MXPA97003275A - Process for the production of tocopherol and concentrate of tocoferol / tocotrie - Google Patents

Abstract

An improved process for the preparation of tocopherol and tocopherol / tocotrienol concentrates from vegetable oil distillates is described. The tocopherol concentrates are obtained containing 20-80% tocopherol by weight, with a total recovery of tocopherol from 72% to 97%. The process consists first of an esterification reaction, where the more volatile alcohols are converted to their less volatile fatty acid esters, followed by a series of distillation steps, where the components with higher boiling point and lower than the tocopherols, are separated from Tocopherols and other substances of similar boiling point. The advantages of the process are that the tocopherol and tocopherol / tocotrienol concentrates are efficiently and economically produced in a minimum number of stages without the use of solvents and with a relatively small capital investment.

Description

PROCESS FOR THE PRODUCTION OF TOCOPHEROL AND CONCENTRATE OF TOCOPHEROL / TOCOTRIENOL DESCRIPTION OF THE INVENTION This invention belongs to the field of organic chemistry. In particular, this invention relates to a process for the manufacture of tocopherol concentrate from the by-products of the vegetable oil refining. Alpha, beta, gamma, and delta tocopherol (hereinafter referred to as tocopherols) can be found in different ratios and concentrations in unpurified vegetable oils such as soybean oil, sunflower oil, canola oil, rapeseed oil, oil of cottonseed, sesame oil, corn oil, palm oil, palm kernel oil and rice husk oil. Palm oil and rice husk oil in particular contain high levels of both tocopherols and tocotrienols, while other vegetable oils contain mainly tocopherols. Typical crude palm oils contain 600-700 mg / kg of tocopherols and tocotrienols (50% tocotrienols) and unpurified rice husk oil contains 800-900 mg / kg tocopherols and tocotrienols (57% tocotrienols) (See, for example, Proc. Malavs. Biochem. Soc. Conf. (1983) pp. 15-17 and Lipids Handbook, 2d Ed., (1994) Chap an & Hall, p. 129). Tocopherols and tocotrienols are valuable constituents of vegetable oil that can help prevent oxidation and deterioration. Tocotrienols are of special interest because of their hypocholesterolemic effects, since they lower the blood level of the low-density lipoprotein fraction of cholesterol and total serum cholesterol, while increasing the ratio of the high-density lipoprotein fraction of cholesterol a low density lipoprotein fraction. Such effects have been shown to be clinically significant in decreasing the risk of heart disease. (T. Gordon, et al., "High Density Lipoproteins as a Protective Factor Against Coronary Heart Disease," The American Journal of Medicine, 62, pp. 707-714 (1977)). These tocopherols are a valuable constituent of vegetable oils as they help prevent oxidation and deterioration. During the refinement of vegetable oils a large fraction of the tocopherols are lost in various byproducts and waste streams. These waste streams and by-products include, but are not limited to, deodorizing distillates, steam refining distillates and acidic soap dets. Vegetable oil that is refined by by-products typically contains less than 1% to more than 20% by weight of tocopherol. The by-products of oil refining are a valuable source of raw material for the production of natural vitamin E and other antioxidants tocopherol. However, the by-product currents also contain from 20 to 99% by weight of free fatty acids, less than 1% to 20% by weight of sterols, less than 1% to 20% by weight of fatty acid sterol esters , less than 1% to 40% by weight of mono, di, and triglycerides, less than 1% to 30% by weight of hydrocarbons and various percentages by weight of other compounds, in addition to tocopherols. In this way, in order to obtain a current of tocopherol concentrate useful for the production of high purity vitamin E, it is necessary to eliminate these substances. Numerous methods have been prod for the recovery of tocopherols from the byproducts of vegetable oil refining. For example, U.S. Patent No. 2,432,181 teaches that tocopherols can be recovered from vegetable oils and fats by reacting the fatty acid glycerides with an aliphatic monohydric alcohol in the presence of an alkaline alcoholysis catalyst, followed by distillation. snapshot of the residual glycerol alcohol and the fatty acid esters. U.S. Patent No. 3,153,055 teaches a process for the isolation of sterols and tocopherols from the deodorizing distillate by esterification of free fatty acids and glycerides in lower monohydric alcohol esters under strongly acidic conditions. The sterols and tocopherols are fractionally extracted from the esterification product with a combination of polar and non-polar solvents. United States Patent No. 3, 335,154 teaches that the deodorizing distillate can be saponified and acidulated to convert the glycerides and sterol esters to free fatty acids and free alcohols (glycerol, sterols, respectively). The free fatty acids are esterified with a lower monohydric alcohol and mineral acid catalyst. The sterols are precipitated / crystallized by the addition of water to the mixture and the tocopherols are concentrated by removal of the fatty acid esters by molecular distillation. All the above processes experience serious disadvantages. They require the addition of foreign monohydric alcohols and result from the production of fatty acid esters, which are not normally present in the by-product feedstock of the vegetable oil. The excess of monohydric alcohol must be eliminated in an additional processing stage. To produce a highly concentrated tocopherol product, the sterols must either be removed by crystallization or by other means. Saponification requires large amounts of sodium hydroxide and acid for acidification, creating excessive salt waste.

U.S. Patent No. 4,454,329 teaches that a tocopherol concentrate can be obtained from deodorizing distillates by esterification of the free fatty acids with a dihydric or polyhydric alcohol, in the presence of an acid catalyst. The esterification is preferably carried out in the presence of an aromatic solvent such as benzene, toluene or xylene. The esterified mixture is then subjected to either solvent extraction or molecular distillation to produce the final tocopherol concentrate. Preferably, solvent extraction is carried out by hydrogenation to convert the unsaturated triglycerides to saturated triglycerides, thereby decreasing the solubility of the triglycerides in the solvent phase of the extraction. The distillation of the esterified mixture concentrates tocopherols, sterols, hydrocarbons and other components with similar boiling points in the distillate. Triglycerides and other high-boiling components are left in the distillation residue. The above process is not satisfactory for many reasons. Deodorizing distillates and the like, typically contain a ratio of 1/1 to 3/1 of sterols to tocopherols, depending on the source of the vegetable oil. The tocopherols and sterols have very similar boiling points and therefore can not be separated by distillation alone. The esterification does not run in such a way as to ensure that the sterols are converted to sterol esters (which have a boiling point much higher than tocopherol). The distillate containing the tocopherols and sterols produced by the above process must also be treated by other separation techniques to produce a tocopherol concentrate essentially free of sterols. In the solvent extraction version of the process, the solvent must be removed from the tocopherol extract adding additional cost and complication to the process. The preferred modality of solvent extraction, preceded by hydrogenation, adds yet another stage, with the attendant cost and complication. In addition, typical copper and nickel hydrogenation catalysts are known to be prooxidants, which promote the destruction of tocopherol, thereby decreasing the tocopherol yield of the process. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a diagram that delineates an aspect of the method of the present invention, in which an esterification reaction is carried out in the reactor (2), which is then subjected to a series of steps distillation (5), (8), and (9) to provide the desired tocopherol. Figure 2 is a diagram that delineates the preferred method of the present invention, in which an esterification reaction is carried out in the reactor (2) and subjected to two distillation stages. Figures 1 and 2 are described more fully in the following. An object of this invention is to provide an economical, efficient process for the isolation of tocopherols from vegetable oil processing by-products. The raw material for the process can be deodorizing distillate, steam refining distillate, soap supply, acidulated or any other by-product of vegetable oil typically containing less than 1% tocopherol to 20% tocopherol by weight. For the purpose of convenience, the term "tocopherol concentrate" will be used herein to describe concentrates containing both of the tocopherols and any of minor or greater amounts of tocotrienols, depending on the source of the vegetable by-product. Since tocotrienols and tocopherols are very similar in physical properties, they are isolated together as described in the following. In this invention, the vegetable oil by-product is subjected to an esterification step, with or without an acid catalyst, in which the sterols react with the free fatty acid already present in the mixture to form high-boiling sterol esters. Any of the other alcoholic moieties, triterpenoid alcohols, methyl steroids and the like, are converted to high boiling point fatty acid esters and waxes. In addition, any of the mono- and di-fatty acid glycerides are largely converted to triglycerides by reaction with the free fatty acids. Tocopherols also react to a limited extent; the extent of the reaction can be controlled by the appropriate selection of reaction time and temperature. The esterified mixture is then subjected to a series of distillation steps in which the higher and lower boiling components than the tocopherols are separated from the tocopherols and other similar boiling substances. The distillation steps consist of one or more separate distillation operations to remove the higher unreacted free fatty acids, together with any of the low boiling compounds of a product of the tocopherol-rich and a distillation operation to remove a higher tocopherol product of sterol esters, glycerol fatty acid polyesters, waxes and other