CN114940659A - Purification method of vitamin A miscellaneous oil - Google Patents
Purification method of vitamin A miscellaneous oil Download PDFInfo
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- CN114940659A CN114940659A CN202210559573.2A CN202210559573A CN114940659A CN 114940659 A CN114940659 A CN 114940659A CN 202210559573 A CN202210559573 A CN 202210559573A CN 114940659 A CN114940659 A CN 114940659A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C403/00—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone
- C07C403/06—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms
- C07C403/12—Derivatives of cyclohexane or of a cyclohexene or of cyclohexadiene, having a side-chain containing an acyclic unsaturated part of at least four carbon atoms, this part being directly attached to the cyclohexane or cyclohexene or cyclohexadiene rings, e.g. vitamin A, beta-carotene, beta-ionone having side-chains substituted by singly-bound oxygen atoms by esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/006—Refining fats or fatty oils by extraction
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention provides a method for purifying vitamin A miscellaneous oil. Dissolving vitamin A miscellaneous oil by using an alkane solvent, adding an acetonitrile solution of organic base containing an auxiliary agent, fully stirring and mixing for a certain time at a certain temperature, then adding pure water for phase splitting, separating an acetonitrile water phase containing impurities, and removing the solvent under reduced pressure to obtain purified vitamin A essential oil. The method can improve the content of VA in the miscellaneous oil to more than 230 ten thousand IU and the recovery rate of VA is as high as more than 90 percent.
Description
Technical Field
The invention relates to the field of organic compound purification, in particular to a method for purifying vitamin A miscellaneous oil.
Background
Vitamin a (VA for short) is a fat-soluble vitamin, one of the essential vitamins for human and animals. Has important application in the industries of medicine, food, feed additive, cosmetics and the like. The concrete structure is as follows:
although vitamin A can be extracted from animal tissues, the vitamin A is relatively dispersed in resources, complicated in steps and high in cost, so that the commercial vitamin A is a chemical synthesis product. The main synthetic routes at present are: 1) the C6+ C14 route from Roche; 2) route C5+ C15 from BASF. The crude vitamin A product is oily liquid, and is generally dissolved in ethanol to obtain vitamin A crystals with the purity of more than or equal to 270 ten thousand IU through low-temperature crystallization. The oily liquid obtained after the solvent is removed from the crystallization mother liquor is called VA miscellaneous oil. The VA content in the VA miscellaneous oil is generally 50-100 ten thousand IU, and how to further utilize the VA in the miscellaneous oil is the key for reducing the production cost and improving the market competitiveness. According to the market price and the gross profit rate of the related products at present, the most economic benefit mode is to crystallize and separate VA miscellaneous oil again to obtain more vitamin A crystal products, but because the content of impurities in the VA miscellaneous oil is higher, VA crystals are difficult to separate out at normal crystallization temperature, and when the crystallization temperature is further reduced, part of impurities can be gelatinized to hinder the normal operation of the crystallization process. Therefore, the purification treatment of VA miscellaneous oil is very important.
In patent CN103936642, VA miscellaneous oil is reported to pass through a normal phase extraction tower and a reverse phase extraction tower in sequence, and VA is repeatedly extracted by two polar solvents, i.e. high and low, to remove impurities with different polarities in the mother liquor, thereby increasing VA content. The purification method has relatively complex process, needs professional continuous extraction equipment, and has complex process operation and higher cost and investment.
In patent CN108218751, VA is separated from impurities by column chromatography. Column chromatography is commonly used in laboratories for purification and separation of small amounts of samples, and some pharmaceutical enterprises also use the column chromatography for separation of high value-added drugs, but the yield is low, and the annual yield generally does not exceed 100 kg. Column chromatography is clearly not applicable for large scale commercial products.
