CN114644609A - Method for extracting natural vitamin E from byproduct residual oil - Google Patents
Method for extracting natural vitamin E from byproduct residual oil Download PDFInfo
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
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- C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols
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Abstract
The invention relates to a method for extracting natural vitamin E from byproduct residual oil, which comprises the following steps: contacting the byproduct residual oil dissolved in the organic solvent with strongly basic anion exchange resin HZ-202, eluting the resin, collecting eluted fractions, and drying to obtain natural vitamin E; wherein the byproduct residue contains vitamin E succinate and/or vitamin E acetate. The method not only can efficiently recover the natural vitamin E, but also can obtain a natural vitamin E product with higher purity, and in addition, the specific optical rotation of the obtained natural vitamin E product is obviously improved.
Description
Technical Field
The invention relates to a method for extracting natural vitamin E from byproduct residual oil.
Background
Natural Vitamin E (VE), also known as tocopherol, is a fat-soluble mixed Vitamin E, mainly composed of four isomers, alpha, beta, gamma, delta. The natural vitamin E is a common medicine and health care product, and is one of the most main natural antioxidants. Is dissolved in organic solvents such as fat, ethanol and the like, is insoluble in water, is stable to heat and acid, is unstable to alkali, is sensitive to oxygen and is insensitive to heat, but the activity of vitamin E is obviously reduced during frying. The tocopherol can promote the secretion of sex hormone, so that the vitality and the quantity of sperms of the male are increased; increase female estrogen concentration, improve fertility, prevent abortion, and can be used for preventing and treating male infertility, burn, cold injury, capillary hemorrhage, climacteric syndrome, and skin care. Recently, vitamin E has also been found to inhibit the lipid peroxidation in the lens of the eye, dilate peripheral blood vessels and improve blood circulation.
The vitamin has become the most useful and high-yield important vitamin variety in the international market at present, and becomes three major products of vitamin series together with vitamin C and vitamin A.
The safety and physiological activity of natural vitamin E are far superior to those of synthetic vitamin E. The natural vitamin E is mainly obtained by converting free fatty acid and neutral oil into fatty acid methyl ester from deodorized distillate (DD oil for short) obtained in the refining process of vegetable oil through esterification and ester exchange, removing most of sterol through crystallization by cold separation, and then separating through molecular distillation. However, the components of the deodorized distillate of vegetable oil are complex, and comprise free fatty acid, neutral oil, natural vitamin E, phytosterol, some odorous substances, pigments and the like, and the properties of the components are similar, so that the deodorized distillate of vegetable oil is usually subjected to certain pretreatment in industrial production and then is separated by a separation means to obtain the mixed tocopherol.
CN 03112620.0 discloses a preparation method of high-purity mixed tocopherol, which has the technical points that: hydrolyzing and acidifying raw materials to obtain free fatty acid, adding methanol to esterify into fatty acid methyl ester, distilling out methanol, removing fatty acid methyl ester, saponifying, esterifying, freezing to remove sterol in raw materials, reacting neutral oil to obtain fatty acid methyl ester, distilling to separate out fatty acid methyl ester, and finally adsorbing to separate out mixed tocopherol. The purity of the product is as high as more than 95%.
CN 02137090.7 discloses a method for extracting high content mixed tocopherol, which comprises extracting high content mixed tocopherol from low tocopherol content raw material and medium content tocopherol raw material. The process comprises the steps of esterification, adsorption separation, freezing separation, solvent extraction and the like, but the separation effect is poor and the environment is polluted to a certain extent.
CN 104211674A discloses a method for producing high-content natural vitamin E by a hydrolysis reduction method, which comprises esterifying, extracting and crystallizing low-content tocopherol to obtain high-content natural tocopherol succinate, hydrolyzing and reducing the natural tocopherol succinate into natural mixed tocopherol under an alkaline condition, and finally extracting, separating and distilling to obtain the high-content natural vitamin E.
Generally, the methods and processes described above all have certain disadvantages, as follows:
1) the process steps are complex, and the number of intermediate control points is large. The low-content tocopherol needs to be subjected to the processes of esterification, separation, molecular distillation, resin adsorption, secondary molecular distillation and the like, and each step needs to be controlled by corresponding process parameters and a central control index.
2) The production equipment is complex, the occupied area is large, more workers are used, and each process step needs different equipment to complete.
3) The risk of environmental pollution is large, a large amount of sulfuric acid or sodium hydroxide is needed in the esterification or saponification treatment process, the sewage treatment amount after natural tocopherol is extracted is large, and sewage treatment equipment with higher requirements needs to be equipped.
4) The molecular distillation method has high concentration ratio and yield, but has high requirements on equipment and high equipment investment cost due to high operation vacuum degree.
