CN1204331A - Recovery of tocopherols - Google Patents
Recovery of tocopherols Download PDFInfo
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- CN1204331A CN1204331A CN 96199004 CN96199004A CN1204331A CN 1204331 A CN1204331 A CN 1204331A CN 96199004 CN96199004 CN 96199004 CN 96199004 A CN96199004 A CN 96199004A CN 1204331 A CN1204331 A CN 1204331A
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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.
Description
Invention field
The present invention relates to a kind of method that from mixture, reclaims tocopherol and the dispensable sterol of arbitrariness, this mixture contains tocopherol, fat and/or fat derivant, dispensable sterol of lipid acid and the arbitrariness of more specifically saying so and/or sterol derivative.
Background technology
Tocopherol compound is present in various plants oil and the animal oil, is also referred to as vitamin-E sometimes.Vitamin-E is relevant with the physiological action of these food composition.
Have the active naturally occurring material of vitamin-E and have 8 kinds.They are derivatives of 6-chromanol, belong to two compounds.The first kind derives from tocol, has a saturation classes isoprene side chains that contains 16 carbon atoms.This compounds comprises alpha-tocopherol, 5,8-dimethyl tocol, Gamma-Tocopherol and Delta-Tocopherol.These compound differences are degree of the methylating difference on the tocol phenyl ring.Alpha-tocopherol is the material with the strongest biological vitamin-E effect, and its technological value and economic worth are also maximum.It is a tocopherol main in the humans and animals tissue.
Having the active second class material of vitamin-E is the derivative of tocotrienols (tocotrienol).They are different from the unsaturated isoprenoid side chain that other tocopherol anologs parts are to contain 16 carbon atoms.The tocotrienols of natural origin also shows the activity of vitamin-E, generally separates from its natural origin with saturated tocopherol anologs in the recovery of vitamin-E.In the context of the present invention, " tocopherol " this title has also comprised these tocopherol anologs, and the tocopherol of promptly finding in vegetables oil is as wheat germ oil, Semen Maydis oil, soybean oil and palm-kernel oil.Yet, in other plant oil, also find to contain tocopherol, for example Thistle oil, peanut oil, Oleum Gossypii semen, Trisun Oil R 80, rapeseed oil, plam oil and other plant oil.
Crude vegetal only contains a spot of tocopherol.The low needs that can not satisfy commercial applications of concentration.In addition, in order to improve the activity of antioxygenation and vitamin-E, must remove impurity.Therefore, the most important natural origin of tocopherol is not a vegetables oil itself, but handles the steam distillate that obtains by the deodorizing of vegetables oil and animal oil, claims the vapour generator distillate yet.Although resulting is the conc forms of tocopherol, also it to be mixed with sterol and sterol ester, free fatty acids and triglyceride level.What attract people's attention especially is to handle the distillate that obtains by the deodorizing of soybean oil.The deodorizing distillate that for example compared soybean oil and rapeseed oil in 39 and 41 pages of 1989 91 volumes of " fat science and technology " (Fat Sci.Technol.), having mentioned soybean oil is to suit especially as the source of tocopherol.The vapour generator distillate of soybean oil contains the mixed tocopherol of 10 weight % (the highest) and the main sterol that exists with the form of ester of equivalent approximately.
Known have several different methods to be used for the concentrating of tocopherol, to be esterification, saponification and fractionation extraction.Therefore, according to DE3126110A1, tocopherol concentrate is to obtain from the secondary species that the oil and the deodorizing of fat are handled, make the free fatty acids esterification that is contained in oil and the fat by adding a kind of alcohol, perhaps from distillate, remove free fatty acids by distillation method, then these products are carried out hydrogen treatment, carry out solvent fractionation again, the extraction tocopherol.From the another kind of as can be known method that concentrates tocopherol of the document.In this method the deodorizing distillate is carried out transesterification with methyl alcohol and handle, distillation weeding of grease fatty acid methyl esters.Resistates concentrates with molecular distillation method.
From the another kind of as can be known method of EP171009A2, this method makes the raw material that contains tocopherol contact with a kind of polar organic solvent of capacity, this organic solvent solubilized tocopherol, but dissolved impurity not.Separate the polar phase that is rich in tocopherol, therefrom reclaim tocopherol.
By the separable tocopherol of the absorption of basic anion exchanger, this also is a kind of known method.If fatty acids hardly in the mixture, even have also seldom, this alternative is feasible.Sterol, glyceryl ester and other neutrality or alkaline matter are not adsorbed (" Ulmanns Enzyklop dieder Technischen Chemie " the 4th edition, volume was 645 pages in 1984 23).