high-boiling substances. Any of the distillation operations to remove fatty acid and low boiling materials or the distillation operation to remove the high boiling materials can be done first. The product resulting from the process is tocopherol concentrate consisting mainly of tocopherol and hydrocarbons with similar boiling points, which is essentially free of fatty acids, sterols, sterol esters, fatty acid polyesters of glycerol, waxes and other high-point compounds. boiling. As another aspect of this invention, the catalyst for the esterification step is an onoalkyltin compound, a zinc salt of an organic acid, titanium (IV) alkoxides, zinc oxide, phosphoric acid or other mild mineral acids. The present invention provides a method for preparing a tocopherol concentrate, which comprises the steps of: (a) heating a by-product of the vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid sterol esters, sterols, triterpenoid alcohols, methyl sterols and mono-, di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally containing additional C-LQ-C22 fatty acids, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr at 760 torr while the formed water is continuously removed, to provide a mixture consisting of sterol esters, high boiling point fatty acid esters, waxes and glycerides; and (b) followed by subjecting the mixture to a series of distillation operations, comprising: (i) one or more of the separate distillation operations, in which the distillation or distillation is carried out at a temperature of about 200 ° C at 320 ° C and a pressure of about 0.01 torr to 10 torr, in series, in which the unreacted fatty acids and the low-boiling components are removed as a vapor effluent and a liquid effluent consisting of Tocopherols is eliminated; and (ii) wherein the liquid effluent from step (b) (i) is subjected to one or more series distillations, in which the distillation or distillation is carried out at a temperature of about 170 ° C to 270 ° C. ° C and a pressure of about 0.005 torr to 2 torr, in which a concentrate of tocopherol is removed as a vapor effluent and in which the liquid effluent consists of sterol esters, fatty acid esters, glycerides, waxes and other substances of high boiling point are eliminated. As another preferred aspect of this invention, the by-product of the vegetable oil will also contain significant amounts of tocotrienols. In such cases, the tocotrienols will be present in a proportion of approximately 0.5 to 10, by weight based on the amount of tocopherols present, thus producing a concentrate rich in both of the tocopherols and the tocotrienols. The description of a preferred aspect of the present invention is made with reference to the process diagrams of Figures 1 and 2. The by-product of the vegetable oil is fed via line (1) to a stirred tank or reactor discontinuous, unit (2), which operates at a temperature of about 70-300 ° C, preferably in the range of 150-230 ° C, and at a pressure of about 50 torr to 760 torr, preferably of about 100-200 torr. . The residence time in the reactor is preferably from about 1 to 24 hours, more preferably from 90 minutes to 2 hours in the presence of an acid catalyst and from two hours to 10 hours, when no catalyst is used. Preferred catalysts include monoalkyltin compounds, zinc salt of an organic acid, titanium (IV) alkoxides, zinc oxide, phosphoric acid, and other mild mineral acids. During the reaction step, the free fatty acid, which is already present in the feed mixture, reacts with the sterols to form high boiling point sterol esters and water. Other alcoholic moieties, triterpenoid alcohols, methyl sterols and the like also react with the free fatty acids to form high boiling point fatty acids, waxes and water. In addition, any of the glycerol mono- and di-fatty acid esters are largely converted to triglycerides by esterification with the free fatty acids. The tocopherols and tocotrienols also react to a limited extent with the free fatty acid to form tocopherol esters and water. The relative speeds of the esterification reactions is glycerides >; sterols > tocopherols / tocotrienols. In this way, the reaction of tocopherols / tocotrienols can be controlled by the appropriate selection of temperature and reaction time. Recovery of tocopherol / tocotrienol from the reaction step is typically from 80% to 97%, more typically from 85 to 92%. The conversion of sterols to sterol esters of the fatty acid is typically from 75% to 100%, more typically from 85% to 95%. In a preferred embodiment, the C22"C22 fatty acids are added to the initial by-product material, more preferably an amount of up to about 40% by weight, based on the total weight of the initial byproduct material. means for the elimination of the esterification water, line (3) The elimination of the esterification water brings the equilibrium of the reaction towards the formation of the fatty acid ester products.

The esterification product (4) is then subjected to a series of distillation steps, in which the components of higher boiling point and lower boiling point than the tocopherol are separated from tocopherol and other substances of similar boiling point. The distillation steps are one or more separate distillation operations to remove the unreacted free fatty acids from the top together with any of the low-boiling compounds of the tocopherol-rich bottom products, and a distillation operation to eliminate the tocopherol-rich product from the top separating it from sterol esters, glycerol fatty acid polyesters, waxes and other high-boiling compounds. Any of the distillation operations to remove the fatty acids and low boiling materials, or the distillation operation to remove the higher boiling materials can be done first. It should be understood that the reaction and the distillation operations can be carried out in discontinuous, semi-continuous and continuous operation modes. This process produces tocopherol concentrate efficiently and economically in a minimum of stages. No extraneous substances are added to the raw material oil, except possibly an esterification catalyst and added fatty acids of c22"C. No solvents or excess esterification alcohols are needed to be removed from the reaction product. Tocopherol that can be achieved in the final product is in the range of 20-80% tocopherol by weight, depending on the amount of hydrocarbons in the initial material.Most typically the product will have a tocopherol concentration of 30-60% by weight Tocopherol The total recovery of tocopherol from the process is typically from 72% to 97%, more typically from 75% to 92%, more typically from 80% to 85%, One embodiment of the method of the present invention is illustrated by Figure 1. The product (4) of the esterification step is distilled in unit (5) under high vacuum to remove a substantial fraction, typically 50-90%, more typically 60-80%, of the fatty acid without reactant. ction together with a substantial fraction of low boiling materials, stream (6), to leave the product in the bottoms rich in tocopherol (7). The distillation operation is carried out at temperatures and pressures in such a way that the tocopherols are left to a large extent in the product of the bottoms. The temperature and pressure of the distillation operation (5) is in the range of 170 ° to 270 °, from 0.05 to 10 torr. The preferred range is 200 ° C to 240 ° C, from 0.5 torr to 4 torr. The distillation apparatus (5) (as is all the distillation equipment used herein, is preferably a high vacuum design that includes a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, or a falling film evaporator capable of low pressure operation The product (7) from the bottoms of the first distillation operation (5) is distilled a second time in the distillation operation (8) under high vacuum to remove any of the remaining unreacted fatty acids and other low-boiling compounds The distillation temperature (8) must be higher or the pressure lower than the distillation (5) to ensure essentially complete removal of any of the remaining fatty acids. The temperature and pressure of the distillation (8) is in the range of 230 ° C to 300 ° C, from 0.01 to 5 torr.The preferred range is 240 ° C to 280 ° C, 0.1 torr to 2 torr. As a portion, typically 5-30% of the tocopherols will be distilled from the top with the remaining fatty acids in the stream (9), leaving a product (10) in the bottoms rich in tocopherol, without acid. The distillate (9) containing some tocopherols and the remaining free fatty acid can be discarded or recycled to the reactor (2) or to the first operation (5) to improve the total yield of the tocopherols. Since the distillation (5) and the distillation (8) are carried out under different temperature and pressure conditions, act in combination as a stepped device of multiple equilibria, decrease of losses of tocopherol and increase of the elimination of the fatty acid. The distillation apparatus (8) may be of any high vacuum design including a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, or a falling film evaporator. The product (10) of the tocopherol-rich bottoms of the second distillation (8) is then subjected to a third high vacuum distillation (11). The tocopherol and other similar boiling compounds are collected as a final, tocopherol-rich distillation product (12). Triglycerides, sterol esters, other high-boiling fatty acid esters and other high-boiling compounds are removed from the bottoms (13) largely free of tocopherol from distillation. The recovery of tocopherol for stream (12) is typically from 95% to 100%, more typically from 96% to 99.9%. The catalyst, if used, exits in the residue. The temperature and pressure of the distillation operation (11) is in the range of 170 ° to 270 ° C, from 0.005 to 2 torr. The preferred range is 200 ° C to 250 ° C. 0.01 torr to 0.05 torr. The distillation apparatus (11) can be any high vacuum design including a short path evaporator, a capillarity film evaporator, a molecular centrifuge evaporator, or falling film evaporator. Thus, as another aspect of the present invention, there is provided a method for preparing a tocopherol concentrate, which comprises the steps of: (a) heating a by-product of the vegetable oil consisting of tocopherols, fatty acids, sterols, sterol esters of fatty acids, and mono-, di- and triglycerides, the by-product optionally containing additional fatty acids of c? 0-c22, optionally in the presence of an acid catalyst, at a temperature of about 70 ° C to 300 ° C and a pressure from about 50 torr to 760 torr, while the water formed is continuously removed, to provide