At present, no method for preparing natural vitamin E from deodorized distillate by adopting a resin adsorption hydrolysis method, improving the purity of the natural vitamin E and simultaneously improving the specific optical rotation exists.
Disclosure of Invention
The invention provides a method for extracting natural vitamin E from byproduct residual oil, which comprises the following steps: and (3) contacting the byproduct residual oil dissolved in the organic solvent with strongly basic anion exchange resin HZ-202, eluting the resin, collecting eluted fractions, and drying to obtain the natural vitamin E. The method not only can efficiently recover the natural vitamin E (the recovery rate is more than or equal to 90 percent), but also can obtain the natural vitamin E product with higher purity (the content of the natural vitamin E is more than or equal to 85 percent), and in addition, the specific optical rotation of the obtained natural vitamin E product is obviously improved (more than 24 degrees). In addition, the column adsorption medium can be recycled after elution.
In one or more embodiments, the elution step is performed using one or more of eluents selected from the group consisting of lower alcohols, lower alcohol aqueous solutions, acidic lower alcohol solutions, ethyl acetate, and mixed solutions of cyclohexane and ethyl acetate.
In one or more embodiments, the acidic lower alcohol solution is a solution containing CO2Preferably containing saturated CO2A lower alcohol solution of (a).
In one or more embodiments, the acidic lower alcohol solution is a lower alcohol solution comprising acetic acid, preferably a lower alcohol solution comprising 1-3 wt% acetic acid.
In one or more embodiments, the lower alcohol is methanol, ethanol, or isopropanol.
In one or more embodiments, the acidic lower alcohol solution is a solution containing CO2Preferably containing saturated CO295% ethanol solution.
In one or more embodiments, the acidic lower alcohol solution is an ethanol solution containing acetic acid, preferably a 95% ethanol solution containing 1-3 wt% acetic acid.
In one or more embodiments, in the cyclohexane and ethyl acetate mixture, the ratio of cyclohexane: the volume ratio of the ethyl acetate is 3-1: 1-3.
In one or more embodiments, 2 or more elutions are performed.
In one or more embodiments, a total of 2 elutions are performed, wherein elution is performed with a lower alcohol or lower alcohol aqueous solution or ethyl acetate, followed by elution with an acidic lower alcohol solution or a mixture of cyclohexane and ethyl acetate.
In one or more embodiments, the strongly basic anion exchange resin is expanded with a lower alcohol and then loaded into a chromatography column, which is then equilibrated with a lower alcohol.
In one or more embodiments, the lower alcohols used for swelling and equilibration are each independently selected from one or more of methanol, ethanol, and isopropanol.
In one or more embodiments, the organic solvent used to dissolve the by-product residue is selected from the group consisting of lower alcohols and ethyl acetate; preferably, the lower alcohol is selected from one or more of methanol, ethanol and isopropanol.
In one or more embodiments, the byproduct residue is a waste material containing Vitamin E Succinate (VES) and/or Vitamin E Acetate (VEA) produced during the production of natural vitamin E.
In one or more embodiments, the drying is concentrated drying under reduced pressure.
In one or more embodiments, the eluate is subjected to Thin Layer Chromatography (TLC) detection, wherein the developing agent is n-hexane-diethyl ether-acetic acid 8:2: 0.2.
In one or more embodiments, the method comprises:
(1) passing the by-product residue dissolved in the lower alcohol aqueous solution through a chromatography column packed with a gel-type strongly basic anion exchange resin HZ-202 swollen with the lower alcohol aqueous solution, and equilibrated with the lower alcohol aqueous solution;
(2) eluting the chromatographic column with lower alcohol aqueous solution and acidic lower alcohol aqueous solution in sequence, and collecting the eluent containing natural vitamin E; and
(3) concentrating the obtained eluent, thereby preparing the natural vitamin E.
In one or more embodiments, the methods described herein do not include the step of treating the eluate by molecular distillation.
The invention also comprises the application of the gel type strong-base anion exchange resin HZ-202 in extracting the natural vitamin E from the by-product residual oil, thereby improving the content of the vitamin E in the obtained natural vitamin E product and the specific optical rotation of the product, wherein the by-product residual oil is waste material which is generated in the production process of the natural vitamin E and contains vitamin E succinate and/or vitamin E acetate.
Drawings
FIG. 1: the production path of the residual oil.
Detailed Description
It is to be understood that within the scope of the present invention, the above-described technical features of the present invention and the technical features described in detail below (e.g., the embodiments) may be combined with each other to constitute a preferred embodiment.