By the fractional crystallization after concentrating can be from tocopherol sterols separated, this also is a kind of known method.In this method, tocopherol enters solution, and crystallization of sterols is come out.Tocopherol also can separate by distillation method with sterol, unless sterol has to small part destroyed in this case.Therefore after separating tocopherol and sterol, can obtain two kinds of useful products.
In the described a kind of method of DE3126110A1, after with polyvalent alcohol esterification free acid, make tocopherol carry out molecular distillation or vapor distillation, to obtain the high distillate of tocopherol content.But, the processing step of molecular distillation is said so uneconomic from technical scale, and vapor distillation method relates to the exposure to comparatively high temps, and high temperature can destroy sterol at least in part.Therefore in a kind of situation in back, can only obtain the higher tocopherol of thermostability of higher yields.
People have proposed many methods and come to reclaim tocopherol and sterol from deodorizer distillate and relative mixtures.For example, United States Patent (USP) discloses for No. 2432181 and can reclaim tocopherol from the plant oil ﹠ fat, method is to make glycerin fatty acid ester and the reaction of a kind of aliphatic monohydric alcohol in the presence of a kind of alkaline alcoholysis catalysts, and alcohol, glycerine and the fatty acid ester with remnants carries out flash distillation then.
United States Patent (USP) discloses by saponification and acidification for No. 2729655, makes glyceryl ester and sterol ester be converted into free fatty acids and free alcohol (being respectively glycerine and sterol), can reclaim sterol from distillate.Free fatty acids monobasic lower alcohol esterification.Adding a kind of hydrocarbon/water solvent in mixture comes out crystallization of sterols.
United States Patent (USP) disclose for No. 3153055 a kind of by under strong acidic condition, high-grade aliphatic ester being turned to the low-grade monobasic alcohol ester and from the deodorizer distillate method of sterols separated and tocopherol.Combination stepwise solvent extraction sterol and tocopherol from esterification products with polarity and non-polar solvent.
United States Patent (USP) discloses for No. 3335154 distillate has been carried out saponification and acidification, makes glyceryl ester and sterol ester be converted into free fatty acids and free alcohol (being respectively glycerine and sterol).Free fatty acids monobasic lower alcohol and inorganic acid catalyst esterification.In mixture, add entry sterol is precipitated out, remove fatty acid ester with molecular distillation method and concentrate tocopherol.
United States Patent (USP) discloses for No. 3840570 by adding the water-alcohol solvent generation and has been separated, and can concentrate from plant origin and obtain sterol.With a kind of alkali metal base saponification sterol ester, free sterol is crystallized out from a kind of aprotonic solvent.
United States Patent (USP) discloses the separable sterol of transesterification that carries out distillate with methyl alcohol for No. 4148810, and this reaction is carried out with alkali metal alcoholate or alkali metal hydroxide catalysis.By in a kind of aprotonic solvent, generating the adducts with calcium chloride, can be from the transesterification mixture sterols separated.
United States Patent (USP) 4374776 and the method that discloses a kind of concentrated sterol No. 4451564, elder generation carries out the transesterification of distillation residue with a kind of low-grade monobasic alcohol under base catalysis, carry out molecular distillation again.Alkaline catalysts is alkali metal alcoholate or alkali metal hydroxide.A main drawback that uses alkaline transesterification catalyst in aforesaid method is that basic catalyst requires mixture not contain any meeting to make it the neutral acidic component.This point is least can be gratifying to tocopherol because tocopherol is a phenolic compound, can with the methylate ionic reaction.Other shortcomings of aforesaid method are that they require multiple-stage reactor system and procedure of processing, product is refining, productive rate is relatively low and turnout is low.
United States Patent (USP) discloses a kind of like this method for No. 5424457, wherein utilize a kind of lower alcohol and a kind of tin alkyl catalyzer to make the deodorizer distillate carry out esterification/transesterification step, sterol is removed in crystallization, lower alcohol and lipid acid low-carbon-ester are removed in redistillation, concentrate tocopherol with molecular distillation method at last.Perhaps, can before crystallization, remove lower alcohol and/or lipid acid low-carbon-ester.This patent also discloses a kind of esterification/transesterification method of using catalytic free fatty acids of tin alkyl and fatty acid ester in the presence of tocopherol, and about sterol ester of 55 to 90% has been transformed in this method.
