WO2016150025A1

WO2016150025A1 - Method for preparing high-content mixed tocopherols through lyotropic liquid crystal extraction and separation

Info

Publication number: WO2016150025A1
Application number: PCT/CN2015/083070
Authority: WO
Inventors: 邢华斌; 刘献献; 杨启炜; 杨亦文; 任其龙; 苏宝根; 鲍宗必; 张治国; 苏云
Original assignee: 浙江大学
Priority date: 2015-03-24
Filing date: 2015-07-01
Publication date: 2016-09-29
Also published as: CN104803963A; CN104803963B

Abstract

A method for preparing high-content mixed tocopherols through lyotropic liquid crystal extraction and separation, comprising the following steps: dissolving vegetable oil deodorized distillate which is esterified or is subjected to fatty acid removal in a weak-polar organic solvent to prepare a feed solution; mixing ionic liquid or a surfactant with a polar diluent to prepare lyotropic liquid crystals; and separating and purifying the feed solution through countercurrent extraction or fractional extraction by taking the lyotropic liquid crystals as an extraction agent, thus obtaining mixed tocopherols. A lyotropic liquid crystal extraction agent in the present application has high extraction capacity on tocopherols, and the dosage of the extraction agent and the number of theoretical plates required for extraction can be obviously reduced; the lyotropic liquid crystal extraction agent which is adopted still can keep high extraction efficiency and selectivity under a higher feed concentration, the mixed tocopherols of which the purity is larger than 90% can be obtained, and the recovery rate of the mixed tocopherols is more than 90%.

Description

Description: A method for separating and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction

[0001] The present invention relates to a method for extracting and separating mixed tocopherol from a vegetable oil deodorized distillate, and belongs to the field of chemical engineering and natural product separation.

Background technique

[0002] Natural Vitamin E, Tocopherols, also known as mixed tocopherol, is a commonly used medicine and health care product. It has become an international market due to its important antioxidant and physiological functions. An important vitamin variety with a wide range of uses and production and sales, and vitamins. Vitamin A is the three pillars of the vitamin series. The safety and physiological activity of natural vitamin E is much better than that of synthetic vitamin E, so the preparation of high content of natural vitamin E has important economic value. Vegetable oil is the main source of natural vitamin E, but its content is only 0.04~0.1%. Therefore, the direct extraction of mixed tocopherol from it has no industrial application value. The amount of mixed tocopherol in the by-product _ deodorized distillate produced in the vegetable oil refining process is generally higher than 2%, so the deodorized distillate is often the starting material in the mixed tocopherol extraction production.

[0003] However, the vegetable oil deodorized distillate has complex components, including free fatty acids, neutral oils, natural vitamin E and phytosterols, as well as some odorous substances and pigments. The properties of the components are similar, and industrial production often has to It is subjected to a certain pretreatment, and the difference between the components is widened, and then the mixed tocopherol is obtained by using a separation means. The esterification method is a relatively common and mature means, and the vegetable oil deodorized distillate after esterification mainly contains fatty acid esters, mixed tocopherols and the like. The methods for purifying mixed tocopherols include multiple distillation methods, molecular distillation methods, adsorption chromatography, ion exchange methods, supercritical fluid extraction methods, and organic solvent extraction methods.

[0004] US Pat. No. 5,122,691, US Pat. No. 5,582,692, US Pat. No. 4, 232, 218, and US Pat. No. 5,627,289, each of which is assigned a higher content of mixed tocopherol from the degraded vegetable oil deodorized distillate by means of multiple distillations and a more efficient separation. The method can well separate the mixed tocopherol from the low-boiling fatty acid ester, and has a high yield, but it is difficult to separate it from the high-boiling glyceride. Moreover, distillation and rectification need to be very expensive The esterified vegetable oil deodorized distillate is treated by vacuum distillation and molecular distillation, respectively, by the methods of vacuum distillation and molecular distillation, respectively, in US Pat. No. 5,616,735, US Pat. No. 5, 017, 920, CN 101, 445 498 A, CN 177, 577, PCT, PCT, PCT, PCT, PCT, PCT. Although the concentration ratio and yield of the molecular distillation method are high, a high content of tocopherol products cannot be obtained.

[0006] Patent CN102432584A, JP59167585, US3122565, CN1234703C

And CN101323607A utilizes an adsorption method to separate tocopherol by utilizing different adsorption properties of tocopherol and impurities on the adsorbent, but the adsorption amount is small, and the adsorbent needs to consume a large amount of solvent.