It is generally believed that the by-product (i.e., residue) containing Vitamin E Succinate (VES) and/or tocopherol acetate (VEA) is a waste material in which the VES specific optical rotation has been destroyed and cannot be reused. However, the invention discovers that when the strongly basic anion exchange resin HZ-202 is used for treating the byproduct residual oil containing Vitamin E Succinate (VES) and/or tocopherol acetate (VEA), the resin can simultaneously achieve the functions of hydrolysis and purification, so that high-content and high-purity natural vitamin E can be extracted from the byproduct residual oil, and the specific optical rotation of the obtained natural vitamin E product can be obviously improved.
Accordingly, the present invention provides a process for extracting natural vitamin E from a by-product residue, the process comprising: and (3) contacting the byproduct residual oil dissolved in the organic solvent with strongly basic anion exchange resin HZ-202, eluting the resin, collecting eluted fractions, and drying to obtain the natural vitamin E.
In the present invention, unless otherwise specified, lower alcohols generally refer to C1-C4 monohydric alcohols, such as methanol, ethanol, isopropanol, and the like; the aqueous solution of a lower alcohol generally means an aqueous solution of a lower alcohol having a concentration of 80% or more, preferably 85% or more, more preferably 90% or more, and still more preferably 95% or more.
In the present invention, various strongly basic anion exchange resins HZ-202 suitable for use in the process of the present invention are commercially available.
In the present invention, the by-product generated during the production of natural vitamin E may be various residual oils generated during the processing of natural vitamin E, which are well known in the art, as long as it contains VES and/or VEA. The production path of the residue is shown in fig. 1.
Typically, the by-product residue is first dissolved with an organic solvent and the resulting product is then contacted with a resin. Suitable organic solvents may be selected from lower alcohols and ethyl acetate; preferably, the lower alcohol is selected from methanol, ethanol and isopropanol. The amount of the organic solvent to be used is not particularly limited, and it is preferable to completely and sufficiently dissolve the residual oil as a by-product. For example, the mass ratio of by-product residue to organic solvent is at least 1:1, preferably at least 1: 2, for example, may be in the range of 1:1 to 1: 5, in the above range. In a particularly preferred embodiment, the present invention uses a 95% aqueous ethanol solution to dissolve the by-product residue, and the mass ratio of the by-product residue to the aqueous solution can be in the range of 1: 2 to 1: 4 in the middle.
The strongly basic anion exchange resin HZ-202 may be swollen with a lower alcohol or an aqueous solution thereof before use. Suitable lower alcohols for swelling the resin may be those conventionally used in the art for swelling strongly basic anion exchange resins, such as ethanol or aqueous ethanol, e.g., 95% aqueous ethanol.
In general, the amount of the lower alcohol used for swelling the resin is not particularly limited as long as the purpose of swelling is achieved. In an exemplary embodiment, more than 1200mL of lower alcohol can be used to swell per 1000g of resin.
Swelling the resin, filling the column, balancing with lower alcohol or its water solution, and loading. Preferably, the lower alcohol used for equilibration is the same as the lower alcohol used for swelling. Preferably, ethanol or aqueous ethanol is used for both swelling and equilibration. Generally, 1500mL or more of a lower alcohol is used per 1000g of the resin.
Elution may be carried out using an eluent selected from the group consisting of lower alcohols, aqueous lower alcohol solutions, acidic lower alcohol solutions, ethyl acetate, and a mixture of cyclohexane and ethyl acetate. Preferred acidic lower alcohol solutions are solutions containing CO2More preferably a lower alcohol solution containing saturated CO2A lower alcohol solution of (a); more preferably, the acidic lower alcohol solution is a solution containing CO2Preferably containing saturated CO295% ethanol solution. Preferably, the acidic lower alcohol solution is a lower alcohol solution containing acetic acid, preferably a lower alcohol solution containing 1-3 wt% acetic acid; more preferably, the acidic lower alcohol solution is an ethanol solution containing acetic acid, preferably a 95% ethanol solution containing 1-3 wt% acetic acid. If a mixture of cyclohexane and ethyl acetate is used, the ratio of cyclohexane: the volume ratio of the ethyl acetate is 3-1: 1-3.
Elution may be performed 2 or more times. Preferably, a total of 2 elutions are performed, whichEluting with the lower alcohol or lower alcohol aqueous solution or ethyl acetate, and then eluting with the acidic lower alcohol solution or a mixture of cyclohexane and ethyl acetate. In a particularly preferred embodiment, the elution is carried out with an aqueous solution of 95% ethanol and then with a saturated CO2Eluting with 95% ethanol solution. The amount of the eluent is determined by those skilled in the art according to conventional technical means, so as to sufficiently elute the natural vitamin E adsorbed by the resin. For example, in the elution process, the content of the natural vitamin E in the eluent is detected by performing Thin Layer Chromatography (TLC) on the eluent, the fraction containing the natural vitamin E is collected, and the elution can be stopped when the eluent does not contain the natural vitamin E any more. The developing solvent for TLC may be, for example, n-hexane-ether-acetic acid in a volume ratio of 8:2: 0.2.