In patent CN113292467, it is reported that VA miscellaneous oil is extracted and washed by using an alcohol-water solution of an inorganic base, and impurities in a mother liquor are extracted into the alcohol-water solution within a certain PH range, thereby realizing the purification of VA miscellaneous oil. Although the method is simple and convenient to operate, the purification effect and the VA recovery rate are relatively low, and according to the embodiment report in the patent, the maximum content of VA in the purified VA essential oil is only 207 ten thousand IU, and the maximum recovery rate of VA is only about 81%. And the process can generate a large amount of wastewater containing alkaline inorganic salt, thereby increasing the production cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for purifying VA miscellaneous oil. The method can improve the VA content in the miscellaneous oil to more than 230 ten thousand IU and the VA recovery rate is as high as more than 90 percent.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a method for purifying vitamin a miscellaneous oil, the method comprising the steps of;
s1: dissolving organic base in acetonitrile, and adding an auxiliary agent to obtain an acetonitrile solution of the organic base;
s2: adding an alkane solvent into vitamin A miscellaneous oil, uniformly mixing, adding an acetonitrile solution of organic base, and fully mixing to obtain a mixed solution;
s3: adding water into the mixed solution, fully stirring, standing for phase splitting, removing the lower acetonitrile water phase, and removing the solvent to obtain the purified vitamin A essential oil.
The purification process is carried out in an organic base system, which is beneficial to dissolving impurities in the vitamin A miscellaneous oil in an acetonitrile water system, and the added aromatic ether auxiliary agent can improve the distribution coefficient of the impurities in the acetonitrile water system, thereby improving the purification effect.
In the invention, the organic base in S1 is an alcamines compound containing C1-C4 saturated aliphatic, preferably one or more of ethanolamine, diethanolamine, triethanolamine, isopropanolamine and triisopropanolamine; preferably, the concentration of the acetonitrile solution of the organic base is 1 to 10 wt%, preferably 3 to 8 wt%.
In the invention, the auxiliary agent of S1 is an aromatic ether compound, preferably one or more of 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 3-chloroanisole and 4-chloroanisole; preferably, the mass ratio of the auxiliary agent to the organic base is (0.2-1.0): 1, preferably (0.4-0.8): 1.
in the invention, the alkane solvent of S2 is a straight-chain alkane of C5-C18, a branched-chain alkane of C5-C18 and a cycloalkane of C5-C18, and is preferably one or more of n-pentane, n-hexane and n-heptane; preferably, the mass ratio of the alkane solvent to the vitamin A miscellaneous oil is (1-9): 1, preferably (1.5-4): 1.
in the invention, the mass ratio of the acetonitrile solution of the organic base S2 to the vitamin A miscellaneous oil is (1-5): 1, preferably (2-4): 1.
in the invention, the S2 is added with an acetonitrile solution of an organic base and then stirred for 30-120 min at-5-25 ℃, preferably for 60-90 min at 5-15 ℃.
In the present invention, the mass ratio of the water added in S3 to the acetonitrile solution of the organic base is (0.1-0.5): 1, preferably (0.2-0.4): 1.
In the invention, the solvent for removing the S3 is distilled under reduced pressure under the conditions of the temperature of 30-50 ℃ and the vacuum degree of 5-160 kPaA.
Another object of the present invention is to provide the use of a purification method.
The application of a purification method is used for purifying vitamin A mixed oil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the VA content in the VA essential oil purified by the process is up to more than 230 ten thousand IU, and the VA recovery rate is up to more than 90%;
(2) the VA essential oil purified by the process can be crystallized and separated again to obtain VA crystals, so that the product yield is improved to the maximum extent, and the market competitiveness of the product is improved;
(3) the invention has simple and convenient process operation flow, low equipment cost and investment, does not need expensive professional extraction equipment, and is suitable for large-scale production.
Detailed Description
The present invention is further illustrated by the following specific examples, which are intended to be illustrative of the invention and are not to be construed as limiting the scope of the invention.
(1) Liquid chromatography conditions:
high performance liquid chromatograph, Agilent LC-1200, chromatographic analysis conditions: the measurement was carried out under the conditions specified in GB 14750-2010. Vitamin a content was determined by external standard method.
(2) The organic base sources in the examples of the invention are as follows:
ethanolamine: AR 99%, Aladdin
Diethanolamine: AR 99%, Aladdin
Triethanolamine: not less than 99% (GC), Alatin
Isopropanolamine: greater than 93% (GC), Aladdin
Triisopropanolamine: 95%, isomer mixture, Aladdin
Butanol amine: 97% of Aladdin
N-butyldiethanolamine: 98% of Aladdin
2-fluoroanisole: 98% of Aladdin
3-fluoroanisole: 99% of Aladdin
4-fluorophenylmethyl ether: 99% of Aladdin
3-chloro-anisole: 98% of Aladdin
4-Chlorobenzene methyl Ether: 99% of Aladdin
(3) The VA miscella source and the composition adopted by each embodiment and comparative example of the invention are as follows:
miscellaneous oil A: from a small test process for synthesizing Wanhua chemical vitamin A, the content of VA in the miscellaneous oil is 53 ten thousand IU, and the balance is heavy component impurities.