[0007] US Patent Nos. 4,939,276, JP 5612383, US Pat. No. 3,122,565, US Pat. No. 5,478,717, US Pat. No. 3,402,282, CN1018 51561A, CN103012352A, and CN103709133A use ion exchange to obtain high-purity mixed tocopherols, but the obvious disadvantages of using anion exchange resins are: To use a large amount of organic solvents, resins Regeneration requires a process of acid-base regeneration, which produces a large amount of wastewater, and the loading of the same resin is low.

[0008] The patents US4550183, US3122565, US5371246, CN1418877 and CN101074258 are applied to supercritical extraction and supercritical chromatography, etc., which is a relatively green process, and the method for separating and mixing tocopherol is mild, and the product is safe to use. The method is high, but the method has low selectivity for tocopherol extraction, low separation efficiency, complicated equipment and high cost, and economic feasibility.

[0009] Patent CN1382689 combines a urea-packing method and a saponification method to extract a natural mixed tocopherol from a soybean oil distillate, which removes a part of the fatty acid and the alcohol, and then saponifies and separates it with NaOH. The method has simple steps, but alkaline is easy to destroy tocopherol, and the extraction rate and purity of the same tocopherol are not high.

[0010] Patent US3108120, US6706898, JP60048981A, US4550183, EP0171009, US31 53055 and CN103467431A, etc. use solvent extraction method to concentrate and mix tocopherol. The extraction method has the advantages of simple equipment and easy operation, but most of the extractants used in the report are Conventional organic solvents, such as acetone, petroleum ether, methanol, etc., have poor extraction selectivity, low concentration ratio and low yield, and low product purity. technical problem

[0011] The present invention provides a method for separating and preparing a high content of mixed tocopherol by lyotropic liquid crystal extraction, and solves the problem that the high content of mixed tocopherol can not be separated by high efficiency and low energy consumption in the prior art, and is environmentally friendly. Problem solution

Technical solution [0012] A method for separating and preparing a high content mixed tocopherol by lyotropic liquid crystal extraction comprises the following steps:

[0013] The esterified or de-acidified vegetable oil deodorized distillate is dissolved in a weakly polar organic solvent to prepare a raw material liquid; the ionic liquid or surfactant is mixed with a polar diluent to form a solvent Liquid crystal; using the lyotropic liquid crystal as an extracting agent, separating and purifying the raw material liquid by countercurrent extraction or fractional extraction to obtain mixed tocopherol.

[0014] Dispersing an ionic liquid or surfactant with a polar diluent into a lyotropic liquid crystal means mixing the ionic liquid with a polar diluent or mixing the surfactant with a polar diluent.

[0015] In the present invention, the ionic liquid may be mixed and dispersed with a polar diluent or a surfactant and a polar diluent into a lyotropic liquid crystal by stirring, shearing, shaking or ultrasonication.

[0016] Preferably, the ionic liquid in the present invention is an anionic surface active ionic liquid or a cationic surface active liquid, and the anionic surface active ionic liquid and the cationic surface active ionic liquid are both composed of a cationic M ÷ and an anionic N - .

[0017] Further, in the anionic surface active ionic liquid:

The cation is a substituent-containing imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole cation or a piperidine cation, and the substituent is an alkyl group having a carbon chain length of 1-4, an olefin group or a An alkyl group of a hydroxy substituent; that is, an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole cation, and a piperidine cation each containing the substituent;

The anion N - is a carboxylate anion having a long carbon chain, an amino acid anion of a long carbon chain, an anion of a long chain sulfonic acid, a long chain sulfate anion or a long chain phosphate anion.

[0020] in the cationic surface active ionic liquid:

[0021] The cation is an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole cation or a piperidine cation having a long straight carbon chain substituent; that is, an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole Both the cation and the piperidine cation contain a long straight carbon chain substituent, and the long straight carbon chain means that the carbon number is ≥8;

[0022] The anion N - is a halide ion, a perchlorate ion, a dihydrogen phosphate ion, a hydrogen sulfate ion, a nitrate ion, a short chain carboxylate anion or a short chain amino acid anion.

[0023] Preferably, the surfactant is a nonionic surfactant, an anionic surfactant or a zwitterionic surfactant. [0024] The nonionic surfactant is a nonionic surfactant containing a saturated or unsaturated long straight carbon chain (carbon number ≥ 8), for example, a long-chain fatty alcohol polyoxyethylene ether, a long-chain fatty acid polyoxyethylene An ether or fatty acid methyl ester polyoxyethylene ether; the anionic surfactant is a carboxylate, an alkyl sulfate, a phosphate, and an alkyl sulfonate anionic surfactant having a cation of a metal ion, for example, dodecyl Sodium sulfonate, potassium laurate, etc.; the zwitterionic surfactant is a betaine type, imidazoline type or amino acid type zwitterionic surfactant containing a long carbon chain (carbon number ≥ 8), such as dodecylamino group. Sodium propionate, dodecyl dimethyl betaine, and the like.