The eluent can be dried by a conventional method, so as to extract the natural vitamin E. For example, the eluate may be concentrated under reduced pressure.
The present invention will be illustrated below by way of specific examples. The specific optical rotations in the examples were determined as described in GB1886.233-2016, items A.5.3.1, A.5.3.2 and A.5.3.3, and were determined as follows:
a.5.3.1, d-alpha-tocopherol, Mixed tocopherol concentrate
Weighing a proper amount of sample (about 400mg equivalent to total tocopherol), accurately obtaining the sample to 0.2mg, placing the sample in a separating funnel, dissolving the sample by using diethyl ether 50mL, adding 10% of sodium hydroxide solution of potassium ferricyanide 50mL, shaking for 3min, washing the diethyl ether solution by using water for four times, using 50mL of water each time, drying the diethyl ether solution by using anhydrous sodium sulfate, placing the dried diethyl ether solution in a water bath for decompression or evaporating and concentrating the solution to about 7mL to 8mL under atmospheric pressure nitrogen flow, stopping heating, continuously volatilizing the diethyl ether until the solution is dry, immediately dissolving the residue by using isooctane 25.0mL, measuring the optical rotation at 25 +/-0.5 ℃ according to the method specified in GB/T613, and calculating the specific optical rotation according to the following formula:
in the formula:
α — measured optical rotation;
l-length of the tube in decimeters (dm);
m is the sample mass in grams (g);
x-total tocopherol content,%;
m/25-determine solution concentration in grams per milliliter (g/mL).
A.5.3.2, d-alpha-tocopheryl acetate concentrate
An appropriate amount of sample (about 0.4g corresponding to alpha-tocopherol) was weighed to an accurate amount of 0.0002g, placed in a 150mL round bottom flask, dissolved by adding 25mL of absolute ethanol, added with 120mL of ethanol sulfate solution, refluxed for 3h, and cooled. Quantitatively transferring the mixture into a 200mL measuring flask by using sulfuric acid ethanol solution 2, diluting the mixture to a scale mark, and shaking up. Precisely weighing 100mL, placing in a separating funnel, adding 200mL of water, mixing, extracting with diethyl ether, 75mL for the first time, and 25mL for the second and third times. Mixing the ether solutions, adding 50mL of 10% potassium ferricyanide sodium hydroxide solution, and shaking for 3 min; the following procedure was followed as described in A.5.3.1. And the specific rotation was calculated as follows:
in the formula:
α — measured optical rotation;
l-length of the tube in decimeters (dm);
x-tocopherol acetate content,%, in the sample;
m is the sample mass in grams (g);
m/25-determine solution concentration in grams per milliliter (g/mL);
0.911-unit conversion index relative to d-alpha-tocopherol.
A.5.3.3, d-alpha-tocopheryl succinate
Weighing a proper amount of sample (about equivalent to 400mg of alpha-tocopherol) to be accurate to 0.2mg, placing the sample in a 250mL round-bottom flask, adding 50mL of absolute ethyl alcohol to dissolve the sample, and refluxing for 1 min; when the solution is boiled, 1g of granular potassium hydroxide is slowly added into the condenser, so that overheating is avoided; continuously refluxing for 20min, dropwise adding 2mL of hydrochloric acid through a condenser tube, cooling, transferring the solution to 500mL, washing the flask with 100mL of water and 100mL of ether in a separating funnel, placing the washing solution in the separating funnel, violently shaking, standing for layering, separating, and extracting the water layer with ether for 2 times, 50mL each time; combining the ether extracts, washing with water for 4 times, and each time washing with 100 mL; placing the ether solution in a water bath, reducing the pressure or concentrating under nitrogen flow until the volume is about 7-8 mL, stopping heating, continuously volatilizing ether until the ether is dry, immediately adding 220mL of sulfuric acid ethanol solution into the residue for dissolving, transferring the residue into a separating funnel, washing the container with a small amount of sulfuric acid ethanol solution 2, transferring the container into the separating funnel, adding 200mL of water, extracting with ether for 3 times, 75mL for 1 time and 25mL for 2 and 3 times respectively, combining the ether solutions, adding 50mL of 10% sodium hydroxide solution of potassium ferricyanide, and shaking for 3 min; the procedure is as follows for the A.5.3.1 process. Specific rotation was calculated as follows:
in the formula:
α — measured optical rotation;
l-length of the tube in decimeters (dm);
x-tocopherol succinate content,%, in the sample;
m is the sample mass in grams (g);
m/25-determine solution concentration in grams per milliliter (g/mL);
0.811-unit conversion index relative to d-alpha-tocopherol.