The present invention's general introduction
The present invention relates to a kind of method that is used for reclaiming tocopherol from the tocopherol mixture that contains lipid acid and tocopherol, described method is included in a kind of zinc oxide that is selected from, the zinc catalyst of zinc hydroxide and composition thereof exists down, described tocopherol mixture and a kind of lower alcohol (being preferably a kind of monobasic primary alkanol that is less than five carbon atoms and lower alcohol of monobasic sec alkanol of being selected from) are mixed in reaction vessel, form reaction mixture, the temperature of described reaction mixture is more than the atmospheric boiling point of described alcohol, it is liquid phase that pressure in the described reaction vessel is enough to keep most of at least described alcohol, thereby makes the free fatty acids esterification that contains in the described tocopherol mixture and make the glycerin fatty acid ester transesterification that contains in the described tocopherol mixture.This method comprises further usually that from product distillation removes excessive lower alcohol, and washed product (preferred earlier with aqueous inorganic acid, wash with pure water again) is to remove described zinc catalyst and by glycerine that described transesterification was produced.
In preferred embodiments, product drying with aforesaid method, and in the presence of a kind of alkoxide catalysis of the alkali metal alcoholates that is selected from a kind of lower alcohol, in reaction vessel, mix with described alcohol (being preferably a kind of monobasic primary alkanol that is less than five carbon atoms and lower alcohol of monobasic sec alkanol of being selected from), form reaction mixture, the temperature of described reaction mixture is more than the atmospheric boiling point of described alcohol, and it is liquid phase that the pressure in the described reaction vessel is enough to keep most of at least described alcohol.In these embodiment preferred, this method comprises further usually that from described transesterification product distillation removes excessive lower alcohol (and the described methyl alcohol recirculation that distills of at least a portion is entered in described esterification and the transesterification step), washs described transesterification product (preferred earlier with aqueous inorganic acid, wash with pure water again) to remove the glycerine that is produced by described transesterification.Detailed description of the present invention
The inventive method is raw materials used to be the mixture that contains fatty cpd and sterol compound and tocopherol.Major advantage according to method of the present invention is that this method is applicable to the multiple mixture that contains tocopherol and the dispensable sterol of arbitrariness.But, it is especially favourable being begun by the soybean oil vapour generator distillate that obtains by the vapor distillation as the thick soya-bean oil in first stage of deodorisation process." Bailey industry oil and fatty prod " the 3rd volume 127-165 page or leaf (New York John Wiley﹠amp; Sons company, New York, 1985) in oily deodorization has been discussed, the disclosure content is incorporated herein by reference.Tocopherol, about 20 to 35% the free fatty acids of distillate contains 8 to the 20% approximately sterol of (according to appointment 12%), about 3 to 5% (according to appointment 8%) and make the triglyceride level (Ullmans is as above-mentioned quoted passage) of main composition.But, also can be used to process other oily vapour generator distillates according to method of the present invention, as the rapeseed oil distillate.
According to method of the present invention never be limited to vegetables oil and fat the vapour generator distillate in application.This method also can be advantageously used in tall oil.Tall oil is one of the most important secondary species of economically valuable that is used for the sulfate cellulose method of papermaking.It is got through acidification by the sodium salt mixt that generates in this method or resinous acid and lipid acid.Tall oil is the natural mixture of abietic type acid, saturated and unsaturated fatty acids and fatty acid ester and a kind of not saponification fraction.Except higher alcohols and hydrocarbon, the sponifiable fraction does not contain sterol yet.
Other mixtures that contain tocopherol also can adopt method processing of the present invention, and for example resulting resistates in the preparation rapeseed methylester wherein also contains sterol and sterol ester.
In this method, free fatty acids that contains in the starting mixt and glycerin fatty acid ester and the reaction of a kind of lower alcohol generate fatty acid alkyl ester, the more definite fatty acid methyl ester of saying so.Partial glyceride and triglyceride level reaction generate glycerine and fatty acid alkyl ester.In certain embodiments, sterol fatty acid ester reacts in second separating step and generates sterol and fatty acid alkyl ester.The tocopherol that contains in the mixture does not react in two steps.
The esterification of the lipid acid in the tocopherol mixture and the transesterification of glycerin fatty acid ester preferably carry out with a kind of lower alcohol, and lower alcohol is preferably C
1To C
4Monobasic alkanol, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the trimethyl carbinol.Generally pure and mild zinc catalyst is joined in the reaction vessel that contains tocopherol mixture.In the esterification process, the amount of alcohol in reaction mixture preferably is in excess in the stoichiometric quantity of lipid acid and ester in the product.Generally, the consumption of alcohol is about 20% to 80%, more generally, is about 50% to 60%, and this is to come out according to the Mass Calculation that contains the raw material of tocopherol at first, is converted into fatty acid alkyl ester to promote lipid acid and glycerin fatty acid ester.
The carrying out of the zinc oxide of significant quantity and/or zinc hydroxide catalyzed reaction.The scope of catalytic amount generally is about 0.005 weight % to 5 weight % of tocopherol mixture, more generally, is about 0.01% to 1%, is more preferably 0.05% to 0.2%.