a mixture consisting of sterol esters, high boiling point fatty acid esters, waxes and glycerides; and (b) followed by injection of the mixture by distillation at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.05 to 10 torr, while removing the unreacted fatty acids and low boiling components. as a vapor effluent and a liquid effluent formed of tocopherols; (c) followed by subjecting the liquid effluent from step (b) to distillation at a temperature of about 230 ° C to 300 ° C and a pressure of about 0.01 to 5 torr, while removing the remaining fatty acids and about from 5 to 30% of the total tocopherols as a vapor effluent and a liquid effluent, which is a product enriched with tocopherol; and (d) followed by the subjection of the liquid effluent from step (c) to distillation at a temperature of about 170 ° C to 270 ° and a pressure of about 0.005 to 2 torr, and the collection and isolation of a tocopherol concentrate as a vapor effluent. In a preferred embodiment, the starting material will contain a significant amount of tocotrienols. As mentioned in the above, the preferred apparatus for the distillation steps includes any high vacuum design including a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, or a falling film evaporator. Accordingly, as another aspect of the present invention, there is provided a method for preparing a tocopherol concentrate, which comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, sterol esters of fatty acids, sterols, triterpenoid alcohols, methyl- and mono-, di-, and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally containing additional CJ-C22 fatty acids, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while the formed water is continuously removed, to provide a mixture formed of sterol esters, esters of high boiling point fatty acids, waxes and glycerides; (b) followed by feeding the mixture to a first distillation zone comprising: a first distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, and a falling film evaporator, operated at a temperature of approximately 170 ° C to 270 ° C and a pressure of approximately 0.05 to 10 torr, in which a vapor effluent formed from a substantial fraction of the unreacted fatty acids and materials of low boiling point are eliminated, in which a liquid effluent which is formed of an enriched mixture of tocopherol is removed; (c) followed by feeding the liquid effluent from step (b) to a second distillation zone, comprising: a second distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator and a falling film evaporator, operated at approximately 240 ° C to 280 ° C and at a pressure of 0.01 to 2 torr, in which the steam effluent consists of the remaining fatty acids and approximately 5 to 30 percent of the total tocopherols is removed, in which the liquid effluent comprised of an enriched mixture of tocopherol is removed; and (d) followed by feeding the liquid effluent from step (c) to a third distillation zone, comprising: a third distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator , a molecular centrifuge evaporator and a falling film evaporator, operated at a temperature of approximately 170 ° C to 270 ° C and a pressure of 0.005 to 2 torr, in which a steam effluent, which is a concentrate of tocopherol, is eliminated and isolated. It should be noted that the order of removal of the fatty acid and the distillation of high-boiling materials can be reversed, that is, steps (b) and (d) of the above aspects of the invention can be reversed. In this embodiment, the product of the esterification reactor (4) is first fed to the distillation operation (11). Free fatty acids, low-boiling materials and tocopherols are distilled from the top first of sterol esters, fatty acid polyesters of glycerol, waxes and other high-boiling compounds. The tocopherol-rich distillate is then fed to the distillation operation (5) to remove a substantial fraction of the fatty acids and the materials with low boiling point and then to the distillation operation (8) to remove the remaining fatty acids and the materials of low boiling point. The concentrate rich in tocopherol is the product of the bottoms of the distillation operation (8). The distillate of the unit (8) can be recycled to the reactor (2), the first distillation (11), or the second distillation (5) to increase the recovery of total tocopherol. A more highly preferred embodiment of the present invention is illustrated from Figure 2. The byproduct (1) of the vegetable oil is esterified in a batch or continuous reactor (2) with or without a catalyst. The esterification water is continuously removed by means of line (3) during the reaction. The product of the esterification step (4) is distilled under high vacuum to remove essentially all of the unreacted fatty acid, typically from 90% to 99%, more typically from 97% to 99.9%, together with a substantial fraction of other materials of low boiling point by means of stream (8) to leave a product (10) of the bottoms rich in tocopherol. The temperature and pressure of the distillation is in the range of 220 ° C to 320 ° C, from 0.1 to 8 torr. The preferred range is 260 ° C to 290 ° C, from 0.5 to 4 torr. In the preferred embodiment of the invention, the distillation apparatus for the fatty acid removal stage is a multi-stage, reflux fractionating column. The column must contain at least 1, preferably 2 to 4 stages in rectification equilibrium (5), as well as an optional washing section (6). The column must also have the ability to provide reflow via line (7) for the rectification section (5). The fractionation capacity of the device greatly decreases the loss of tocopherol for the distillate to typically less than 5%, more typically from 0.2% to 2.0%, and increases the removal of the free fatty acid from the product from the bottoms. The optional washing section also increases the elimination of free fatty acids from the bottom product. The extent of the loss of tocopherol is highly dependent on the reflux ratio, defined as the ratio of the mass flow velocity of the stream (7) to the mass flow velocity of the stream (8). In the preferred embodiment of the invention, the reflux ratio is in the range of 0.3 to 5.0, more preferably 0.5 to 2.0. The staggering in the optional grinding and washing sections can be provided by any vapor-liquid contacting device, including bubble cap trays, screen trays, random packing and structured packing. In the preferred embodiment of the invention, stepped balancing is provided by structured packing of high efficiency, low pressure drop, to decrease residence time, and reduce the temperature required for distillation. The boiler of the distillation apparatus may be of any high vacuum, low residence design including a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, or a falling film evaporator. The product (10) of the tocopherol-rich bottoms of the first distillation is then subjected to a second high vacuum distillation (11). Tocopherol and other similar boiling compounds are collected as the tocopherol-rich distillate product (12). Triglycerides, sterol esters, other high-boiling fatty acid esters and other high-boiling compounds are largely eliminated in the tocopherol-free bottoms, the distillation stream (13). The recovery of tocopherol for stream (12) is typically from 95% to 100%, more typically from 96% to 99.9%. The catalyst, if any is used, comes out in the waste. The temperature and pressure of the second distillation is in the range of 170 ° C to 300 ° C, from 0.005 to 2 torr. The preferred range is 200 ° C to 250 ° C, from 0.01 torr to 0.05 torr. The distillation apparatus (11) can be of any high vacuum design including a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator, or a falling film evaporator. Thus, as another aspect of the present invention, there is provided a method for preparing a tocopherol concentrate, which comprises the steps: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid sterol esters, sterols, triterpenoid alcohols, methyl sterols and mono-, di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally contains fatty acids of r <Additional ^ 22, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while continuously removing the formed water, to provide a mixture consisting of sterol esters, fatty acid esters of high boiling point, waxes and glycerides; (b) followed by feeding the mixture (a) to a first distillation zone comprising: a first distillation apparatus consisting of a reflux fractionating column, multi-stage and a boiler, in the column has a section of rectification having at least one step in rectifying equilibrium and means for providing reflux to the rectification section and optionally a washing section, the apparatus operates at a temperature of about 220 ° C to 320 ° C and a pressure of about 0.1 to 8 torr, in which a vapor effluent which is formed of free fatty acids and low boiling materials is removed; and wherein a liquid effluent which is formed of an enriched mixture of tocopherol is removed; (c) followed by feeding the liquid effluent from step (b) to a second distillation zone, comprising: one or more separate distillation apparatuses, in series, selected from the group consisting of a short path evaporator, a capillarity film evaporator, a molecular centrifuge evaporator and a falling film evaporator, operating at a temperature of approximately 200 ° C to 320 ° C and a pressure of approximately 0.01 torr to 10 torr, in which a liquid effluent which consists of the sterol esters, esters of fatty acids, glycerides, waxes, or other high-boiling materials is removed; wherein a vapor effluent which is a concentrate of tocopherol is withdrawn and isolated. It should also be understood that the order of removal of the fatty acid and the distillation of the higher boiling materials can be reversed in this embodiment. In this embodiment, the product of the esterification reactor (4) is first fed to the distillation operation (11). The free fatty acids, the low-boiling materials and the tocopherols are distilled at the top first of the sterol esters, fatty acid polyesters of glycerol, waxes and other high-boiling compounds. Then, the tocopherol-rich distillate is fed to a multistage fractionation distillation operation to remove essentially all of the fatty acids and a substantial fraction of the low-boiling materials. The distillation operation consists of a rectification section with reflux (5), a coil (9) and an optional washing section (6). The final tocopherol-rich concentrate is the product of the bottoms of the second multi-stage distillation operation.