Other methods and materials are described in the examples, unless otherwise indicated, as conventional in the art.
Example 1
1000g of gel-type strongly basic anion exchange resin HZ-202 was taken, and was fully swollen with 1600mL of 95% ethanol aqueous solution, and loaded into a chromatography column, and the equilibrium chromatography column was eluted with 2000mL of 95% ethanol.
Samples of VES residue (from Fengyi)Biological science and technology Jiangsu Co., Ltd.) 150g, adding 95% ethanol water solution with 3 times of mass, dissolving, loading, eluting the chromatographic column with 3000mL of 95% ethanol water solution, and then 4500mL of saturated CO2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 107.99g vitamin E product 1.
Through detection, the VES content of a sample before being loaded on the resin column is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the vitamin E product 1 after resin hydrolysis and purification, the content of the vitamin E is 86.70 wt%, the specific rotation is 24.8 degrees, the VES content is not detected, and the recovery rate of the vitamin E is 91.77%.
Example 2
1000g of gel-type strongly basic anion exchange resin HZ-202 was taken, fully swollen with 1600mL of 95% ethanol aqueous solution, loaded into a chromatographic column, and eluted with 2000mL of 95% ethanol from the equilibrium chromatographic column.
Collecting 200g VEA residual oil sample (from Jiangsu Co., Ltd., science and technology of Fengyi Probiotics), adding 3 times of 95% ethanol water solution, dissolving, loading, eluting with 2500mL 95% ethanol water solution, and eluting with 4000mL saturated CO2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 111.90g vitamin E product 2.
Through detection, the VEA content in a sample before being loaded on a resin column is 52.31 wt%, the VE content is 6.32 wt%, and the specific optical rotation is 16.8 degrees; in the vitamin E product 2 after resin hydrolysis and purification, the content of the vitamin E is 89.09 wt%, the specific rotation is 25.2 degrees, the content of VEA is not detected, and the recovery rate of the vitamin E is 92.34 percent.
Comparative example 1
Taking 200g of VES residual oil sample (from Jiangsu Co., Ltd., Probiotics technology), adding 400g of NaOH-methanol solution containing 10%, stirring in a water bath at 65 ℃ for reaction for 3 hours, adding 100g of hydrochloric acid aqueous solution containing 20% and 400mL of n-hexane after the reaction is ended, neutralizing for half an hour, then washing with water for 3 times, wherein 200g of water is neutralized each time, and obtaining 165.31g of VE product 3 after desolventization.
Through detection, the VES content in the sample before hydrolysis is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the hydrolyzed vitamin E product 3, the content of vitamin E is 58.09 wt%, the content of VES is 1.56 wt%, the specific rotation is 16.6 degrees, and the recovery rate of vitamin E is 92.68 degrees.
Comparative example 2
Taking 200g of VES residual oil sample (from Jiangsu Co., Ltd., Probiotics technology), adding 450g of KOH-methanol solution containing 10%, stirring in a water bath at 65 ℃ for reaction for 3 hours, adding 100g of hydrochloric acid aqueous solution containing 20% and 400mL of n-hexane after the reaction is ended, neutralizing for half an hour, then washing with water for 3 times, wherein 200g of water each time is neutral, and obtaining 164.62g of VE product 4 after desolventization.
Through detection, the VES content in the sample before hydrolysis is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the hydrolyzed vitamin E product 4, the content of vitamin E was 57.89 wt%, the content of VES was 1.86%, the specific rotation was 16.4 °, and the recovery rate of vitamin E was 91.98%.
Comparative example 3
Taking 200g of VES residual oil sample (from Jiangsu Co., Ltd., Probiotics technology), adding 130g of 30% sodium methoxide-methanol solution, stirring in a water bath at 68 ℃ for reaction for 4 hours, adding 70g of 10% hydrochloric acid aqueous solution and 500mL of n-hexane for neutralization reaction for half an hour after the reaction is ended, then washing with water for 3 times, wherein 200g of water is neutralized each time, and obtaining 164.83g of VE product 5 after desolventization.
Through detection, the VES content in the sample before hydrolysis is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the hydrolyzed vitamin E product 5, the content of the vitamin E is 58.63 wt%, the content of VES is 0.75 wt%, the specific rotation is 16.5 degrees, and the recovery rate of the vitamin E is 93.27 degrees.
Comparative example 4
Taking 200g of VES residual oil sample (from Jiangsu Co., Ltd., Probiotics technology), adding 150g of 30% potassium methoxide-methanol solution, stirring in a 68 ℃ water bath for reaction for 5 hours, adding 80g of 10% hydrochloric acid aqueous solution and 500mL of n-hexane for neutralization reaction for half an hour after the reaction is finished, then washing with water for 3 times, wherein 200g of water is neutralized each time, and obtaining 173.48g of VE product 6 after desolventization.