Esterification and transesterification preferably carry out under the temperature between 150 ℃ and 240 ℃, and the reaction times is 10 minutes or longer, for example about 1 to 3 hour.Pressurization is a liquid reaction phase to remain under this temperature to container.Reaction is carried out till reaching required esterification and transesterification degree, and preferably lipid acid and the glycerin fatty acid ester esterification until larger proportion (for example more than the 50 weight %, generally at least about 90%) produces fatty acid alkyl ester.Should use the sour catalyst neutralisation of first-class substantially stoichiometric quantity then, acid is preferably aqueous sulfuric acid (preferably being about 1-10 weight % acid).Excessive alcohol (and any higher alcohols of free) should be distilled away from mixture and (for example carry out the simple distillation of lower alcohol earlier then, carry out the simple distillation of higher alcohols again), arbitrariness is handled with a kind of chelating agent (as xitix (vitamins C), phosphoric acid, toxilic acid, citric acid or tartrate) not essentially then, is that washing (with deglycerizin and salt), the dispensable nitrogen of arbitrariness spray and drying afterwards.
If used in the step in front be short chain alcohol, be methyl alcohol specifically, to next procedure of processing, i.e. it is particularly advantageous that excessive lower alcohol is removed in distillation.Exposure at high temperature can be reduced to minimum like this.Before fatty acid alkyl ester is removed in distillation, preferably not only the glycerine that generates in the transesterification step to be separated from the triglyceride level (if any) that exists, but also will remove esterification/transesterification catalyzer.Catalyzer exists in a large number with the form of zinc salt, might have problems in still-process, for example may cause the elevation of boiling point.Obtain highly spissated tocopherol/sterol mixture after removing fatty acid alkyl ester.Tocopherol in the mixture and sterol can be separated from one another by known method own, for example crystallization process.
If desired the sterol ester in the tocopherol mixture is converted into free sterol basically fully, in the presence of a kind of alkoxide catalysis, make product generation transesterification so again, the for example rudimentary alkoxide of alkoxide catalysis (being preferably the solution of this low-level chain triacontanol) as the methanol solution of sodium methylate.(Kirk-Othmer edits " chemical technology complete works " (Encyclopedia of Chemical Technology) the 9th volume 306-308 page or leaf, New York John Wiley﹠amp; Sons company, New York, 1980) in transesterification has been discussed, the disclosure content is incorporated herein by reference.
The preferred available a kind of lower alcohol of sterol ester in esterification/transesterification product carries out transesterification, the preferred C of lower alcohol
1To C
4Monobasic alkanol, for example methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol or the trimethyl carbinol.Pure and mild alkoxide catalysis joins in the reaction vessel as sodium methylate.Alcohol amount in reaction mixture in esterification process preferably is in excess in the stoichiometric quantity of the fatty acid sterols ester in the product.Generally, the amount of alcohol is about 20% to 80%, more generally, is about 50% to 60%, and this is to come out according to the Mass Calculation that contains the raw material of tocopherol at first, is converted into fatty acid alkyl ester and free sterol to promote the fatty acid sterols ester.In the transesterification process, reaction medium should be substantially free of water (for example less than about 0.1 weight %), with generation and/or the destruction catalyzer of avoiding the soap class.Therefore esterification/transesterification products drying for example should be used the air vaporizing extract process.
The carrying out of this reaction of alkoxide catalysis catalysis of significant quantity.The scope of catalytic amount generally is about 0.01% to 10 weight % of tocopherol mixture, more generally, is about 0.05% to 2%, is more preferably 0.1% to 0.5%.
The transesterification of sterol ester preferably carries out under the temperature between 150 ℃ and 240 ℃, and the reaction times is 10 minutes or longer, for example about 1 to 3 hour.Pressurization is a liquid reaction phase to remain under this temperature to container.Reaction is carried out till reaching required esterification and transesterification degree, and preferably lipid acid and the glycerin fatty acid ester esterification until larger proportion (for example more than the 50 weight %, generally at least about 90%) produces fatty acid alkyl ester.Should use the sour catalyst neutralisation of first-class substantially stoichiometric quantity then, acid is preferably aqueous sulfuric acid (preferably being about 1-10 weight % acid).Excessive alcohol (and any higher alcohols of free) should be distilled away from mixture and (for example carry out the simple distillation of lower alcohol earlier then, carry out the simple distillation of higher alcohols again), arbitrariness is handled with a kind of chelating agent (as xitix (vitamins C), phosphoric acid, toxilic acid, citric acid or tartrate) not essentially then, is that washing (with deglycerizin and salt), the dispensable nitrogen of arbitrariness spray and drying afterwards.