Accordingly, as another aspect of the present invention, there is provided a method for preparing a tocopherol concentrate, which comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, sterol esters of fatty acids, sterols, triterpenoid alcohols, methyl- and mono-, di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally contains additional C10-C22 fatty acids, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while continuously removing the water formed, to provide a mixture consisting of sterol esters, high boiling fatty acid esters, waxes and glycerides; (b) followed by feeding the mixture (a) to a first distillation zone comprising: one or more separate distillation apparatuses, in series, selected from the group consisting of a short path evaporator, a film evaporator capillarity, a molecular centrifuge evaporator and a falling film evaporator, the apparatus operates at a temperature of about 200 ° C to 320 ° C and a pressure of about 0.01 torr to 10 torr, in which a liquid effluent consisting of the sterol esters, esters of fatty acids, glycerides, waxes, or other high-boiling materials is removed; wherein a vapor effluent consisting of tocopherols, free fatty acids and low boiling materials is removed; (c) followed by feeding the steam effluent from step (b) to a second distillation zone, comprising: a distillation apparatus consisting of a fractionating, refluxing, multi-stage column and a coil, column has a rectification section having at least one rectifying balance stage and means for providing reflux to the rectification section and optionally a washing section, the apparatus operates at a temperature of approximately 220 ° C to 320 ° C and a pressure of about 0.1 torr to 8 torr, in which a vapor effluent which is formed of free fatty acids, and materials of low boiling point is removed; wherein an effluent of liquid, which is a concentrate of tocopherol is removed and isolated.

EXAMPLES Example 1 A 3-liter necked flask, equipped with a mechanical stirrer, a heating mantle, a Dean-Stark trap, a reflux condenser, an N2 inlet and a thermowell is charged with 500 g of deodorizing distillate from soybean oil and 0.5 g zinc acetate. The resulting mixture is stirred and heated for 3 hours at 230 ° C. A nitrogen flow of 250 ml / min is bubbled through the mixture, while heating. The mixture is analyzed for tocopherols, sterols, sterol esters, fatty acids and glycerides. The results are listed in the following Table 1. Example 2 The procedure described in the above is followed, except that 500 g of the canola oil deodorizing distillate is charged to the reactor and 0.25 g and butylstanoic acid is used as the catalyst. The results are listed in Table 2. EXAMPLE 3 The procedure described in Example 1 is followed except that 1.8 g of phosphoric acid is used as the catalyst. The results are listed in Table 3.

Example 4 The procedure described in example 1 is followed, except that no catalyst is added. The mixture is stirred and heated for 24 hours at 170 ° C. The results are listed in Table 3. Example 5 The procedure described in the above is followed, except that the reactor was charged with 500 g of sunflower deodorizing distillate. No catalyst added. The mixture is stirred and heated for 3 hours at 210 ° C. The results are listed in Table 5. Example 6 The effect of temperature on the reaction rates was examined using the same reactor equipment as described in example 1. The reactor was charged with 500 g of soybean deodorizing distillate for each run at 132 ° C, 150 ° C and 170 ° C. No catalyst was added. Each mixture is stirred and heated for 19-20 hours and kept at the temperature. The results are listed in Table 6. Example 7 A stainless steel reactor of 568.65 liters, equipped with an anchor stirrer, a steam jacket, a nitrogen inlet, a vacuum system and outlet pipe for water removal , it is charged with approximately 363.20 kg (800 lbs) of canola oil deodorizing distillate for each of the four runs of the reactor. For each run, the vacuum is adjusted to 200 mm Hg and the mixture is stirred and the steam is applied to the heating jacket for three hours until a heat of 210 ° C. The reactor is maintained at 210 ° C and 200 mm Hg, with stirring for two hours. Then the reactor is rapidly cooled to less than 100 ° C. The esterification water is collected during the heating and maintenance times. The reactor product of each run is sampled and analyzed for tocopherols and sterols. The results for each of the four runs of the reactor are listed in Table 7. Example 8 A stainless steel reactor of 568.65 liters (150 gallons) equipped with an anchor stirrer, a steam jacket, a nitrogen inlet, a system vacuum and an outlet pipe for water removal, is charged with 141.10 kg (310.8 pounds) of soy oil deodorizing distillate. No catalyst was added. The vacuum is adjusted to 200 mm Hg and the mixture is stirred and steam is applied to the jacket under heating for five hours until a heating of 210 ° C. The reactor is maintained at 210 ° C and 200 mm Hg, with stirring for two and a half hours. Then the reactor is rapidly cooled to less than 100 ° C. The esterification water is collected during the heating and retention times. The reaction product is sampled at 5 hours and 7.5 hours and analyzed for tocopherols and sterols. The results are listed in Table 8. Example 9 A 3-necked, one liter flask with a mechanical stirrer, a heating mantle, a Dean-Stark trap, a reflux condenser, an N2 inlet and a thermowell, is charged with 500 g of soy triglycerides, 5.1 g of mixed tocopherols and 0.5 g of dibutyltin oxide. The resulting mixture is stirred and heated for two hours at 230 ° C. A nitrogen flow of 250 ml / min is bubbled through the mixture, while heating. The mixture is shown at one hour intervals and analyzed for tocopherols. The results are listed in Table 9. Example 10 With reference to Figure 1, distillation step 5, the deodorizing distillate of the soybean is fed continuously to a 0.42m ^ single-stage thin film evaporator unit, which It works from 1.3 to 1.4 torr. The unit is heated by a hot oil system at a constant temperature of 238 ° C. The flow velocity for the column is varied and the synchronized samples of the distillate and the products of the funds are collected. The flow velocities of distillate streams and bottoms are calculated from the masses of the synchronized samples and a portion of each sample is analyzed for the tocopherol and fatty acid content. The effect of the flow rate on the removal of fatty acid and recovery of tocopherol in the residue is shown in Table 10. Example 11 The effect of temperature on the removal of the fatty acid and recovery of tocopherol in the residue was examined using the same thin film evaporator as described in Example 11. The pressure system varied from 2.2 torr to 2.8 torr. The synchronized samples are collected to calculate the distillate and bottom velocities and a portion of each sample is analyzed for the tocopherol and fatty acid content. The results are shown in Table 11. Example 12 A bottom product rich in tocopherol resulting from the removal of a substantial fraction of the fatty acids, it