Through detection, the VES content in the sample before hydrolysis is 56.31 wt%, the VE content is 6.11 wt%, and the specific rotation is 16.5 degrees; in the hydrolyzed vitamin E product 6, the content of vitamin E is 58.27 percent by weight, the content of VES is 1.25 percent by weight, the specific rotation is 16.6 degrees, and the recovery rate of the vitamin E is 93.13 degrees.
The results of comparative examples 1-4 above show that hydrolyzing VES alone, while increasing VE content and recovery, does not substantially alter the specific optical rotation of the resulting product.
Comparative example 5
1000g of macroporous strongly basic anion exchange resin D-201 was taken, swollen well with 1600mL of 95% ethanol aqueous solution, packed into a column, and the column was equilibrated with 2000mL of 95% ethanol.
Taking 150g of VES residual oil sample (from Jiangsu Co., Ltd., science and technology of Fengyi Probiotics), adding 3 times of 95% ethanol water solution for dissolving, then loading, eluting a chromatographic column with 3000mL of 95% ethanol water solution, and then eluting with 5000mL of saturated CO2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 82.66g vitamin E product 7.
Through detection, the VES content of a sample before being loaded on the resin column is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the vitamin E product 7 after resin hydrolysis and purification, the content of vitamin E is 78.70 wt%, the specific rotation is 24.4 degrees, the content of VES is 1.33 wt%, and the recovery rate of vitamin E is 83.72%.
Comparative example 6
1500g of gel-type strongly basic anion exchange resin 717 are swollen with 2400mL of 95% ethanol aqueous solution and loaded into a chromatographic column, and the equilibrium chromatographic column is eluted with 3000mL of 95% ethanol.
Taking 200g of VES residual oil sample (from Jiangsu Co., Ltd., science and technology of Fengyi Probiotics), adding 3 times of 95% ethanol water solution by mass, dissolving, loading, eluting a chromatographic column with 4000mL of 95% ethanol water solution, and then using 6000mL of saturated CO2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 110.73g vitamin E product 8.
Through detection, the VES content of a sample before being loaded on the resin column is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the vitamin E product 8 after resin hydrolysis and purification, the content of the vitamin E is 77.38 wt%, the specific rotation is 24.5 degrees, the content of VES is 1.46 wt%, and the recovery rate of the vitamin E is 82.70%.
Comparative example 7
1000g of macroporous strongly basic anion exchange resin AB-8 was taken, fully swollen with 1600mL of 95% ethanol aqueous solution, loaded into a chromatographic column, and eluted with 1800mL of 95% ethanol from the equilibrium column.
Taking 150g of VES residual oil sample (from Jiangsu Co., Ltd., science and technology of Fengyi Probiotics), adding 3 times of 95% ethanol water solution for dissolving, then loading, eluting a chromatographic column with 2000mL of 95% ethanol water solution, and then using 3000mL of saturated CO2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 99.03g vitamin E product 9.
Through detection, the VES content in the sample before the sample is loaded on the resin column is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; in the vitamin E product 9 after resin hydrolysis and purification, the content of vitamin E is 71.68 wt%, the specific rotation is 16.6 degrees, the content of VES is 1.24 wt%, and the recovery rate of vitamin E is 91.35%.
The results of comparative examples 5-6 above show that the use of other types of strongly basic anion exchange resins, while providing specific optical rotation of the product, have VE contents below 80%; the results of comparative example 7 show that, after treatment with an anion exchange resin of this type, not only the VE content is less than 80%, but also the specific optical rotation is not substantially different from that before the treatment.
Comparative example 8
1000g of gel type strongly basic anion exchange resin HZ-202 was taken, fully swollen with 1600mL of 95% ethanol aqueous solution, loaded into a chromatographic column, and eluted with 1800mL of 95% ethanol to equilibrate the chromatographic column.
Taking 190g of mixed tocopherol sample (from Jiangsu limited science and technology of Probiotics), adding 3 times of 95% ethanol water solution by mass, dissolving, loading, eluting a chromatographic column with 2200mL of 95% ethanol water solution, and then 3000mL of saturated CO2Eluting with 95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid as developing agent at ratio of 8:2:0.2, collecting eluate fraction containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 98.21g vitamin E product 10.
Through detection, the content of vitamin E (including the sum of d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol and d-delta-tocopherol) in the mixed tocopherol sample before the mixed tocopherol sample is applied to the resin column is 49.69 wt%, and the specific optical rotation is 23.5 degrees; in the resin purified vitamin E product 10, the content of vitamin E (including the sum of d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol and d-delta-tocopherol) was 91.78 wt%, the specific rotation was 24.4 °, and the recovery rate of vitamin E was 95.47%.