Above-mentioned esterif iotacation step obtains containing the mixture of tocopherol, sterol and fatty acid alkyl ester.Fatty acid alkyl ester can separate from mixture as distillate.Distillatory carries out avoiding tocopherol and/or sterol that the degraded that can not make us accepting takes place.E.Hafslund rolls up 849-891 page or leaf in " distillation ", " chemical technology complete works " the 7th, and (Kirk-Othmer edits, New York John Wiley﹠amp; Sons company, 1979 the 3rd edition) in distillation is discussed, (Kirk-Othmer edits F.Standiford, New York JohnWiley﹠amp at " evaporation ", " chemical technology complete works " the 9th volume 472-493 page or leaf; Sons company, 1980 the 3rd edition) in evaporation is discussed, the disclosure content is incorporated herein by reference.
The distillation of fatty acid alkyl ester can be undertaken by No. 5190618 (people such as Top) described methods of United States Patent (USP), and the disclosure content is incorporated herein by reference.In this patent, distillation plant by the distillation tower of high heat transfer, be that the falling film type distillation tower and the distillate gathering system of high thermal conductivity formed.Still-process is a successive.The condition of distillation alkyl ester is to be lower than about 10 mmhg (1333N/m
3) high vacuum under, temperature is between 100 ℃ and 200 ℃.The alkyl ester that distills is collected by condensation, discharges as by product.Tocopherol and the sterol retention time in distillation tower is shorter, so the loss minimum.Distillation can be more than the cyclical operation once, and still obviously this is worthless, because bottoms, particularly tocopherol can be degraded (the thermal induction degraded especially easily takes place tocopherol).
But, disclosed PCT application on February 16 nineteen ninety-five WO 95/04731 disclosed method is preferably adopted in the distillation of fatty acid alkyl ester, and the disclosure content is incorporated herein by reference.This distillating method uses at filling type distillation tower under the mild temperature (promptly being lower than the temperature of the vaporizer that heavily boils) and a kind of vaporizer under comparatively high temps (promptly being higher than the heating temperature that packed tower reached), the residence time minimum of liquid phase in this vaporizer is as changeing film-type evaporator.When distilling, be that a kind of liquid of preheating is injected in the position of mid point basically preferably to packed tower, the bottoms of packed tower is moved into changes film-type evaporator, and the bottoms that will change film-type evaporator again moves to the zone with envrionment temperature.Come the vapor phase of rotation film-type evaporator to enter in the packed tower once more by the packed tower bottom.Generally make packed tower be configured to more than decanting point, have about 5-12 theoretical tray, below decanting point, has about 5-12 theoretical tray, the service temperature of top of tower and pressure generally are about 120 ℃ to 150 ℃ and 0.1 millibar to 3 millibars, the service temperature of tower bottom and pressure generally are about 180 ℃ to 220 ℃ and 3 millibars to 9 millibars, reflux ratio is about 0.4 to 0.6, and the per-cent (by weight) that distillate is equivalent to charging is about 60% to 80%.The service temperature of this tower is lower than like this changes the employed temperature of film-type evaporation reboiler.
Change film-type evaporator and generally use as the reboiler of packed tower, service temperature is about 200 ℃ to 300 ℃, generally is about 260 ℃, and working pressure is about 3 to 12 millibars.The mechanical agitation of changeing film in the film-type evaporator has guaranteed that the residence time of mixture under used high temperature of tocopherol and sterol is shorter.This will make the Degradation of tocopherol and sterol be reduced to minimum level, thereby improve ultimate production.The mechanical agitation of film will guarantee preferably that any specific part of the mixture of tocopherol and sterol is instantaneous with contacting of heat exchanger surface basically, the two (is for example promptly removed once contact, this specific part is brought to the film surface, contact with the reduced atmosphere that is kept in the vaporizer, the transpiration cooling in the vaporizer will reduce the temperature of this mixture specific part).Certainly, this part film can contact with the surface of interchanger once more, and mechanical agitation can be removed it once more from point of contact.Mechanical agitation further plays the effect of shortening the total residence time of any specific part of mixture in vaporizer.
Above-mentioned distillation order generally can make fatty acid alkyl ester separate fully from the mixture of itself and tocopherol and sterol basically.For example, final bottoms will contain the fatty acid alkyl ester less than about 1%, be generally to be lower than about 0.5%.But in some cases, it also is desirable only removing the partial fatty acid alkyl ester from a kind of like this mixture.Can realize advantageously that according to the method described above the part of fatty acid alkyl ester removes, but needn't use packed tower, that is to say, use a kind of falling film evaporator or change film-type evaporator.
