WO2000012533A1 - Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, dual phase - Google Patents

Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, dual phase Download PDF

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Publication number
WO2000012533A1
WO2000012533A1 PCT/US1999/014135 US9914135W WO0012533A1 WO 2000012533 A1 WO2000012533 A1 WO 2000012533A1 US 9914135 W US9914135 W US 9914135W WO 0012533 A1 WO0012533 A1 WO 0012533A1
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Prior art keywords
neutrals
tall oil
sterols
hydrocarbon
sterol
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PCT/US1999/014135
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French (fr)
Inventor
Zhiquan Q. Yan
Jane F. Byrne
Thomas J. Cuff
Philip L. Robinson
Raymond S. Vincente
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Westvaco Corporation
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Publication date
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Priority to AU49583/99A priority Critical patent/AU4958399A/en
Publication of WO2000012533A1 publication Critical patent/WO2000012533A1/en

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Classifications

    • 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
    • C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
    • C11B13/005—Recovery of fats, fatty oils or fatty acids from waste materials of residues of the fabrication of wood-cellulose (in particular tall-oil)
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07J—STEROIDS
    • C07J9/00—Normal steroids containing carbon, hydrogen, halogen or oxygen substituted in position 17 beta by a chain of more than two carbon atoms, e.g. cholane, cholestane, coprostane
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/74—Recovery of fats, fatty oils, fatty acids or other fatty substances, e.g. lanolin or waxes