Comparative example 9
1000g of gel type strongly basic anion exchange resin HZ-202 was taken, fully swollen with 1600mL of 95% ethanol aqueous solution, loaded into a chromatographic column, and eluted with 2000mL of 95% ethanol from the equilibrium chromatographic column.
Taking 150g of crude natural d-alpha-tocopherol succinate (VES) sample (from Jiangsu Co., Ltd., Probiotics technology), adding 3 times of 95% ethanol water solution by mass, dissolving, loading, eluting with 2000mL of 95% ethanol water solution, and then eluting with 3000mL of saturated CO2Eluting with 95% ethanol water solution, collecting eluate continuously, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid as developing agent at ratio of 8:2:0.2, and collecting eluate containingThe fractions of the tocopherol eluate were combined and concentrated at 50 ℃ under reduced pressure to constant weight to obtain 102.42g of vitamin E product 11.
Through detection, the VES content in a crude product sample of the d-alpha-tocopherol monoester before being loaded on a resin column is 83.10 wt%, and the specific optical rotation is 24.5 degrees; the vitamin E product 11 after resin hydrolysis and purification had a vitamin E (containing only d-alpha-tocopherol) content of 94.21 wt%, a specific rotation of 24.5 degrees, and a vitamin E recovery of 95.39 degrees.
The results of comparative example 9 show that purification and hydrolysis of crude natural d- α -tocopherol succinate (VES) using HZ-202 resin, although highly pure VE can be obtained, the specific optical rotation of the product is not improved.
Comparative example 10
1000g of macroporous adsorption resin D301 is taken, fully swelled by 2400mL of methanol, loaded into a chromatographic column, and eluted by 3000mL of methanol to balance the chromatographic column.
Taking 100g of a crude product sample (from Jiangsu Probiotics science and technology Jiangsu Co., Ltd.) of natural d-alpha-tocopherol succinate (VES), adding 2.5 times of methanol to dissolve the crude product sample, loading the sample, eluting a chromatographic column by 10000mL of methanol, eluting the natural d-alpha-tocopherol monoester adsorbed on resin, continuously collecting eluent, detecting by Thin Layer Chromatography (TLC), collecting eluent fractions containing tocopherol, merging the eluent fractions, and concentrating the eluent fractions at 50 ℃ under reduced pressure to constant weight to obtain 84.50g of a vitamin E product 12.
Through detection, the VES content in a VES crude product sample before being loaded on a resin column is 83.10 wt%, and the specific optical rotation is 24.5 degrees; in the vitamin E product 12 after resin purification, the VES content is 93.78 wt%, the specific rotation is 24.5 degrees, and the VES recovery rate is 95.36 degrees.
Comparative example 11
1000g of gel type strongly basic anion exchange resin HZ-202 was taken, and was fully swollen with 1600mL of 95% ethanol aqueous solution, and loaded into a chromatographic column, and the equilibrium column was eluted with 2000mL of 95% ethanol.
Taking 220g of a mixed tocopherol sample (from Jiangsu Co., Ltd., Probiotics science and technology), adding 3 times of 95% ethanol water solution by mass, dissolving, then loading, and using 2500mL of chromatographic columnIs eluted with a 95% aqueous ethanol solution and then saturated CO (3000 mL)2Eluting with-95% ethanol water solution, continuously collecting eluate, detecting by Thin Layer Chromatography (TLC) with n-hexane-diethyl ether-acetic acid 8:2:0.2 as developing agent, collecting eluate fractions containing tocopherol, mixing, and concentrating under reduced pressure at 50 deg.C to constant weight to obtain 72.91g vitamin E product 13.
Through detection, the content of vitamin E (including the sum of d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol and d-delta-tocopherol) in the mixed tocopherol sample before the mixed tocopherol sample is applied to the resin column is 30.69 wt%, and the specific optical rotation is 22.1 degrees; in the resin-purified vitamin E product 13, the content of vitamin E (including the sum of d-alpha-tocopherol, d-beta-tocopherol, d-gamma-tocopherol and d-delta-tocopherol) was 86.38 wt%, the specific rotation was 24.4 °, and the recovery rate of vitamin E was 93.28%.
Comparative example 12
600g of silica gel (Qingdao ocean chemical engineering, 200 meshes and 300 meshes) is taken, and is fully swelled with 1200mL of petroleum ether and then loaded into a chromatographic column, and the chromatographic column is eluted with 1000mL of petroleum ether.