is continuously fed to a short path evaporator unit of 0.42 p ^ which operates a short path evaporating unit of 0.05 to 0.099 torr. The temperature is varied from 239 ° C to 279 ° C and synchronized samples of distillate products and bottoms products are collected. The flow velocities of the distillate streams and bottom currents are calculated from the mass of the synchronized samples and a portion of each sample is analyzed for the tocopherol and fatty acid content. The effect of temperature on the recovery of tocopherol in the distillate is shown in Table 12. Example 13 A glass distillation column of 0.54 cm in diameter is equipped with a vacuum pump, the reflux distillation head, the condenser of the reflux ratio, the measured feed pump, the hot feed line, the heated feed tank and the collection vessels for the distillate products and the bottoms. The column consists of a rectification section containing 15.24 cm (6 inches) of structured packing, a wash section containing 45.72 cm (18 inches) of structured packing and a coil section containing 30.48 cm (12 inches) of beads Spherical glass of 0.38 cm (1/8 inch). The coil is adapted with a brass block heater and the rectification and washing sections are made with heat tape and insulated. A portion of the esteriferous deodorizing distillate of Example 7 is fed continuously to the column at a rate of 300 ml / hr, while the coil temperature is varied from 240 ° C to 300 ° C and the reflux ratio of 0.33. at 2.00-. The pressure at the top of the column is maintained at 0.7 torr and all the heat tapes of the column at 220 ° C. In each temperature coil and the reflux ratio that calibrates in the column, they are allowed to reach equilibrium and samples of distillate streams and bottoms are collected and analyzed for fatty acids and tocopherols. The results are shown in Table 14. Example 14 The esterified sunflower deodorizing distillate of Example 5 is fed continuously at a rate of 400 ml / hr to a capillarity film of 15.24 cm (6 inches) single stage, fixed, equipped with a heating mantilla, a feed pump, a high vacuum pump and distillate receivers and the residue. The distiller is maintained at a pressure of 0.1 torr and a temperature of 240 ° C throughout the distillation. Distilled product and bottoms are collected and analyzed for fatty acids, tocopherols, sterols, sterol esters and glycerides. Essentially all of the fatty acid (98.6% of that in the feed) and 78% of the tocopherol was recovered for the distilled product.

Example 15 [ASPENMR Run] The esterified soybean deodorizer containing 34% fatty acids, 8.5% tocopherols, 9% hydrocarbons and 40% glycerides, the sterol esters and other heavy esters are continuously fed to a purification system of three-stage distillation as shown in Figure 1. The first single stage high vacuum evaporator is operated at 202 ° and 2.0 torr, the second single stage high vacuum evaporator at 235 ° C, 1.2 torr , and the third high vacuum evaporator of a single stage at 220 ° C, 0.01 torr. The product distilled from the second evaporator is recycled to the feed of the first evaporator to increase the recovery of the tocopherol. The Aspen ™ computer program simulated the results shown in Table 15. The total recovery of tocopherol was 91%, with a 32% concentration of tocopherol. Example 16 An esterified soy deodorizer portion of Example 8 is continuously fed to the multi-stage reflux column described in Example 13 at a rate of 300 ml / hr, a pressure higher than 0.7 torr, the temperature of the 285 ° C coil and the reflux ratio of 2.00. The distillate and bottoms product is collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol for the product from the bottoms of the first distillation stage was 99.3%. Next, the product of the tocopherol-rich bottoms is continuously fed to the capillary film evaporator described in Example 14 at a rate of 300 ml / hr, system pressure of 0.05 torr and temperature of 235 ° C. Distillate and product from the bottoms of this second distillation were collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol for the distillate product from the second distillation stage was 96.2%. The total recovery of the average tocopherol from both distillation stages was 95.5%. Other results are given in Table 16. Example 17 A portion of the esterified, soybean deodorizing distillate of Example 8 is continuously fed to the capillary film evaporator described in Example 14 at a rate of 300 ml / hr, the system pressure of 0.05 torr and the temperature of 235 ° C. The distillate and bottoms product is collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol to the distillate product of the first distillation step was 73.3%. Next, the tocopherol-rich distillate is continuously fed to the multi-stage reflux column described in Example 14 at a rate of 300 ml / hr, a pressure higher than 0.7 torr, the coil temperature of 285 ° C and the Reflux ratio of 2.0. The product of the distillate and the bottoms of this second distillation were collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol for the product from the bottoms of the second distillation stage was 98.8%. The total recovery of tocopherol by means of both distillation stages was 72.4%. Other results are given in Table 17. Example 18 A portion of the esteriferous deodorizing distillate of Example 7 is continuously fed to the capillary film evaporator described in Example 14 at a rate of 335 ml / hr., the system pressure of 0.01 torr and the temperature of 235 ° C. The distillate product and the funds are collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol to the distillate from the first distillation stage was 84 ° C. Next, the tocopherol-rich distillate is fed continuously to the multi-stage reflux column described in Example 14 at a rate of 346 ml / hr, at a pressure higher than 2.5 torr, coil temperature 260 ° C and ratio of reflux of 0.33. The distillate product and the bottoms of that second distillation are collected and analyzed for fatty acids, tocopherols, sterols and sterol esters. The recovery of tocopherol to the product from the bottoms of the second distillation stage was 84.6%. The total recovery of tocopherol by means of both distillation stages was 71.0%. Other results are given in Table 17. Example 19 A 3-liter necked flask, equipped with a mechanical stirrer, a heating blanket, a Dean-Stark trap, reflux condenser, nitrogen inlet and thermowell is charged with 500 g of rice husk oil distillate consisting of tocols (2% tocotrienol and 1% tocopherol), sterols (1%), sterol esters (9%), free fatty acids (35%), hydrocarbons and glycerides. The resulting mixture is stirred and heated for 7 hours at 200 ° C. A nitrogen flow of 100 ml / min is bubbled through the mixture during heating. The mixture is sampled and analyzed for touches, sterols, sterol esters, fatty acids and glycerides. The product mixture is distilled as described in Example 13. The distillate was formed mainly of fatty acids and squalene. The distillation residue is fed to a capillary film distillation apparatus as described in Example 14. The results of the distillations are listed in Table 19.