Miscellaneous oil B: from a small test process for synthesizing Van Hua chemical vitamin A, the content of VA in the miscellaneous oil is 79 ten thousand IU, and the balance is heavy component impurities.
Miscellaneous oil C: from a small test process for synthesizing Van Hua chemical vitamin A, the content of VA in the miscellaneous oil is 97 ten thousand IU, and the balance is heavy component impurities.
Other raw materials and reagents were obtained from commercial sources unless otherwise specified.
(4) The information of the vacuum distillation equipment used in the examples of the present invention is as follows:
a vacuum system: a KNF series SC 920G vacuum pump is adopted;
distillation equipment: xinweier D54102 type micro weeping distiller.
Example 1
Weighing 7.5g of triethanolamine, dissolving the triethanolamine in 142.5g of acetonitrile to prepare 5% triethanolamine acetonitrile solution, weighing 4.5g of 2-fluorophenylmethyl ether, adding the solution, and stirring until the solution is completely dissolved; weighing 50.0g of the mixed oil A, and dissolving in 125.0g of n-hexane; adding acetonitrile solution into alkane solution, and stirring at 10 deg.C for 80 min; adding 45.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and then standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum of 37kPaA to obtain purified essential oil D (10.3g), and the content of VA in essential oil D was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 2
Weighing 1.8g of ethanolamine, dissolving the ethanolamine in 58.2g of acetonitrile to prepare an acetonitrile solution of ethanolamine with the concentration of 3%, weighing 1.8g of 3-fluorobenzene ether, adding the solution into the solution, and stirring until the ethanolamine is completely dissolved; weighing 30.0gVA miscellaneous oil B, and dissolving in 120.0g n-pentane; adding acetonitrile solution into alkane solution, and stirring at 15 deg.C for 60 min; adding 12.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and then standing for phase splitting; the lower acetonitrile-water phase was separated, and the solvent n-pentane was removed by distillation under reduced pressure at 30 ℃ and a vacuum of 82kPaA to obtain purified essential oil E9.0 g, and the content of VA in essential oil E was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 3
Weighing 19.2g of diethanolamine to dissolve in 220.8g of acetonitrile to prepare an acetonitrile solution of 8% diethanolamine, weighing 3.84g of 4-fluorophenylmethyl ether to add into the solution, and stirring until the solution is completely dissolved; 60.0g of the miscella C is weighed and dissolved in 90.0g of n-heptane; adding the acetonitrile solution into the alkane solution and fully stirring for 90min at the temperature of 5 ℃; adding 96.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum degree of 12kPaA to obtain 22.9g of purified essential oil F, and the content of VA in the essential oil F was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 4
Weighing 1.8g of isopropanolamine, dissolving in 178.2g of acetonitrile to prepare 1% isopropanol amine acetonitrile solution, weighing 1.44g of 3-chloro-anisole, adding into the solution, and stirring until the solution is completely dissolved; weighing 36.0g of the mixed oil B, and dissolving in 324.0g of n-hexane; adding the acetonitrile solution into the alkane solution and fully stirring for 30min at 25 ℃; adding 90.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 50 ℃ under a vacuum of 54kPaA to obtain purified essential oil G10.8g, and the VA content in essential oil G was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 5
Weighing 9.0g of triisopropanolamine, dissolving the triisopropanolamine in 81.0g of acetonitrile to prepare an acetonitrile solution of triisopropanolamine with the concentration of 10%, weighing 3.6g of 4-anisole, adding the 4-anisole into the solution, and stirring until the 4-anisole is completely dissolved; weighing 90.0gVA of the mixed oil A, and dissolving the mixed oil A in 90.0g of n-pentane; adding acetonitrile solution into alkane solution, and stirring at-5 deg.C for 120 min; adding 9.0g of pure water into the mixed solution, continuing to fully stir for 5min, and then standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum degree of 115kPaA to obtain purified essential oil H18.4g, and the VA content in essential oil H was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 6