[0025] Surfactants are substances having amphiphilic properties, ie, a "hydrophilic" head group and a "hydrophobic" tail, thereby enabling hydrophobic interaction through the tail in a polar solvent such as water or a non-polar solvent. Electrostatic interaction with the head group to form various types of aggregate structures (micelles, microemulsions, liquid crystals, etc.), which have good solubilizing ability for some substances which have little or no solubility in conventional solvents. . The ionic liquid, as an ionic compound, also possesses the properties of an anionic surface active or cationic surfactant when the structure contains a hydrophobic long carbon chain enthalpy. By designing the structure of the ionic liquid, it has the ability to form agglomerated structure with the strong affinity with tocopherol, forming a liquid crystal aggregate structure in an organic solvent, and forming an extraction system with a weakly polar organic solvent. Relying on the specific structure in the ionic liquid and the liquid crystal structure formed in the extraction phase synergistically increases the partitioning of tocopherol in the extract phase.

[0026] The present invention has found through a series of scientific experiments that a long carbon chain ionic liquid or a surfactant can form an aggregate structure such as an emulsion or a liquid crystal by self-assembly in a polar solvent, and these lyotropic liquid crystal extractants have both microstructures. Strong hydrogen bonding interface, which can form selective hydrogen bonding interaction with the phenolic hydroxyl group of tocopherol, and nanometer-sized hydrophobic alkyl aggregation structure, which can form strong hydrophobic interaction with weakly polar tocopherol. Role, through the synergy of hydrogen bonding and hydrophobic interaction, the lyotropic liquid crystal extractant exhibits a very high tocopherol extraction capacity, concentration of 100mg / ml 吋, tocopherol in a weak polar solvent - lyotropic liquid crystal extractant The partition coefficient in the two phases is as high as 50-60, which is 800-1000 times that of conventional organic solvents, conventional ionic liquids, and oligomer extractants. For example, the partition coefficient of lyotropic liquid crystal extractant composed of choline lauric acid ionic liquid and dimethyl sulfoxide (DMSO) can reach 49.52, respectively, and tetraethyl quaternary ammonium lauric acid ionic liquid and DMSO The partition coefficient of the lyotropic liquid crystal extractant is as high as 54.21. At the same time, the lyotropic liquid crystal has good back extraction performance, and the liquid crystal structure can be destroyed by adding an excessive amount of polar solvent, and the tocopherol is released to achieve high-efficiency back extraction. [0027] Still more preferably, the ionic liquid is a long-chain fatty acid radical (carbon number ≥ 8), choline, tetraethyl quaternary ammonium long-chain fatty acid salt (carbon number ≥ 8), 1-ethyl-3 -methylimidazole long-chain fatty acid salt (carbon number ≥ 8), tetraethyl quaternary phospholong long-chain fatty acid salt (carbon number ≥ 8), tetraethyl quaternary phosphododecyl sulfonate, N-ethyl Pyridyl lauryl hydrogen sulfate, N-butyl-N-methylpiperidine dodecyl phosphate dihydrogen salt, 1-hydroxyethyl-3-methylimidazole long-chain fatty acid salt (carbon number ≥ 8 , N-butyl-N-methylpyrrolidine tetradecanoate, 1-vinyl-3-methylimidazolium dodecylsulfonate, dodecyltrimethylammonium chloride, dodecane Pyridinium chloride, 1-mercapto-3-methylimidazolium hydrogensulfate, 1-dodecyl-3-methylimidazolium acetate or 1-dodecyl-3-methylimidazolium salt.

Still more preferably, the surfactant is sodium dodecyl sulfate, nonylphenol ethoxylate or sodium dodecylaminopropionate.

[0029] The molar fraction of the ionic liquid or surfactant in the extractant is 5<3⁄4~50<3⁄4. The ionic liquid or surfactant has the lowest concentration of the aggregate structure in the polar diluent, so the content of the ionic liquid or surfactant is required to be high enough to ensure the formation of liquid crystal, and it is found through experiments that when the ionic liquid or surfactant accounts for The lyotropic liquid crystal obtained by the molar percentage of the extracting agent is 5% to 50%, and the ionic liquid has a high molar fraction, and the liquid crystal phase has a high viscosity, which is not favorable for the extraction mass transfer.