50g of VES residual oil sample (from Jiangsu Co., Ltd., Probiotics technology) is taken, petroleum ether with the mass being 3 times that of the sample is added, the sample is loaded after being dissolved, a chromatographic column is eluted by 2000mL of mixed solution of petroleum ether and dichloromethane (1:1/V: V), then by 2000mL of mixed solution of dichloromethane and methanol (7:3/V: V), eluent is continuously collected and is subjected to Thin Layer Chromatography (TLC) detection, a developing agent is n-hexane-ethyl ether-acetic acid 8:2:0.2, eluent fractions containing VES are collected, and after being combined, the mixture is decompressed and concentrated to constant weight at 50 ℃, and 21.73g of VES product 12 is obtained.
Through detection, the VES content of a sample before being loaded on the resin column is 56.31 wt%, the VE content is 6.11 wt%, and the specific optical rotation is 16.5 degrees; the VES product 12, purified on silica gel, had a VES content of 96.68 wt%, a specific rotation of 16.6 °, and a VES recovery of 78.05%.
The results of comparative examples 10 and 12 show that a simple purification of crude d-alpha-tocopheryl succinate monoester or residue samples, while increasing the VES purity, does not increase the specific optical rotation of the resulting product.
The results of the above examples and comparative examples show that the relationship between the purification of vitamin E and the specific optical rotation is complicated. An increase in the VE content of the product does not mean that the specific optical rotation of the product is also increased at the same time. The invention adopts the specific resin HZ-202 to treat the waste residual oil in the grease processing, thereby not only preparing the natural VE with high content, but also obviously improving the specific optical rotation of the obtained VE product. Treatment with other resins does not simultaneously achieve high levels of native VE and increase its specific optical rotation.
Claims (10)
1. A process for extracting natural vitamin E from a by-product residuum, comprising: contacting the byproduct residual oil dissolved in the organic solvent with strongly basic anion exchange resin HZ-202, eluting the resin, collecting eluted fractions, and drying to obtain natural vitamin E; wherein the byproduct residue contains vitamin E succinate and/or vitamin E acetate.
2. The method according to claim 1, wherein the resin is eluted using an eluent selected from one or a combination of any one or more of a lower alcohol, a lower alcohol aqueous solution, an acidic lower alcohol solution, ethyl acetate, and a mixed solution of cyclohexane and ethyl acetate; wherein the lower alcohol has 1-4 carbon atoms.
3. The method of claim 2,
the acidic lower alcohol solution is a solution containing CO2Preferably containing saturated CO2More preferably a lower alcohol solution containing CO2More preferably, the ethanol solution of (2) contains saturated CO295% ethanol solution of (2); or the acidic lower alcohol solution is lower alcohol solution containing acetic acid, preferably lower alcohol solution containing 1-3 wt% acetic acid, more preferably ethanol solution containing acetic acid, more preferably 95% ethanol solution containing 1-3 wt% acetic acid;
the lower alcohol is methanol, ethanol or isopropanol;
in the mixed solution of cyclohexane and ethyl acetate, the weight ratio of cyclohexane: the volume ratio of the ethyl acetate is 3-1: 1-3.
4. The method of claim 1, wherein 2 or more elutions are performed; preferably, a total of 2 elutions are performed, wherein elution is performed with a lower alcohol or a lower alcohol aqueous solution or ethyl acetate, and then with an acidic lower alcohol solution or a mixture of cyclohexane and ethyl acetate.
5. The method of claim 1 wherein said strongly basic anion exchange resin is swollen with a lower alcohol and loaded into a column and then equilibrated with a lower alcohol.
6. The method of claim 1, wherein the organic solvent used to dissolve the by-product residue is a lower alcohol and/or ethyl acetate; preferably, the lower alcohol is selected from one or more of methanol, ethanol and isopropanol.
7. The process of claim 1 wherein the by-product residue is a waste material containing vitamin E succinate and/or vitamin E acetate produced during the production of natural vitamin E.
8. The method of claim 1, wherein the method comprises:
(1) passing the by-product residue dissolved in the lower alcohol aqueous solution through a chromatography column packed with a gel-type strongly basic anion exchange resin HZ-202 swollen with the lower alcohol aqueous solution, and equilibrated with the lower alcohol aqueous solution;
(2) eluting the chromatographic column with lower alcohol aqueous solution and acidic lower alcohol aqueous solution in sequence, and collecting the eluent containing natural vitamin E; and
(3) concentrating the obtained eluent, thereby preparing the natural vitamin E.
9. The method of claim 1, wherein the method does not include the step of treating the eluate by molecular distillation.
10. The application of the gel type strongly basic anion exchange resin HZ-202 in extracting natural vitamin E from byproduct residual oil so as to improve the content of the vitamin E in the obtained natural vitamin E product and the specific optical rotation of the product, wherein the byproduct residual oil is waste material containing vitamin E succinate and/or vitamin E acetate generated in the production process of the natural vitamin E.
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