Table 1 Esterification of the Soybean Deodorizer Distillate Temperature: 230 * C Pressure: 1 to n Oil load: 500 g Acids Steroids Monoglyceride No. of Time Tocopherols Esteróles céridos free esters reference íinl ZníOAc) (q) (a) roí í < rt ful fa) 2 1 0 0.5 38.7 42.6 43.7 184.6 5.5 39 2 30 38, 3 10.4 105.6 142.0 1.5 28.5 3 60 36.5 5.0 120.2 127.8 4 90 33.8 2.2 121.0 113.6 > 0.5 15 5 120 31.0 0.8 124.9 113.6 6 180 25.2 0.0 124.6 99.4 > 0.5 11.5 Table 2 Esteriffication of Cánola Deodorizer Distillation Temperature: 23 ° ßc Pressure: atn Oil load: 500 g Acid Butyl-Steroids - Monoglycerides - No. of Diglycerides Stanoic time Tocof roles Esteróles esters free céridos reference din), íg) f f) íg) íg) fg) íal 7 0 0.25 35.5 39.2 26.5 241.4 48.5 31 8 30 33.1 15.8 109.0 170.4 3.5 14.5 9 60 31.7 5.7 126.2 156.2 10 90 30.3 2.3 139.5 156.2 4.0 8.5 11 120 28.7 1.0 142.0 142.0 12 180 25.2 1.1 144.5 142.0 3.5 5.5 Table 3 Esterification of the Soybean Deodorizer Distillate Temperature: 230 '»C Pressure: 1 ate Oil charge;: 500 g Acids Acid Sterol Fatty Trigli- "- No. Phosphoric Time No. Tocopherols Stearic esters free cerides reference í» in) ía. a) (a) (Q) 13 0 1.8 38.7 42.6 43.7 184.6 14 30 36.9 6.7 105.4 151.2 107.5 15 60 34.4 1.8 119.4 137.2 16 90 31.4 0.0 122.0 128.8 135 17 120 28.6 0.4 125.8 123.2 18 180 22.3 0.4 121.3 114.8 260 Table 4 Esterification of Soy Deodorizer Distillate Temperature: 170 '»c Pressure: 1 atn Oil load: 500 9 without catalyst Sterol ¬ Acids No. of fatty Monogii- Time Tocopherols Sterols free esters. Diglycerides céridos Triglycerides reference (pin) íol fg) -... íg) íq)., ". íq) íg) 19 0 39.1 41.8 53.2 184.8 7.5 32.5 67.5 20 60 38.4 32.6 66.7 170.8 5.5 35 79 21 120 37.9 25.8 76.7 165.2 3.5 36 95 22 240 37.5 17.6 99.5 148.4 2.5 34.5 100 23 360 37.7 12.1 113.0 138.9 2.5 31.5 110 24 480 37.7 8.8 115.5 133.0 2.0 29 115 25 1440 35.9 1.5 138.1 106.4 0.0 14.5 150 Table 5 Sterilization of Sunflower Seed Deodorizer Distillate Temperature: 210ßC Pressure: l at »Oil load: 500 g without catalyst Acids No. of Steroids «^ Time Tocopherols Esterols ISI reference free esters, Triglycerides in) fq). fq) _ fq) 26 0 11. 5 8. 8 36.1 211.7 20 27 30 11.7 4.0 48.1 199.1 116 28 60 11.8 2.0 53.3 196.0 29 90 11. 6 0.9 54.3 189.8 160 30 120 11.6 0.6 55. 1 187. 6 31 180 11.4 0.0 57. 1 165 Table 6 Effect of Temperature on the Esterification of Distillate from Soy Deodorizer Pressure: i atn Oil charge: 500 g at each temperature indicated without catalyst Acids No. of Sterol-Fat Temperature Time Tocopherols Sterols esters ii res iTriqlycerides reference fC) MI fq) (and ta) (a) (a) Material "- 39.2 42.5 47.5 196.0 69.0 Initial 32 170 19 36.2 2.1 140.9 112.0 135.0 33 150 19 36.9 12.0 119.8 109.2 110.0 34 132 20 39.7 17.7 102.1 151.2 80.5 Table 7 Casting deodorizer distillation esterification Pressure: 200 torr without catalyst Tempera «i» No. of Time Time Tocopherol Tocopherol Tocopherol from Ester les Estherles reference fßC | Initial final rl Recovery Final initials socket 210 210 2.0 hr retension 6.9 6.7 97.1 * 12.14 0.97 canopy 92 210 2.0 re-tensioning unit 6.4 5.94 92.8 * 10.98 0.91 canopy 95 210 2.0 retraction power 7.08 6.46 91.2 * 11.91 0.84 canopy 210 2.0 reloading 6.78 6.19 91.3 * 11.43 0.42 Table 8 Soybean Deodorizate Distillation Esteriffication 1 Pressure: 200 torr without catalyst «F- Tempera- 00 Time Time Tocopherol Tocopherol Tocopherol Sterols Sterile Reference (< > c? Fhr) Initial Final Recovery Final Initials Soya 190 5 hr 11.1 8.66 78 * 4.0 0.18 Brazilian sample S ° ya 210 7.5 hr 11.1 7.43 67 * 4.0 0.0 Brazilian sample Table 9 Balance of Tocopherols Mixed with Triglycerides Temperature: 230 ° C Pressure: 1 atn Reactor load: 500 g of triglycerides, 5.1 g of mixed tocopherols of soybean Catalyst charge: o .5 g of dibutyltin oxide 5 No. of Tocopherol reference time fhr > (to) 0 5. 1 36 1 2.0 37 2 1.9 Table 10 Effect of Feed Flow Rate on the Thin Film Distillation of a Single Stage of Distillation of Soy Diluent Pressure Yield of Speed Performance of Velocity Rate of Ratio of C or Fatty Tocopherol for System Oil Hot feed distillation Distillation to for Distillate Waste No. of Corrida (torr) »C (ko hrl. Ka hrl Food \ 38 1.4 238 176 50.4 0.29 60 94 39 1.4 238 146 51.7 0.35 73 92 40 1.3 238 132 49.6 0.38 77 91 41 1.3 238 127 49.1 0.39 81 89 Table 11 Effect of Temperature on the Distillation of Thin Film of a Single Stage of Distillation of Soy Deodorant (_p Pressure Performance of the Velocity Velocity Velocity Ratio of Fatty Acid Tocopherol for Hot Oil System feed distillation Distillation for the Distillate the Waste No. of Run (torrl ° C flw / hr) ftq hr) Feeding 42 2.2 249 120 54.2 0.45 90 83 43 2.8 264 117 58.0 0.495 95 75 Table 12 Effect of Temperature on the Short Path Distillation of the Residue of Example 10, 11 Pressure Yield of ui of the Temperature of the Velocity Velocity of Tocoferol Relation for System Oil Hot feed distillation Distillation to the Residue Mo. of Corrida f torr) ° C f hr) _ g / r) Feeding \ _ 44 0.050 239 30.7 16.4 0.53 95 45 0.051 264 60.9 35.3 0.58 98 46 0.099 279 66.0 41.2 0.62 99 Table 13 Effect of Temperature and Reflux on the Fractionation of «Multiple Stages of Distillation of Esterified Canola Performance Rate of Tocopherol Pressure Temperature Feeding Speed Fatty Acid for the Upper Boiler Speed Feeding for the distillate Residue Reference No. of Reflux (? l / hJC) Distillation m 47 0.7 240 0.33 300 0.366 93.9 92.4 48 0.7 255 0.33 300 0.381 96.3 91.2 49 L? 0.7 270 0.33 300 0.388 97.1 87.3 L 50 0.7 240 1.0 300 0.342 92.6 99.6 51 0.7 255 1 * 0 300 0.358 94.0 99.5 52 0.7 270 1.0 300 0.329 95.8 99.1 53 0.7 285 1.0 300 0.370 100.0 99.6 54 0.7 300 1.0 300 0.376 100.0 99.6 55 0.7 255 2.0 300 0.359 95.0 99.6 56 0.7 270 2.0 300 0.374 96.5 99.4 57 0.7 285 2.0 300 0.365 97.7 99.6 58 0.7 300 2.03 300 0.358 99.4 100.0 Table 14 Short Path Distillation of Sunflower Seed of Example 5 Acids MA Añ Esterol "Monoglycerides Digigléridos Triglycerides N0- to Weight Tocopherols Esterolles esters Udres céridos reference Jal (91 IsL. JtflL J3L Jal- M fg) 59 196.48 7.8 0.0 0.0 163.8 1.0 4.52 0.78 60 255.23 2.2 0.0 51.9 2.4 0.0 1.28 122.6 Table 15 ASPEN R-Balance Program of Generated Material for the Three Stage Recycled Distillation Scheme of Figure 1 Fatty Acids Tocopherols Current Mass (q / frr) Free iq l) (g / hr) freshly prepared 764 260 65 Distilled i 280 253 4.5 Funds 1 1760 498 305 Distilled 2 1276 492 244.5 Funds 2 484 6.0 60.5 Distilled 3 182 6.0 59.0 Funds 3 301 0.0 1.0 Table 16 Distillation in Two Stages of Sterilated Soy Deodorizer Distillate Contents Contents Contents Acid Content Sodium Tocopherol Mass No. Steroidal Fat Free Ester? P Current Reference (a) m í «m ... _ (*). food distillate 1063.28 6.80 < 0.1 25.04 23.26 esterified soybean 61 distillate # 1 348.95 0.14 < 0.1 0.0 69.09 62 residue f 714.33 10.48 < 0, 1 36.45 0.56 63 distillate '2 143.63 48.01 0.64 0.20 3.85 64 residue # 2 545.55 0.5 < 0, 1 53.82 0.66 Table 17 Distillation in Two Stages of Sterilated Soy Deodorizer Distillate Contents Contents Contents Acid Content Mass No. of Steroidal Tocopherol Esteroléster Free Fat U1 Reference Current Jai m í *) food distillate 628.74 6.80 < 0.1 25.04 23.26 esterified soybean 65 distillation l 260 12.25 < 0.1 0.0 53.37 66 residue ¿368.74 3.15 < 0.1 43.95 0.0 67 distillate '2 192.9 < 0.1 0.0 69.52 68 residue # 2 64.4 45.75 0.47 0.0 0.0 Table 18 Distillation in Two Stages of Distillation of Esterified Acetone Oil Deodorizer Contents Contents Contents Acid Content Mass No. of Steroidal Tocoferol Sterol Free Fatty Reference Current Reference Jal m ui 03 food distillate 780.93 5.9 0.9 32.8 sternolene canola 69 distillate f 409.3 9.5 0.7 0.003 62, 15 residue ¿70 367.78 2.0 0.2 65.9 0.0 71 distilled 307.6 1.8 < 0.1 0.0 79.4 72 residue 2 86.24 35.0 0.1 0.6 5.3 Table 19 Distillation in Two Stages of Distilled Esterified Rice Casting Contents Content Content of Contents Acid Content Mass No. of Tocopherol Steroid Tocotrienol Fatty Free Fathersterol Reference Refer to the) m ti) ül_ f *) f% > 73 power 464 1.0 2.0 0.2 22.9 74 distillate ll1 89 0.0 0.0 0.0 0.0 98.9 l 3 2 75 residue # 1 374 0.7 0.8 0.2 25.5 2. 1 3 76 distillate Í2 55 6.8 11.3 0.7 1.0 3.6 77 residue §2 305 0.1 0.0 0.1 32.8 5. 6 1 • Fractionated Distillation 2. Fractionated Residue 3. Distillation of Wicking Film 4. Wicking Film Residue

