesterified mixture to separate carotenoids; and esterifying the second fraction in the presence of an alcohol and an acid catalyst to convert fatty acids therein to fatty acid esters, forming an esterified mixture comprising fatty acid esters and tocotrienols or tocopherols, followed by distilling the esterified mixture to separate the tocotrienols or tocopherols. ### Claim 76 (depends on 75) The process according to claim 75, wherein the transesterifying step is conducted at a temperature of 35 to 80° C. under atmospheric pressure, with or without agitation, for 0.50 to 12 hours. ### Claim 77 (depends on 75) The process according to claim 75, wherein the distilling step, after the transesterifying step, is performed using two distillation columns, in a sequential arrangement, each column operating under vacuum condition and at a temperature of 120 to 180° C., with the first column having an operating temperature lower than the second column. ### Claim 78 (depends on 75) The process according to claim 75, wherein the esterifying step is conducted at a temperature of 5 to 90° C. for 0.5 to 6 hours, with or without agitation. ### Claim 79 (depends on 75) The process according to claim 75, wherein the distilling step, after the esterifying step, is performed using two distillation columns, in a sequential arrangement, each column operating under vacuum condition and at a temperature of 120 to 180° C., with a first column having an operating temperature higher than a second column. ### Claim 80 (depends on 75) The process according to claim 75, further comprising the steps of separating the glycerine from the transesterified mixture to produce an ester-rich portion, prior to distilling the transesterified mixture. ### Claim 81 (depends on 80) The process according to claim 80, wherein the glycerine is separated from the transesterified mixture by centrifugation or gravitational settling, producing a glycerine-rich portion and the ester-rich portion, wherein the glycerine-rich portion is extracted and neutralized using an acid to recover glycerine therefrom. ### Claim 82 (depends on 80) The process according to claim 80, further comprising the steps of: washing the transesterified mixture with a washing agent to remove catalyst, unreacted alcohols and other impurities; and heating the washed and transesterified portion to reduce moisture content therein to less than 0.30 wt %, in which the heating step is conducted at a temperature of 35 to 80° C. under vacuum or a pressure of 100 kPa for 0.5 to 12 hours. ### Claim 83 (depends on 75) The process according to claim 75, further comprising the steps of: adding an organic solvent into the distilled transesterified mixture; chilling the mixture to produce crystallised carotenoids; centrifuging the resulting mixture to produce a top layer and a bottom layer; wherein the bottom layer comprises crystallised carotenoids in an amount of 28 to 45% by weight. ### Claim 84 (depends on 83) The process according to claim 83, further comprising the steps of: heating the bottom layer at a temperature of 45 to 80° C. under vacuum condition of 70 to 75 cm Hg to evaporate the solvent contained therein to a level of less than 1% or lower for recovery of carotenoids. ### Claim 85 (depends on 83) The process according to claim 83, further comprising the steps of: transesterifying the top layer in the presence of an alcohol and a basic catalyst to increase the carotenoid content therein; and washing the mixture obtained thereof with a methanolic acid solution to remove impurities present therein. ### Claim 86 (depends on 75) The process according to claim 75, further comprising the steps of: transesterifying the distilled esterified mixture in the presence of an alcohol and a basic catalyst to convert the fatty acids therein to fatty acid esters, forming a product mixture comprising glycerine and fatty acid esters. ### Claim 87 (depends on 86) The process according to claim 86, wherein the transesterifying step is conducted at a temperature of 5 to 90° C. with or without agitation for 0.5 to 6 hours. ### Claim 88 (depends on 86) The process according to claim 86, further comprising the steps of: distilling the product mixture with reduced moisture content to obtain a composition with a pre-determined concentration of tocotrienols, tocopherols and sterols. ### Claim 89 (depends on 88) The process according to claim 88, wherein the distilling step is performed using two distillation columns, in a sequential arrangement, one column operating at a temperature of 120 to 180° C. and a pressure of 0.01 to 10 kPa and a second column operating at a temperature of 120 to 180° C. and a pressure of 0.01 to 3 kPa. ### Claim 90 (depends on 88) The process according to claim 88, further comprising the steps of: separating the sterols from the composition. ### Claim 91 (depends on 90) The process according to claim 90, wherein the sterols are separated by treating the composition with