[0030] The extraction process in the present invention may be a countercurrent extraction or a fractionation extraction process, and the two processes operate as follows:

(1) Countercurrent extraction:

[0032] using lyotropic liquid crystal as an extracting agent, introducing an extractant at the top of the extraction tower, passing the raw material liquid at the bottom of the column, collecting the extract liquid flowing out from the bottom of the column; adding one or several kinds to the extract obtained above The polar organic solvent or elevated temperature destroys the original lyotropic liquid crystal structure in the extracted phase, and is back-extracted with a fresh weak polar solvent. The stripped extract is subjected to vacuum distillation, water washing and drying to obtain a high-purity mixed tocopherol. The remaining extractant can be recycled after being distilled under reduced pressure to remove the polar diluent. Here, the polar organic solvent may be selected from methanol, N, N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, water or ethylene glycol.

(2) Fractionation extraction:

[0034] using lyotropic liquid crystal as an extractant, an extractant is introduced at the top of the fractionation extraction column, a weakly polar organic solvent is introduced as a detergent at the bottom of the column, and a raw material liquid is introduced into the column for fractional extraction, and the bottom of the column is collected. The extract obtained by adding one or more polar organic solvents or increasing the temperature to destroy the original lyotropic liquid crystal structure in the extract phase, and performing back extraction with a fresh weak polar solvent, the back extract Distillation under reduced pressure High purity mixed tocopherol is obtained after washing with water and drying. The remaining extractant can be recycled after being distilled under reduced pressure to remove the polar diluent.

In the present invention, the tocopherol can be better distributed in the extractant under the dual action of hydrogen bonding and liquid crystal structure to be better separated from impurities such as fatty acid methyl ester. To separate the tocopherol and ionic liquid or surfactant from the extract phase, it is only necessary to destroy the liquid crystal structure in the extracted phase, restore the aggregated tocopherol to a free state, and then realize the tocopherol by back extraction of a weakly polar organic solvent. Stripping and recovery of ionic liquids or surfactants.

[0036] The flow ratio of the countercurrent extraction bismuth extractant and the raw material liquid is 1: 0.5-10; the flow ratio of the fraction extraction extraction hydrazine extractant, detergent and raw material liquid is 0.1~10: 0.1-5: 0.1-5= detergent A weakly polar solvent used to dissolve the raw material liquid.

[0037] The polar diluent is methanol, N,N-dimethylformamide, dimethyl sulfoxide, acetonitrile, N-methylpyrrolidone, water or ethylene glycol.

[0038] The weakly polar organic solvent is n-hexane, n-heptane, n-octane, ethyl acetate, petroleum ether having a boiling range of 60 to 90 ° C or petroleum ether having a boiling range of 90 to 120 ° C.

[0039] The operating temperature of the countercurrent extraction or fractional extraction is 10 to 50 °C. If the temperature is too low, the viscosity of the raw material solution, extractant and detergent will become large, which is not conducive to the production operation. If the temperature is too high, the distribution ratio and selectivity will be lowered, and the too high or too low temperature will need to be larger. Energy consumption is achieved, resulting in an increase in production costs.

[0040] The vegetable oil deodorized distillate is a frequently seen esterification or removal of fatty acid pretreatment, which is a reaction product obtained by transesterification of a vegetable oil deodorized distillate with methanol or ethanol, or by molecular distillation.

And complex extraction and other methods for removing fatty acid products; the main components thereof include fatty acid esters, tocopherols and a small amount of glycerides, alcohols, etc., wherein the total weight percentage of mixed tocopherols is 2% to 60%; The concentration of mixed tocopherol in the raw material liquid is 10 to 150 g/liter.

Advantageous effects of the invention

Beneficial effect

[0041] Compared with the existing separation and extraction technology, the present invention has the following beneficial effects:

[0042] (1) The lyotropic liquid crystal extractant of the present invention has a high extraction capacity for tocopherol, and the amount of the extractant is significantly reduced and the number of theoretical plates required for extraction; and the lyotropic liquid crystal extractant used in the present invention At a higher The extraction efficiency and selectivity are still maintained at the raw material concentration, and the extraction efficiency of the conventional extractant decreases rapidly with the increase of the feed concentration.

[0043] (2) The preparation method of the lyotropic liquid crystal extracting agent is simple, stable, and easy to back-extract, and the recovery of the tocopherol can be achieved by destroying the aggregate structure in the lyotropic liquid crystal, which has a good application prospect.

[0044] (3) The present invention utilizes lyotropic liquid crystal extraction to obtain mixed tocopherol with a purity greater than 90% under optimized conditions, and the recovery rate of mixed tocopherol is above 90%.