Claims (21)

1. CLAIMS 1. A method for preparing a tocopherol concentrate, characterized in that it comprises the steps of: (a) heating a by-product of the vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid esters, sterols, triterpenoid alcohols, methyl sterols and mono-, di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally containing additional fatty acids of c c or "c22, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr at 760 torr while the formed water is continuously removed, to provide a mixture consisting of sterol esters, high boiling point fatty acid esters, waxes and glycerides, and (b) followed by subjecting the mixture to a series of distillation, comprising: (i) one or more of the separate distillation operations, in which the distillation or distillation is carried out at a temperature from about 200 ° C to 320 ° C and a pressure of about 0.01 torr to 10 torr, in series, in which the unreacted fatty acids and low-boiling components are removed as a steam effluent and an effluent liquid consisting of tocopherols, is eliminated; and (ii) wherein the liquid effluent of step (b) (i) is subjected to one or more series distillations, in which the distillations are carried out at a temperature of about 170 ° C to 270 ° C. and a pressure of about 0.005 torr to 2 torr, in which a concentrate of tocopherol is removed as a vapor effluent and in which the liquid effluent consists of sterol esters, fatty acid esters, glycerides, waxes and other high-point substances Boiling are eliminated.
2. 2. The method of compliance with the claim 1, characterized in that the vegetable oil by-product is formed of tocotrienols in a proportion of approximately 0.5 to 10, by weight, based on weight of the tocopherols present.
3. The method according to claim 1 or 2, characterized in that step (a) is carried out at a temperature of about 150 ° C to 230 ° C and a pressure of about 100 torr to 200 torr and in which the additional C10-C22 fatty acids are added to the vegetable oil by the by-product used in stage (a).
4. 4. The method according to claim 1, characterized in that an acid catalyst is used in step (a).
5. 5. A method for preparing a tocopherol concentrate, characterized in that it comprises the steps of: (a) heating a by-product of the vegetable oil consisting of tocopherols, fatty acids, sterols, fatty acid sterol esters, and mono-, di- and triglycerides , the by-product optionally containing additional fatty acids (22), optionally in the presence of an acid catalyst, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while the formed water is continuously removed, to provide a mixture consisting of sterol esters, high boiling point fatty acid esters, waxes and glycerides, and (b) followed by the distilling of the mixture at a temperature of about 170 ° C to 270 ° C and a pressure of approximately 0.05 to 10 torr, while the unreacted fatty acids and the low boiling point components are removed as a vap effluent or and a liquid effluent formed from tocopherols; (c) followed by subjecting the liquid effluent from step (b) to distillation at a temperature of about 230 ° C to 300 ° C and a pressure of about 0.01 to 5 torr, while removing the remaining fatty acids and about from 5 to 30% of the total tocopherols as a vapor effluent and a liquid effluent, which is a product enriched with tocopherol; and (d) followed by the subjection of the liquid effluent from step te) to distillation at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.005 to 2 torr., and the collection and isolation of a tocopherol concentrate as a vapor effluent.
6. 6. The method according to claim 5, characterized in that the vegetable oil by-product is formed of tocotrienols, in a proportion of about 0.5 to 10, by weight, based on the weight of the tocopherols present.
7. The method according to claim 5 or 6, characterized in that step (a) is carried out at a temperature of about 200 ° C to 240 ° C and a pressure of about 0.5 to 4 torr.; step (b) is carried out at a temperature of about 240 ° C to 280 ° C and a pressure of about 0.1 to 2 torr; step (c) is carried out at a temperature of about 200 ° C to 240 ° C and a pressure of about 0.01 to 0.05 torr; step (d) is carried out at a temperature of about 260 ° C to 290 ° C and a pressure of about 0.5 to 4 torr.
8. The method according to claim 5 or 6, further characterized in that it comprises the step of recycling the removed tocopherols as a vapor effluent in step (c) in the mixing step (b).
9. 9. The method for preparing a cacarterized tocopherol concentrate because it comprises the steps of: (a) heating a by-product of the vegetable oil consisting of tocopherols, fatty acids, sterols, fatty acid esters, and mono-, di-, and triglycerides, the by-product optionally containing < -i? ~ < Additional 22, optionally in the presence of an acid catalyst, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, to form a mixture consisting of sterol esters, high fatty acid esters boiling point, waxes and glycerides, and (b) followed by subjecting the mixture to distillation at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.005 to 2 torr, while removing the tocopherols, acids free fatty acids, and low-boiling materials such as a steam effluent; (c) followed by the subjection of the steam effluent from step (b) to distillation at a temperature of approximately 230 ° C to 300 ° C and a pressure from approximately 0.01 to 5 torr, while the remaining fatty acids and approximately 5 to 30% of the total tocopherols are removed as a vapor effluent and a liquid effluent, "which is a product enriched with tocopherol l; Y (d) followed by subjecting the liquid effluent from step (c) to distillation at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.05 to 10 torr, while removing unreacted fatty acids and low-boiling components such as a steam effluent and a liquid effluent which is a tocopherol concentrate.
10. 10. The method of compliance with the claim 9, characterized in that the vegetable oil by-product consisting of tocotrienols, in a proportion of about 0.5 to 10, by weight, based on the weight of the tocopherols present.
11. 11. The method according to the claim 9 or 10, characterized in that step (a) is carried out at a temperature of about 200 ° C to 240 ° C and a pressure of about 0.5 to 4 torr; step (b) is carried out at a temperature of about 260 ° C to 290 ° C and a pressure of about 0.5 to 4 torr; step (c) is carried out at a temperature of about 200 ° C to 240 ° C and a pressure of about 0.01 to 0.05 torr; step (d) is carried out at a temperature of about 240 ° C to 280 ° C and a pressure of about 0.1 to 2 torr.