Weighing 5.4g of butanol amine, dissolving in 54.60g of acetonitrile to prepare an acetonitrile solution of butanol amine with the concentration of 9 percent, weighing 1.62g of 2,4, 6-trifluoroanisole, adding into the solution, and stirring until the solution is completely dissolved; weighing 40.0g of the mixed oil B, and dissolving in 200.0g of n-hexane; adding the acetonitrile solution into the alkane solution and fully stirring for 110min at the temperature of 0 ℃; adding 9.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and then standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum of 37kPaA to obtain purified essential oil I12.4g, and the VA content in essential oil I was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Example 7
Weighing 6.3g N-butyldiethanolamine to dissolve in 308.7g acetonitrile to prepare acetonitrile solution of N-butyldiethanolamine with the concentration of 2 percent, weighing 5.67g of 3-bromo-4-chloroanisole to add into the solution and stirring until the 3-bromo-4-chloroanisole is completely dissolved; weighing 70.0g of mixed oil C, and dissolving in 490.0g of n-hexane; adding acetonitrile solution into alkane solution, and stirring at 20 deg.C for 50 min; 141.75g of pure water is added into the mixed solution, and the mixed solution is kept fully stirred for 5min and then kept stand for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum of 37kPaA to obtain 26.5g of purified essential oil J, and the content of VA in the essential oil J was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Comparative example 1
Weighing 4.5g of 2-fluorobenzene methyl ether, adding into 150g of acetonitrile, and stirring until the 2-fluorobenzene methyl ether is completely dissolved; weighing 50.0g of the mixed oil A, and dissolving in 125.0g of n-hexane; adding acetonitrile solution into alkane solution, and stirring at 10 deg.C for 80 min; adding 45.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and then standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum of 37kPaA to obtain 26.6g of purified essential oil K, and the content of VA in the essential oil K was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Comparative example 2
Weighing 7.5g of triethanolamine, dissolving in 142.5g of acetonitrile to prepare 5% triethanolamine acetonitrile solution; weighing 50.0g of the mixed oil A, and dissolving in 125.0g of n-hexane; adding acetonitrile solution into alkane solution, and stirring at 10 deg.C for 80 min; adding 45.0g of pure water into the mixed solution, continuously and fully stirring for 5min, and then standing for phase splitting; the lower acetonitrile water phase was separated, the solvent was distilled off under reduced pressure at 40 ℃ under a vacuum of 37kPaA to obtain purified essential oil L11.3g, and the content of VA in the essential oil L was analyzed by high performance liquid chromatography, and the results are shown in Table 1.
Comparative example 3
Weighing 7.5g of sodium hydroxide, dissolving in 67.5g of water to prepare a 10% sodium hydroxide aqueous solution; weighing 5.0g of water, dissolving in 45.0g of ethanol to prepare ethanol solution of water with the concentration of 10%; weighing 50.0g of the mixed oil A, and dissolving in 100.0g of n-hexane; adding the sodium hydroxide aqueous solution and the ethanol aqueous solution into a normal hexane solution, fully stirring at 30 ℃ for 80min, standing for phase separation, separating a lower-layer water phase, adding 50g of water for washing once, and continuing the water separation operation; distilling n-hexane phase at 40 deg.C under vacuum degree of 37kPaA under reduced pressure to remove solvent to obtain purified essential oil M11.7g, and analyzing VA content in essential oil M by high performance liquid chromatography, the results are shown in Table 1.
TABLE 1 results of examples 1-7 and comparative examples 1-3
Claims (5)
1. A method for purifying vitamin A miscellaneous oil is characterized by comprising the following steps;
s1: dissolving organic base in acetonitrile, and adding an auxiliary agent to obtain an acetonitrile solution of the organic base;
s2: adding an alkane solvent into vitamin A miscellaneous oil, uniformly mixing, adding an acetonitrile solution of organic base, and fully mixing to obtain a mixed solution;
s3: adding water into the mixed solution, fully stirring, standing for phase splitting, removing the lower acetonitrile water phase, and removing the solvent to obtain the purified vitamin A essential oil.