[0045] (4) The invention adopts an ionic liquid and a surfactant with good biocompatibility as an extracting agent, and is environmentally friendly and environmentally friendly.

Embodiments of the invention

Embodiment 1

[0047] dissolving choline laurate in DMSO to prepare an extractant, wherein the molar fraction of choline laurate is 5%; taking the esterified vegetable oil deodorized distillate (containing 20% of mixed tocopherol), dissolved In n-hexane, a raw material liquid of 150 mg/ml was prepared. The extract phase was collected by a 4-stage countercurrent extraction at 40 ° C under the conditions of an extractant to raw material flow ratio of 1:0.5, and a 2-fold volume of acetonitrile and water were added thereto, and stripped with 3 volumes of n-hexane. The post-treatment steps such as evaporation, water washing, and drying obtain a mixed tocopherol product having a purity of 93% and a yield of 98<3⁄4.

Embodiment 2

[0049] dissolving tetraethyl quaternary ammonium laurate in DMSO to prepare an extractant, wherein the molar fraction of tetraethyl quaternary ammonium laurate is 10%; taking the esterified vegetable oil deodorized distillate (which contains Mixed tocopherol 75 %), dissolved in petroleum ether with a boiling range of 60-90 ° C, formulated into a 100 mg / ml raw material solution. At a ratio of 1:10 to the ratio of the extractant to the raw material, a stage 3 countercurrent extraction at 30 ° C was carried out, and the extract phase was collected, and 3 times the volume of water and acetonitrile were added thereto, and the boiling range was 2 times the volume. The petroleum ether is back-extracted at 60~90 °C, and the mixed tocopherol product is obtained by post-treatment steps such as evaporation, water washing and drying, and the purity thereof is 92%, and the yield is 90%.

Embodiment 3

[0051] 1-ethyl-3-methylimidazolium laurate is dissolved in acetonitrile to prepare an extract, wherein the molar fraction of 1-ethyl-3-methylimidazolium laurate is _15%; The degraded vegetable oil deodorized distillate (containing 25% of mixed tocopherol) is dissolved in petroleum ether having a boiling range of 90 to 120 ° C to prepare a raw material liquid of 125 mg/ml. The extractant phase is subjected to a 3-stage fractionation extraction operation at 30 ° C under the conditions of an extractant, a detergent and a raw material flow ratio of 1:0.2:0.5, and a certain amount of DMF and acetonitrile is added thereto, and the boiling range is 90. The petroleum ether is de-extracted at ~120 °C, and the mixed tocopherol product is obtained by post-treatment steps such as evaporation, water washing and drying, and the purity is 95%, and the yield is 99<3⁄4.

Example 4

[0053] dissolving choline laurate in DMF to prepare an extractant, wherein the molar fraction of choline laurate is 20%; taking the esterified vegetable oil deodorized distillate (containing mixed tocopherol 45%), dissolved In n-hexane, a raw material liquid of 80 mg/ml was prepared. The extractant, the detergent and the raw material flow ratio are 2:1:1, and subjected to a 4-stage fractionation extraction operation at 35 ° C, the extraction phase is collected, and 2 times the volume of acetonitrile and water are added thereto, and 5 times is used. The volume of n-hexane is back-extracted, and the post-treatment steps such as evaporation, water washing, and drying obtain a mixed tocopherol product having a purity of 94% and a yield of 97<3⁄4.

Example 5

[0055] dissolving tetraethyl quaternary phosphonium laurate in water to prepare an extractant, wherein the molar fraction of tetraethyl quaternary phosphonium laurate is 5%; taking the esterified vegetable oil deodorized distillate (which contains the mixture) Tocopherol 55%), dissolved in n-heptane, formulated into a 10 mg/ml stock solution. The extract phase is collected by a 3-stage countercurrent extraction at 50 ° C under the condition of 1:5 ratio of the extractant to the raw material stream, and a certain amount of water and acetonitrile are added thereto, and the mixture is back-extracted with n-heptane, evaporated and washed with water. The post-treatment step of drying, etc., mixed the tocopherol product with a purity of 98% and a yield of 93%.

Example 6

[0057] tetraethyl quaternary phosphododecylsulfonate is dissolved in DMSO to prepare an extractant, wherein the mole fraction of tetraethyl quaternary phosphododecylsulfonate is 8%; the vegetable oil after esterification is taken The deodorized distillate (containing 13% of mixed tocopherol) was dissolved in n-hexane to prepare a raw material liquid of 20 mg/ml. The extractant, the detergent and the raw material flow ratio are 5:10:6, and subjected to a 4-stage fractionation extraction operation at 40 ° C, the extraction phase is collected, a certain amount of acetonitrile and methanol are added thereto, and the mixture is back-extracted with n-hexane. After the post-treatment steps of evaporation, water washing, drying, etc., the mixed tocopherol product has a purity of 99% and a yield of 98%.