It will be particularly advantageous removing a part of fatty acid alkyl ester with the part vaporizing extract process from mixture, and wherein the weight ratio scope of the combination general weight of fatty acid alkyl ester and tocopherol and sterol is about 1.5: 1 to 5: 1.This vaporizing extract process generally can be removed about 30% to 60% described mixture (being the charging of esterification) effectively with the form of fatty acid alkyl ester, meanwhile only remove the tocopherol and the sterol of minute quantity, for example, fatty acid alkyl ester will contain less than the tocopherol of about 5 weight % and sterol combination, be generally to be lower than about 3 weight %.
Be rich in tocopherol and sterol in the product of distilation steps.Many separation methods can be used to tocopherol is separated from mixture with sterol, for example based on other chromatography of poor solubility and/or absorption or other and solid interaction mutually.But preferable methods is, mixture is dispersed in a kind of special solvent system, it is mutually solid-state with one that this solvent system helps to generate a liquid phase, be rich in the mixture of tocopherols compound in the liquid phase, the solid-state mixture that is rich in phytosterin compound in mutually, the physical sepn liquid phase is with mutually solid-state then.This method can be counted as a kind of crystallization method.(Kirk-Othmer edits " chemical technology complete works " the 7th volume 243-285 page or leaf, New York John Wiley﹠amp; Sons company, 1979 the 3rd edition) in crystallization method is discussed, the disclosure content is incorporated herein by reference.
Described the preferred method that separates one or more phytosterin compounds and one or more tocopherols compounds from mixture among disclosed PCT application on the February 16 nineteen ninety-five WO 95/04731, the disclosure content is incorporated herein by reference.It is to be dispersed in a kind of solvent mixture being substantially free of one or more tocopherols compounds of higher fatty acid compounds and the mixture of one or more phytosterin compounds that wherein said method generally begins, and this solvent mixture is made up of a large amount of a kind of low polar organic solvents, a spot of a kind of high polar organic solvent and a spot of water.
In a broad sense, high polar solvent is that than the high organic solvent of the polarity of low polar solvent, vice versa for its polarity (for example represent with the specific inductivity of the pure liquid phase of solvent, in envrionment temperature, record as under the room temperature).The specific inductivity of low polar organic solvent is preferably less than about 25, is more preferably less than approximately 10, and it is about 25 that the specific inductivity of high polar organic solvent is preferably greater than, more preferably greater than about 30." chemistry and physics handbook E-56 to E-58 page or leaf (joslyn hi-voltage city CRC publishing company 1974 the 55th edition) have been listed the specific inductivity of various organic solvents, and the disclosure content is incorporated herein by reference.Low polar organic solvent is generally varsol, promptly only contains the solvent of carbon atom and hydrogen atom, or the oxygenated hydrocarbon solvent, for example only contains carbon, hydrogen and oxygen and each carbon atom and has solvent less than a Sauerstoffatom.
Preferred low polar organic solvent is that the higher alkane class (has sufficiently high molecular weight and goes up exercisable liquid phase to form practice, be preferably straight or branched alkane) with 6 to 12 carbon atoms, for example hexane, heptane, octane, octane-iso, 2,2,4-trimethylpentane, nonane or decane; Monobasic ketone, for example acetone, 2-butanone or methyln-hexyl ketone; Monobasic aldehydes, for example acetaldehyde or propionic aldehyde; Monobasic ester class, for example ethyl formate or ethyl acetate; High alcohol class, for example n-propyl alcohol, Virahol, propyl carbinol, sec-butyl alcohol, n-hexyl alcohol or 2-Ethylhexyl Alcohol.Preferred high polar organic solvent is low-molecular-weight oxidizing hydrocarbons, is preferably such as methyl alcohol or alcoholic acid low-level chain triacontanol.Solvent mixture also preferably contains a spot of water.
Solvent mixture contains a large amount of low polar organic solvents, promptly greater than about 50%, in solvent mixture weight, generally is at least about 80%, preferably is about 90% to 99.5%, for example about 92.0% to 99.0%.The content of high polar organic solvent is less, promptly is less than approximately 50%, in solvent mixture weight, generally is less than approximately 20%, preferably is about 0.5% to 10%, for example about 1.0% to 8.0%.The preferred content of water is substantially equal to high polar organic solvent, and for example, the ratio of high polar organic solvent and water is about 5: 1 to 1: 5, more generally is about 3: 1 to 1: 3.Therefore, preferred solvent mixture is made up of the water of a kind of composition that is selected from the higher alkane hydrocarbon of about 80 weight % to 99 weight %, about methyl alcohol of 0.5% to 20% or ethanol and about 0.5 weight % to 5 weight %.