2. The purification method according to claim 1, wherein the organic base of S1 is an alkanolamine compound containing C1-C4 saturated aliphatic groups, preferably one or more of ethanolamine, diethanolamine, triethanolamine, isopropanolamine and triisopropanolamine;
preferably, the concentration of the acetonitrile solution of the organic base is preferably 1-10 wt%, preferably 3-8 wt%;
and/or the auxiliary agent S1 is an aromatic ether compound, preferably one or more of 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 3-chloroanisole and 4-chloroanisole;
preferably, the mass ratio of the auxiliary agent to the organic base is (0.2-1.0): 1, preferably (0.4-0.8): 1.
3. the purification method according to claim 1, wherein the alkane solvent of S2 is a straight-chain alkane of C5-C18, a branched-chain alkane of C5-C18, and a cycloalkane of C5-C18, and is preferably one or more of n-pentane, n-hexane, and n-heptane;
preferably, the mass ratio of the alkane solvent to the vitamin A miscellaneous oil is (1-9): 1, preferably (1.5-4): 1;
and/or the mass ratio of the acetonitrile solution of the organic base S2 to the vitamin A miscellaneous oil is (1-5): 1, preferably (2-4): 1;
and/or adding an acetonitrile solution of organic base into S2, and stirring at-5-25 ℃ for 30-120 min, preferably at 5-15 ℃ for 60-90 min.
4. The purification method according to claim 1, wherein the mass ratio of the water added in S3 to the acetonitrile solution of the organic base is (0.1-0.5): 1, preferably (0.2-0.4): 1;
and/or the solvent for removing the S3 is distilled under reduced pressure under the conditions of the temperature of 30-50 ℃ and the vacuum degree of 5-160 kPaA.
5. Use of a purification process according to any one of claims 1 to 4 for the purification of vitamin A heterooils.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB306881A (en) * | 1929-02-18 | 1930-05-19 | Tayei Shimizu | A process for preparing vitamine-a in free or combined condition |
| DE660621C (en) * | 1933-06-03 | 1938-05-31 | Hoffmanni La Roche & Co Akt Ge | Method of separating the components of vitamin A. |
| US3367985A (en) * | 1966-04-18 | 1968-02-06 | Hoffmann La Roche | Process for the manufacture of polyene compounds |
| US3429928A (en) * | 1966-03-28 | 1969-02-25 | Hoffmann La Roche | Polyene compounds and processes |
| US3441623A (en) * | 1967-03-24 | 1969-04-29 | Hoffmann La Roche | Process for the preparation of beta-carotene and intermediates thereof from waste mother liquors |
| US3989758A (en) * | 1962-11-16 | 1976-11-02 | Hoffmann-La Roche Inc. | Monoacetals of unsaturated aliphatic dialdehydes |
| CN106866481A (en) * | 2016-12-30 | 2017-06-20 | 浙江海洋大学 | Green grass or young crops accounts for the preparation method and purposes of vitaminAD extract in fish guts |
| CN113292467A (en) * | 2021-06-09 | 2021-08-24 | 安徽智新生化有限公司 | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor |
-
2022
- 2022-05-23 CN CN202210559573.2A patent/CN114940659A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB306881A (en) * | 1929-02-18 | 1930-05-19 | Tayei Shimizu | A process for preparing vitamine-a in free or combined condition |
| DE660621C (en) * | 1933-06-03 | 1938-05-31 | Hoffmanni La Roche & Co Akt Ge | Method of separating the components of vitamin A. |
| US3989758A (en) * | 1962-11-16 | 1976-11-02 | Hoffmann-La Roche Inc. | Monoacetals of unsaturated aliphatic dialdehydes |
| US3429928A (en) * | 1966-03-28 | 1969-02-25 | Hoffmann La Roche | Polyene compounds and processes |
| US3367985A (en) * | 1966-04-18 | 1968-02-06 | Hoffmann La Roche | Process for the manufacture of polyene compounds |
| US3441623A (en) * | 1967-03-24 | 1969-04-29 | Hoffmann La Roche | Process for the preparation of beta-carotene and intermediates thereof from waste mother liquors |
| CN106866481A (en) * | 2016-12-30 | 2017-06-20 | 浙江海洋大学 | Green grass or young crops accounts for the preparation method and purposes of vitaminAD extract in fish guts |
| CN113292467A (en) * | 2021-06-09 | 2021-08-24 | 安徽智新生化有限公司 | Method for purifying vitamin A oil mother liquor by using alcohol-containing alkali liquor |
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