Example 7

[0059] choline laurate is dissolved in methanol to prepare an extractant, wherein the molar fraction of choline laurate is 10%; the esterified vegetable oil deodorized distillate (containing 30% of mixed tocopherol) is dissolved in In n-hexane , formulated into a 20mg / ml raw material solution. The extract phase was collected by a 4-stage countercurrent extraction at 10 ° C at a ratio of 5:4 of the extractant to the raw material stream, and 2 volumes of DMSO and acetonitrile were added thereto, and 4 times the volume of n-hexane was used. Extract. The obtained stripping solution is subjected to post-treatment by evaporation, water washing, drying, etc. to obtain a mixed tocopherol product having a purity of 83% and a yield of 94%.

Example 8

[0061] Dissolving N-ethylpyridine lauryl hydrogensulfate in DMF to prepare an extractant, wherein the molar fraction of N-ethylpyridine dodecyl hydrogensulfate is 15%; The vegetable oil deodorized distillate (containing 10% of mixed tocopherol) was dissolved in n-octane to prepare a raw material liquid of 15 mg/ml. Under the conditions of extractant, detergent and raw material flow ratio of 0.1:0.1:1, a 7-stage fractionation extraction operation is carried out at 30 ° C, the extraction phase is collected, a certain amount of acetonitrile and water are added thereto, and n-octane is reversed. Extract. The obtained stripping solution is subjected to evaporation, washing with water, drying, etc., to a mixed tocopherol product having a purity of 99% and a yield of 92%.

Example 9

[0063] N-butyl-N-methylpiperidine lauryl phosphate dihydrogen salt is dissolved in N-methylpyrrolidone to prepare an extract ij, wherein N-butyl-N-methylpiperidine The molar fraction of dialkyl dihydrogen phosphate is 9%; the esterified vegetable oil deodorized distillate (containing 5% mixed tocopherol) is dissolved in n-heptane to prepare a 10 mg/ml raw material solution. . Under the conditions of extractant, detergent and raw material flow ratio of 1.5:0.1:5, after 5 ° fractionation extraction operation at 35 ° C, the extraction phase is collected, a certain amount of methanol and acetonitrile are added thereto, and n-heptane is used. Extract. The obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 81% and a yield of 99 < 3⁄4.

Embodiment 10

The extractant is prepared by dissolving 1-hydroxyethyl-3-methylimidazolium myristate in DMSO, wherein the molar fraction of 1-hydroxyethyl-3-methylimidazolium tetradecanoate is 50% The esterified vegetable oil deodorized distillate (containing 2% of mixed tocopherol) was dissolved in n-hexane to prepare a raw material liquid of 20 mg/ml. The extraction phase is collected by a 3-stage fractionation extraction operation at 40 ° C under the conditions of an extractant, a detergent and a raw material flow ratio of 1.5:4:0.1, and a double volume of water and acetonitrile are added thereto, and 5 times is used. The volume of n-hexane is back-extracted, and the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 94% and a yield of 99%.

Example 11 [0067] The N-butyl-N-methylpyrrolidine tetradecanoate is dissolved in DMF to prepare an extractant, wherein the molar fraction of N-butyl-N-methylpyrrolidine tetradecanoate is 5% The esterified vegetable oil deodorized distillate (containing 40% of mixed tocopherol) was dissolved in ethyl acetate to prepare a 40 mg/ml raw material solution. The extractant, the detergent and the raw material flow ratio are 1.5:0.1:1, and subjected to a 4-stage fractionation extraction operation at 30 ° C, the extraction phase is collected, and a certain amount of N-methylpyrrolidone and acetonitrile are added thereto. The ethyl acetate was back-extracted, and the obtained stripping solution was subjected to evaporation, washing with water, and dried to give a mixed tocopherol product having a purity of 93% and a yield of 92%.

Example 12

Dissolving 1-vinyl-3-methylimidazolium lauryl sulfonate in acetonitrile to prepare an extractant, wherein the molar of 1-vinyl-3-methylimidazolium dodecyl sulfonate The fraction was 10%; the esterified vegetable oil deodorized distillate (containing 30% of mixed tocopherol) was dissolved in n-heptane to prepare a raw material liquid of 10 mg/ml. Under the conditions of extractant, detergent and raw material liquid flow ratio of 3:0.5:1, after 4 ° fractionation extraction operation at 35 ° C, the extraction phase is collected, and a certain amount of methanol and ethylene glycol are added thereto, with After the alkane is stripped, the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 93% and a yield of 95<3⁄4.