12. 12. The method according to claim 9 or 10, further characterized in that it comprises the step of recycling a steam effluent in stage (c) in the stage of mixing (b).
13. 13. A method for preparing a tocopherol concentrate characterized in that it comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid sterol esters, sterols, triterpenoid alcohols, methyl sterols and mono- , di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally contains additional C10-C22 fatty acids, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while the water formed is continuously removed to provide a mixture consisting of sterol esters, high boiling point fatty acid esters, waxes and glycerides; (b) followed by feeding the mixture (a) to a first distillation zone comprising: a first distillation apparatus consisting of a reflux fractionating column, multi-stage and a boiler, in the column has a section of rectification having at least one step in rectifying equilibrium and means for providing reflux to the rectification section and optionally a washing section, the apparatus operates at a temperature of about 220 ° C to 320 ° C and a pressure of about 0.1 to 8 torr, in which a vapor effluent which is formed of free fatty acids and low boiling materials is removed; and wherein a liquid effluent consisting of an enriched mixture of tocopherol is removed; (c) after feeding the liquid effluent from step (b) to a second distillation zone, comprising: one or more separate distillation apparatuses, in series, selected from the group consisting of a short path evaporator, a capillarity film evaporator, a molecular centrifuge evaporator and a falling film evaporator, operating at a temperature of approximately 200 ° C to 320 ° and a pressure of approximately 0.01 torr to 10 torr, in which a liquid effluent that consists of the sterol esters, esters of fatty acids, glycerides, waxes, or other high-boiling materials is removed; wherein a vapor effluent which is a concentrate of tocopherol is withdrawn and isolated.
14. 14. The method according to claim 13, characterized in that the vegetable oil by-product consists of tocotrienols in a proportion of about 0.5 to 10, by weight, based on weight of the tocopherols present.
15. The method according to claim 13 or 14, characterized in that the additional C-, Q-C22 fatty acids are added to the vegetable oil by-product used in step (a), and in which the step is carried out out at a temperature of about 150 ° C to 230 ° C and a pressure of about 100 torr to 200 torr; step (b) is carried out at a temperature of about 260 ° C to 290 ° C and a pressure of about 0.5 to 4 torr, and a reflux ratio of 0.5 to 2.0; and step (c) is carried out at a temperature of about 200 ° C to 250 ° C and a pressure of about 0.01 to 0.05 torr.
16. 16. A method for preparing a tocopherol concentrate characterized in that it comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid esters, sterols, triterpenoid alcohols, methyl sterols, and mono -, di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally contains additional fatty acids (- 22), at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr at 760 torr, while continuously removing the formed water, to provide a mixture consisting of sterol esters, high boiling fatty acid esters, waxes and glycerides, (b) followed by feeding the mixture from the stage ( a) to a first distillation zone comprising: one or more separate distillation apparatus, in series, selected from the group consisting of a path evaporator After cutting off a capillarity film evaporator, a molecular centrifuge evaporator and a falling film evaporator, the apparatus operates at a temperature of about 200 ° C to 320 ° and a pressure of about 0.01 torr to 10 torr, in which A liquid effluent consisting of sterol esters, fatty acid esters, glycerides, waxes, or other high-boiling materials is removed; wherein a vapor effluent consists of a tocopherol, free fatty acids and low boiling points are removed; (c) after feeding the liquid effluent from step (b) to a second distillation zone, comprising: a distillation apparatus consisting of a fractionating, refluxing, multi-stage column and a coil, the column has a rectification section having at least one rectifying balance stage and means for providing reflux to the rectification section and optionally a washing section, the apparatus operates at a temperature of about 220 ° C to 320 ° C and a pressure of about 0.1 torr to 8 torr, in which a vapor effluent which is formed of free fatty acids, and materials of low boiling point is removed; wherein an effluent of liquid, which is a concentrate of tocopherol is removed and isolated.
17. The method according to claim 1, characterized in that the vegetable oil by-product is formed of tocotrienols in a proportion of about 0.5 to 10, by weight, based on weight of the tocopherols present.
18. 18. A method for preparing a tocopherol concentrate characterized in that it comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid esters, sterols, triterpenoid alcohols, methyl sterols and mono- , di- and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally containing additional fatty acids of - ^ - c22 ', at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while the water formed is continuously removed, to provide a mixture formed of sterol esters, fatty esters of high boiling point, waxes and glycerides; (b) followed by feeding the mixture to a first distillation zone comprising: a first distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator and an evaporator of falling film, operated at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.05 to 10 torr, in which a vapor effluent formed from a substantial fraction of the unreacted fatty acids and low-grade materials boiling point are eliminated, in which a liquid effluent which is formed of an enriched mixture of tocopherol is removed; (c) followed by feeding the liquid effluent from step (b) to a second distillation zone, comprising: a second distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator and a falling film evaporator operated at approximately 240 ° C to 280 ° C and at a pressure of 0.01 to 2 torr, in which the vapor effluent consists of the remaining fatty acids and approximately 5 30 percent of the total tocopherols is removed, in which the liquid effluent comprises of an enriched mixture of tocopherol is removed, and (d) followed by the feeding of the liquid effluent from stage (c) to a third distillation zone , which comprises: a third distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator and a falling film evaporator operated at a temperature of about 170 ° C to 270 ° and a pressure of 0.005 to 2 torr, in which a vapor effluent, which is a concentrate of tocopherol, is removed and isolated.
19. 19. The method according to the claim 18, characterized in that the vegetable oil by-product is formed of tocotrienols in a proportion of approximately 0.5 to 10, by weight, based on weight of the tocopherols present.
20. 20. A method for preparing a tocopherol concentrate characterized in that it comprises the steps of: (a) heating a by-product of vegetable oil consisting of tocopherols, fatty acids, hydrocarbons, fatty acid esters, sterols, triterpenoid alcohols, methyl sterols and mono-diols; - and triglycerides, optionally in the presence of an acid catalyst, the by-product optionally containing additional C10-C22 fatty acids, at a temperature of about 70 ° C to 300 ° C and a pressure of about 50 torr to 760 torr, while that the water formed is continuously removed to provide a mixture formed of sterol esters, esters of high boiling point fatty acids, waxes and glycerides; (b) followed by feeding the mixture to a first distillation zone comprising: a first distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator, a molecular centrifuge evaporator and an evaporator of falling film, operated at a temperature of about 170 ° C to 270 ° C and a pressure of about 0.005 to 2 torr, in which a vapor effluent consists of tocopherols, unreacted free fatty acids, and low-point materials Boiling is eliminated. (c) followed by the feeding of the steam effluent from step (b) to a second distillation zone, comprising: a second distillation apparatus selected from the group consisting of a short path evaporator, a film evaporator capillarity, a molecular centrifuge evaporator and a falling film evaporator, operated at approximately 170 ° C to 270 ° C and a pressure of 0.05 to 10 torr, in which the steam effluent consists of a substantial fraction of free fatty acids unreacted, and low-boiling materials are removed, and in which the liquid effluent which is a tocopherol concentrate is removed and isolated; and (d) followed by feeding the liquid effluent from step (c) to a third distillation zone, comprising: a third distillation apparatus selected from the group consisting of a short path evaporator, a capillary film evaporator , a molecular centrifuge evaporator and a falling film evaporator, operated at a temperature of about 240 ° C to 280 ° C and a pressure of 0.01 to 2 torr, in which a vapor effluent consists of fatty acid residues and approximately 5 to 30% of the total tocopherols is removed, in which a vapor effluent which is a tocopherol concentrate is withdrawn and isolated.
21. 21. The method according to the claim 20, characterized in that the vegetable oil by-product is formed of tocotrienols in a proportion of about 0.5 to 10, by weight, based on weight of the tocopherols present.