The mixture of solvent mixture with tocopherol and sterol mixed, form the liquid phase that is essentially homogeneous at first.Mixture heating up for example to the atmospheric boiling point of solvent mixture, can be obtained the liquid mixture of homogeneous.The variable ratio of solvent mixture and incoming mixture, but be generally about 10: 1 to 1: 1, be preferably about 5: 1 to 3: 1.The gained mixture generally remains under the cryogenic condition, generates the liquid phase be rich in the tocopherols compound and is rich in the mutually solid-state of phytosterin compound.The temperature of mixture should remain on below the envrionment temperature, for example is lower than about 25 ℃, is generally-40 ℃ to 20 ℃ approximately, more generally is-25 ℃ to 0 ℃ approximately.Mixture can be cooled to low temperature with the temperature of any rate of cooling when disperseing, for example with per hour about 80 ℃ to 120 ℃ very fast speed, or with per hour about 2.5 ℃ to 10 ℃ than slow rate.
Crystallization of sterols or precipitation form solid-state phase, can with the liquid phase physical sepn, for example by filter, centrifugal or decantation.Preferably, collected solid-stately contain at least about the sterol of 90 weight % (being generally at least about 92 weight %) mutually and be lower than the tocopherol of about 5% (be generally and be lower than about 2%), tocopherol and the ratio of sterol were greater than about 5: 1 (generally greater than about 10: 1) in the liquid phase (mother liquor).Be rich in tocopherol (crystallization charging relatively) in the mother liquor, further available distillation method is refining, collects the higher tocopherol of purity with distillate.
Except as otherwise noted, all umber, percentage and ratio be all by weight in this specification and the appended claims.The following example is used to explain the present invention, in no case limits the invention.EXAMPLE Example 1
To contain the zinc oxide that free fatty acids and glycerin fatty acid ester and about 10 weight % tocopherols, about 4% free sterol, the total sterol of about 13 weight % summation of sterol ester (free sterol with) and acid number be about the anhydrous methanol of 76 vegetables oil deodorizer product and the 50 weight % that approximate this product and approximate 0.1 weight % of this product mixes.Mixture is heated to about 200 ℃ in pressurizing vessel, and under this temperature, kept about 2 hours.Product is cooled to below the boiling point of methyl alcohol then, presses the simple distillation distillating carbinol.Earlier with aqueous sulfuric acid (containing 5 weight % sulfuric acid in the water approximately), wash the distillate bottoms with water again, be about 6 to 8 then until the pH of organic phase.Desciccate then.Embodiment 2
Embodiment 1 product is mixed with the sodium methylate that approximates 0.2 weight % of this product with the anhydrous methanol of the 50 weight % that approximate this product.Mixture is heated to about 200 ℃ in pressurizing vessel, and under this temperature, kept about 2 hours.Product is cooled to below the boiling point of methyl alcohol then, presses the simple distillation distillating carbinol.Earlier with aqueous sulfuric acid (containing 5 weight % sulfuric acid in the water approximately), wash the distillate bottoms with water again, be about 6 to 8 then until the pH of organic phase.Desciccate then.
Claims (22)
1. one kind is used for from the method for the tocopherol mixture recovery tocopherol that contains lipid acid and tocopherol, described method is included in a kind of zinc oxide that is selected from, the zinc catalyst of zinc hydroxide and composition thereof exists down, described tocopherol mixture is mixed in reaction vessel with a kind of lower alcohol, form reaction mixture, the temperature of described reaction mixture is more than the atmospheric boiling point of described alcohol, it is liquid phase that pressure in the described reaction vessel is enough to keep most of at least described alcohol, thereby make the free fatty acids esterification that contains in the described tocopherol mixture and make the glycerin fatty acid ester transesterification that contains in the described tocopherol mixture.
2. the process of claim 1 wherein that described lower alcohol is a kind of monobasic primary alkanol that is less than five carbon atoms and lower alcohol of monobasic sec alkanol of being selected from.
3. the method for claim 1, wherein with the product drying of this method, and in the presence of a kind of alkoxide catalysis of the alkali metal alcoholates that is selected from a kind of lower alcohol, in reaction vessel, mix with described alcohol, form reaction mixture, the temperature of described reaction mixture is more than the atmospheric boiling point of described alcohol, and it is liquid phase that the pressure in the described reaction vessel is enough to keep most of at least described alcohol.
4. the method for claim 3, wherein this method comprises that further excessive lower alcohol is removed in distillation from the product of described method.
5. the method for claim 4, wherein said method further comprises the product that washs described method, to remove the glycerine that is produced by described transesterification.
6. the method for claim 5, wherein said washing comprise earlier washs with a kind of aqueous inorganic acid, washs with pure water again.