Example 13

[0071] The dodecyltrimethylammonium chloride is dissolved in methanol to prepare an extractant, wherein the mole fraction of dodecyltrimethylammonium chloride is 15%; the esterified vegetable oil is deodorized and distilled off The mixture (containing 25% of mixed tocopherol) was dissolved in n-hexane to prepare a raw material liquid of 20 mg/ml. The extract phase was collected by a second-stage countercurrent extraction at 10 ° C at a ratio of 5:10 of the extractant to the raw material stream, and a certain amount of methanol and acetonitrile were added thereto, and back-extracted with n-hexane. The obtained stripping solution is subjected to evaporation, water washing, drying, etc. to obtain a mixed tocopherol product having a purity of 85% and a yield of 97%.

Example 14

[0073] The dodecyl chloride is dissolved in DMF to prepare an extractant, wherein the molar fraction of dodecylpyridinium chloride is 8%; the esterified vegetable oil deodorized distillate (which contains mixed fertility) Phenol 50%), dissolved in n-heptane, formulated into a 15 mg/ml stock solution. Under the conditions of extractant, detergent and raw material flow ratio of 5:0.6:2, subjected to a 4-stage fractionation extraction operation at 30 ° C, the extraction phase is collected, and a certain amount of D MF and acetonitrile are added thereto, using n-heptane. After stripping, the obtained stripping solution is treated by evaporation, water washing, drying, etc. The mixed tocopherol product has a purity of 98% and a yield of 93%.

Example 15

[0075] Dissolving 1-mercapto-3-methylimidazolium hydrogensulfate in DMSO to prepare an extraction ij, wherein the molar fraction of 1-mercapto-3-methylimidazolium hydrogensulfate is 5%; The degraded vegetable oil deodorized distillate (containing 55% of mixed tocopherol) is dissolved in petroleum ether having a boiling range of 90 to 120 ° C to prepare a raw material liquid of 10 mg/ml. The extractant, the detergent and the raw material flow ratio of 10:3:1, at 25 ° C through a three-stage fractionation extraction operation, collecting the extract phase, adding a certain amount of DMSO and acetonitrile, using 90 ~ 120 ° The petroleum ether of C is stripped, and the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 98<3⁄4 and a yield of 90<3⁄4.

Embodiment 16

Preparing an extractant by dissolving 1-dodecyl-3-methylimidazolium acetate in DMF, wherein the molar fraction of 1-dodecyl-3-methylimidazolium acetate is 10% The esterified vegetable oil deodorized distillate (containing 5% mixed tocopherol) is dissolved in petroleum ether having a boiling range of 90-120 ° C to prepare a raw material liquid of 10 mg/ml. The extractant phase is subjected to a 4-stage fractionation extraction operation at 15 ° C under the conditions of an extractant, a detergent and a raw material flow ratio of 5:3:10, and a certain amount of water and acetonitrile are added thereto, and the boiling range is 90. The petroleum ether of ~120 °C is back-extracted, and the obtained stripping solution is subjected to evaporation, washing, drying and the like to obtain a mixed tocopherol product having a purity of 90% and a yield of 97<3⁄4.

Example 17

The extracting agent is prepared by dissolving 1-dodecyl-3-methylimidazolium alanine salt in acetonitrile, wherein the molar fraction of 1-dodecyl-3-methylimidazolium alaninate is 6%, the esterified vegetable oil deodorized distillate (containing 33% of mixed tocopherol) was dissolved in n-hexane to prepare a raw material liquid of 20 mg/ml. Under the conditions of extractant, detergent and raw material flow ratio of 1.5:0.1:2, a 5-stage fractionation extraction operation was carried out at 20 ° C, and the extract phase was collected, and a certain amount of methanol and DMF were added thereto, and the mixture was extracted with n-hexane. The obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 90% and a yield of 92%.

Example 18

[0081] dissolving sodium dodecyl sulfonate in water to prepare an extractant, wherein the molar fraction of sodium dodecyl sulfonate is 5%; taking the esterified vegetable oil deodorized distillate (which contains mixed tocopherol) 53%), dissolved in n-heptane, formulated into a 15mg/ml stock solution. In the conditions of extractant, detergent and raw material flow ratio of 8:6:7 After a 3-stage fractionation extraction operation at 50 ° C, the extract phase is collected, a certain amount of methanol and DMF are added thereto, and the mixture is back-extracted with n-heptane, and the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain mixed fertility. The phenol product had a purity of 98% and a yield of 95%.