an alcohol and chilling the resulting mixture to produce crystallised sterols that are to be filtered. ### Claim 92 A process for recovering tocotrienols, tocopherols, carotenoids and sterols from crude vegetable oil, wherein prior to a recovery step, an amount of free fatty acids in the crude vegetable oil is reduced to less than 3.50% by weight by neutralization, comprising the steps of: neutralizing the crude vegetable oil by adding a basic solution thereto so as to convert fatty acids to salts that are to be separated by filtration; transesterifying the neutralized oil in the presence of an alcohol and a basic catalyst to convert glycerides therein to fatty acid esters and glycerine, forming an ester-rich fraction and a glycerol-rich fraction; separating the ester-rich fraction from the glycerol-rich fraction; distilling the ester-rich fraction to produce a concentrated stream comprising tocotrienols, tocopherols, carotenoids and sterols, in which the distilling step is performed using distillation columns arranged sequentially, each column operating at a pressure of 0.001 kPa to 0.01 kPa and at a temperature of 120 to 180° C.; further transesterifying the concentrated stream in the presence of an alcohol and a basic catalyst to form an ester-enriched fraction and a glycerol-rich fraction; and repeating the transesterification, separation and distilling steps sequentially and repeatedly to obtain a composition with a pre-determined concentration of tocotrienols, tocopherols, carotenoids and sterols. ### Claim 93 (depends on 92) The process according to claim 92, wherein the neutralization is performed such that a basic solution is added to the crude vegetable oil to convert the fatty acids to salts that are to be separated by filtration. ### Claim 94 (depends on 92) The process according to claim 92, further comprising the steps of: heating the neutralized oil at a temperature of 40 to 80° C. under vacuum condition or at a pressure equivalent to 100 kPa under agitation for a duration of 0.5 to 12 hours, prior to transesterification, to reduce the moisture content in the neutralized oil to a level of less than 0.20% by weight. ### Claim 95 (depends on 92) The process according to claim 92, further comprising the steps of: washing the ester-rich portion with a washing agent to remove catalyst, unreacted alcohols and any impurities, prior to the distilling step. ### Claim 96 (depends on 95) The process according to claim 95, further comprising the steps of: heating the washed ester-rich portion to reduce moisture content therein to less than 0.30 wt %, in which heating is conducted at a temperature of 40 to 70° C. under vacuum or a pressure of 100 kPa. ### Claim 97 (depends on 92) The process according to claim 92, further comprising the steps of: washing the ester-rich portion with a washing agent to remove catalyst, unreacted alcohols and any impurities. ### Claim 98 (depends on 92) The process according to claim 92, further comprising the steps of: washing the composition with predetermined concentration of tocotrienols, tocopherols, carotenoids and sterols with a methanolic acid solution to remove any impurities present therein, wherein the washing step is performed at a temperature of 28 to 50° C. under atmospheric pressure. ### Claim 99 (depends on 98) The process according to claim 98, further comprising the steps of: crystallizing the dried composition in the presence of an alcohol to separate the sterols and glycerides, if present therein, in a form of crystals, in which the crystallization is performed at a temperature of −30 to 0° C. for a period of 12 hours to 3 days. ### Claim 100 (depends on 98) The process according to claim 98, further comprising the steps of: separating the sterol crystals and glyceride crystals, if present; and evaporating the alcohol contained therein by heating. ### Claim 101 (depends on 92) The process according to claim 92, wherein the basic solution is a caustic solution or sodium hydroxide solution. ### Claim 102 (depends on 92) The process according to claim 92, wherein the basic catalyst is sodium methoxide, sodium hydroxide in methanol, potassium methoxide or potassium hydroxide in methanol. ### Claim 103 (depends on 92) The process according to claim 92, wherein the alcohol is any one of methanol, ethanol, propanol or butanol. ### Claim 104 (depends on 83) The process according to claim 83, wherein the organic solvent is any one of hexane, heptane, iso-octane, acetone or ethyl acetate. ### Claim 105 (depends on 75) The process according to claim 75, wherein the acid catalyst is any one of hydrochloric acid, acetic acid, sulphuric acid or citric acid. ### Claim 106 (depends on 71) The process according to claim 71, wherein the crude vegetable oil is any one of crude palm oil, red palm oil, red palm olein, red palm fiber oil or any crude oil having a free fatty acid content of more than 3.50% by weight of the total crude vegetable oil composition.