7. the process of claim 1 wherein that described lower alcohol is C
1To C
4The monobasic alkanol.
8. the process of claim 1 wherein that described lower alcohol is selected from methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol and the trimethyl carbinol.
9. the process of claim 1 wherein that the quality of described lower alcohol approximates about 20% to 80% of the raw materials quality that contains tocopherol at first.
10. the process of claim 1 wherein that the quality of described lower alcohol approximates about 50% to 60% of the raw materials quality that contains tocopherol at first.
11. the process of claim 1 wherein that the amount of described zinc catalyst is about 0.005% to 5%, with life
Educate phenol mixture weight meter.
12. the process of claim 1 wherein that the amount of described zinc catalyst is about 0.01% to 1%, with fertility
Phenol mixture weight meter.
13. the process of claim 1 wherein that the amount of described zinc catalyst is about 0.05% to 0.2%, with life
Educate phenol mixture weight meter.
14. the process of claim 1 wherein described esterification and transesterification about 150 ℃ to 240
℃ temperature under carry out.
15. it is about 1 to 3 little to the process of claim 1 wherein that described esterification and transesterification carry out
The time time.
16. the major part of the process of claim 1 wherein (for example greater than about 50 weight %, usually at least about
90 weight %) lipid acid and glycerin fatty acid ester are esterified to be fatty acid alkyl ester.
17. the process of claim 1 wherein lipid acid and the glycerin fatty acid ester quilt that about 50 weight % are above
Esterification is a fatty acid alkyl ester.
18. the process of claim 1 wherein lipid acid and glycerin fatty acid ester quilt at least about 90 weight %
Esterification is a fatty acid alkyl ester.
19. the process of claim 1 wherein that this product further takes place in the presence of a kind of alkoxide catalysis
Transesterification makes sterol ester be converted into free sterol basically fully.
20. the method for claim 19, wherein alkoxide catalysis is a kind of rudimentary alkoxide.
21. the method for claim 20, wherein said catalyzer are the sodium methylates that is dissolved in the methyl alcohol.
22. side that is used for reclaiming tocopherol from the tocopherol mixture that contains lipid acid and tocopherol
Method, described method are included in a kind of choosing of 0.005% to 5% that accounts for described tocopherol mixture weight
The zinc catalyst of autoxidation zinc, zinc hydroxide and composition thereof exists down, makes described tocopherol mixture
Mix in reaction vessel with 20% to 80% the methyl alcohol that accounts for described tocopherol mixture weight,
Form reaction mixture, the temperature of described reaction mixture is more than the atmospheric boiling point of methyl alcohol, and is described anti-
Answering pressure in the container to be enough to keep most of at least described alcohol is liquid phase, thereby described tocopherol is mixed
The free fatty acids esterification that contains in the compound and make the lipid acid that contains in the described tocopherol mixture sweet
The grease transesterification.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96199004 CN1204331A (en) | 1995-12-13 | 1996-12-06 | Recovery of tocopherols |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US60/008,762 | 1995-12-13 | ||
| US08/753,460 | 1996-11-25 | ||
| CN 96199004 CN1204331A (en) | 1995-12-13 | 1996-12-06 | Recovery of tocopherols |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1204331A true CN1204331A (en) | 1999-01-06 |
Family
ID=5129273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96199004 Pending CN1204331A (en) | 1995-12-13 | 1996-12-06 | Recovery of tocopherols |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204331A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821238B (en) * | 2005-02-17 | 2012-06-06 | 棕榈营养食品有限公司 | Method for improving the quality of crude oils and fats and recovery of minor components |
| CN107614667A (en) * | 2015-01-12 | 2018-01-19 | 何·大卫树生 | From crude vegetable oil recovery tocopherol/tocotrienols, carotenoid, glycerine, sterol and fatty acid ester and its method |
| CN112321555A (en) * | 2019-08-05 | 2021-02-05 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
-
1996
- 1996-12-06 CN CN 96199004 patent/CN1204331A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1821238B (en) * | 2005-02-17 | 2012-06-06 | 棕榈营养食品有限公司 | Method for improving the quality of crude oils and fats and recovery of minor components |
| CN107614667A (en) * | 2015-01-12 | 2018-01-19 | 何·大卫树生 | From crude vegetable oil recovery tocopherol/tocotrienols, carotenoid, glycerine, sterol and fatty acid ester and its method |
| CN112321555A (en) * | 2019-08-05 | 2021-02-05 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
| CN112321555B (en) * | 2019-08-05 | 2022-05-31 | 浙江医药股份有限公司新昌制药厂 | Method for removing plasticizer from natural tocopherol |
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