Example 19

[0083] The nonylphenol ethoxylate is dissolved in water to prepare an extractant, wherein the phenolic polyoxyethylene ether has a mole fraction of 12%; and the esterified vegetable oil deodorized distillate (which contains mixed tocopherol 45) %), dissolved in n-hexane, formulated into a 10 mg/ml stock solution. The extractant, the detergent and the raw material flow ratio are 1.5:0.7:0.3, and the extracting phase is collected by a 4-stage fractionation extraction operation at 45 ° C, and a certain amount of water and ethylene glycol are added thereto, and n-hexane is used. After stripping, the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 95% and a yield of 96%.

Example 20

[0085] The sodium dodecylaminopropionate is dissolved in water to prepare an extractant, wherein the molar fraction of sodium laurylaminopropionate is 6%; and the esterified vegetable oil deodorized distillate (which contains the mixture) Tocopherol 23%), dissolved in n-octane, formulated into 15mg/ml raw material solution. Under the conditions of extractant, detergent and raw material flow ratio 1:0.1:7, after 5 ° fractionation extraction operation at 45 ° C, the extraction phase is collected, a certain amount of methanol and water are added thereto, and n-octane is reversed. After extraction, the obtained stripping solution is subjected to evaporation, washing with water, drying, etc. to obtain a mixed tocopherol product having a purity of 96% and a yield of 97%.

Claims

Claim

[Claim 1] A method for separating and preparing a high-content mixed tocopherol by lyotropic liquid crystal extraction, comprising the following steps:

Dissolving the fatty acid-treated vegetable oil deodorized distillate in a weakly polar organic solvent to prepare a raw material liquid; mixing an ionic liquid or a surfactant with a polar diluent to form a lyotropic liquid crystal; The lyotropic liquid crystal is an extracting agent, and the mixed tocopherol is separated and purified from the raw material liquid by countercurrent extraction or fractional extraction.

[Claim 2] The method for separating and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1

The ionic liquid is an anionic surface active ionic liquid or a cationic surface active liquid, and the anionic surface active ionic liquid and the cationic surface active ionic liquid are both composed of a cation M + and an anion N -.

[Claim 3] The method for separating and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 2

In the anionic surface active ionic liquid, the cation is a substituent-containing imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole cation or a piperidine cation, and the substituent has a carbon chain length of An alkyl group of 1, 4 or an alkyl group having a hydroxy substituent;

The anion N - is a carboxylate anion having a long carbon chain, an amino acid anion of a long carbon chain, a long chain sulfonate anion, a long chain sulfate anion or a long chain phosphate anion.

[Claim 4] The method for separating and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 2

, in the cationic surface active ionic liquid: the cation is an imidazolium cation, a pyridinium cation, a quaternary ammonium cation, a quaternary phosphonium cation, a pyrrole cation or a piperidine cation having a long straight carbon chain substituent; the anion N - is a halogen Ionic, perchlorate ion, dihydrogen phosphate ion, hydrogen sulfate ion, nitrate ion, short chain carboxylate anion or short chain amino acid anion.

[Claim 5] The method for extracting and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1

It is characterized in that the surfactant is a nonionic surfactant, an anionic surfactant or a zwitterionic surfactant.

[Claim 6] The method for extracting and preparing high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1 It is characterized in that the molar fraction of the ionic liquid or surfactant in the extractant is 5% to 50%.

[Claim 7] The method for extracting and preparing a high content mixed tocopherol by lyotropic liquid crystal according to claim 1, wherein the flow ratio of the countercurrent extraction strontium extractant and the raw material liquid is 1:0.5-10; The extraction ratio of the extractant, detergent and raw material liquid during extraction is 0.1~10: 0.1-5: 0.1-5 =

[Claim 8] The method for preparing a high content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1, wherein the polar diluent is methanol, N, N-dimethylformamide, and dimethyl Sulfone, acetonitrile, N-methylpyrrolidone, water or ethylene glycol.

[Claim 9] The method for extracting high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1, wherein the weakly polar organic solvent is n-hexyl, n-glycol, n-octyl, and acetic acid Ester, petroleum ether with a boiling range of 60-90 ° C or petroleum ether with a boiling range of 90-120 ° C.

[Claim 10] The method for extracting and preparing a high-content mixed tocopherol by lyotropic liquid crystal extraction according to claim 1, wherein the operation temperature of the countercurrent extraction or fractional extraction is 10 to 50 °C.