Definitions

  • the present invention is related to methods of isolating and purifying the valuable constituents from Crude Tall Oil (CTO) recovered from the black liquor residue of wood pulping processes, primarily used in making paper. More particularly, the present invention is related to methods of extraction of valuable constituents from the bottoms, or pitch, fraction of distilled CTO. Most particularly, the present invention is related to methods of isolation and purification of extracted or distilled constituents of the neutrals fraction of CTO pitch which, upon said purification and subsequent modification, are useful as a dietary supplement in foods to reduce cholesterol levels in humans.
  • CTO Crude Tall Oil
  • CTO and Crude Sulfate Turpentine are major, renewable, chemical raw materials obtained from the kraft (sulfate) pulping of various coniferous trees.
  • Coniferous trees, especially pine contain resin acids in the free form, long chain fatty acids, and volatile terpenes . These materials, which are a major part of the wood extractives, are released from the wood during the kraft pulping process.
  • the black liquor residue from wood pulping contains valuable chemicals, which make up the CTO, with various industrial applications.
  • the black liquor contains the soaps of rosin and fatty acids, as well as sodium lignate and the spent cooking chemicals for reuse.
  • the sodium soap of these mixed acids rise to the surface and can be skimmed off.
  • This material is referred to as "soap skimmings" or "tall oil soap.”
  • the soap skimmings are converted to CTO by reaction with sulfuric acid and then separated from the simultaneously- formed spent acid by batch cooking, continuous centrifuging, or continuous decanting.
  • the CTO is normally divided into various fractions by distillation, which first extracts the pitch fraction.
  • the de-pitched CTO is then separated into fractions of heads, tall oil rosin (TOR) , tall oil fatty acids (TOFA) , and distilled tall oil (DTO) .
  • a major ingredient of the neutral fraction of CTO pitch is a class of commercially significant compounds known as sterols, including sitosterol. It is commonly known, however, that a typical method to obtain these sterols is via solvent extraction of tall oil soap, which is practiced commercially in Scandinavia.
  • U.S. Patent No. 5,502,045 disclosed the use (by ingestion) of a ⁇ -sitostanol fatty acid ester for reducing serum cholesterol level.
  • the patent's assignee, Raisio a Finnish manufacturer of foodstuffs, grain, and specialty chemicals, has developed a cholesterol -reducing margarine called Benecol * .
  • the active ingredient (in cholesterol reduction) in Benecol * is the claimed fat-soluble stanol ester which prevents cholesterol from being absorbed into the human digestive system.
  • the stanol ester is produced from plant-derived sterols (phytosterols) via hydrogenation and trans-esterification reactions. Cholesterol reductions (LDL and HDL) of 10-15% are common for individuals with diets containing Benecol * .
  • the above-stated objects of the invention are ultimately achieved by isolating the sterol component of the neutrals fraction of saponified tall oil pitch in the manner disclosed and claimed herein.
  • the first step in the invention sterol isolation process is accomplished by extracting the neutrals from saponified tall oil pitch. Then the extracted neutrals phase in a hydrocarbon, preferably heptane, is mixed with an alcohol solvent, preferably methanol, at a relatively high temperature (preferably greater than 50°C) . To this hydrocarbon/neutrals/alcohol solution is then added small amounts of water of a temperature higher than that of the hydrocarbon/neutrals/alcohol solution to result in two phases.
  • a hydrocarbon preferably heptane
  • an alcohol solvent preferably methanol
  • hydrocarbon/alcohol/neutrals/ water solution is allowed to cool slowly, with agitation, to facilitate crystallization of sterols.
  • the sterol crystals are isolated and washed with hydrocarbon solvent .
  • the Figure represents a flow diagram of the claimed process of isolation and purification of sterols from single-solvent extraction neutrals of tall oil pitch by direct crystallization—dual phase.
  • the invention direct crystallization, dual phase, process involves controlling the growth of sterol crystals from a solution of extracted, or distilled, tall oil pitch neutrals in a hydrocarbon solvent, preferably heptane.
  • a hydrocarbon solvent preferably heptane.
  • an alcohol solvent preferably methanol
  • Water also of a relatively higher temperature (preferably greater than 60°C, more preferably greater than 70°C) is then added to the hydrocarbon/methanol/neutrals solution to produce two liquid phases.
  • the mixture of the two liquid phases is cooled slowly, resulting in the crystallization of the sterols from the neutrals portion of the hydrocarbon/neutrals phase.
  • the two liquid phases are filtered to recover the sterol crystals.
  • Sterol yields up to 80.3%, based on the weight of sterols recovered divided by the available sterols in the neutrals, were achieved. Also, purities of up to 98.4% were achieved, with negligible contamination .
  • the direct crystallization, dual phase, process is seen to involve adding water to the relatively high temperature hydrocarbon/alcohol/neutrals solution to result in two liquid phases.
  • the mixture is allowed to cool slowly, during which time the sterols crystallize.
  • the mixture is then filtered to recover the sterol crystals.
  • the sterols are recovered from a hydrocarbon solution of the pitch- extracted neutrals of tall oil processing.
  • the neutrals may be derived from various sources, such as tall oil soaps or tall oil pitch. Also, such neutrals may be recovered by various means, the more obvious of which include distillation or solvent extraction.
  • the hydrocarbon employed likewise, may be one (or a mixture) of several organic solvents. A preferred hydrocarbon solvent is heptane.
  • extraction neutrals are prepared and concentrated in the laboratory, but the neutrals could remain in residual heptane from the solvent extraction operation.
  • a temperature of 50-60°C is sufficient to dissolve the neutrals in the lab; however, optimization of the invention process involves raising the temperature of the heptane stream phase to a higher temperature.
  • an alcohol preferably methanol, at the same or higher temperature, to create a heptane/sterol/methanol phase.
  • water at a higher temperature preferably greater than 60°C, more preferably greater than 70°C, is added to result in two separate liquid phases .
  • the dual-phase solution is allowed to cool slowly, preferably with sufficient agitation to keep the slurry well stirred throughout.
  • the sterol crystals are filtered using a jacketed Buchner funnel, and the resulting filter cake is washed with copious amounts of heptane.
  • the jacketed Buchner funnel is kept at near 40°C using a water bath. This keeps the temperature of the filter cake from cooling excessively during filtration, which can lead to contamination.
  • Final crystallization temperature is from 20-30°C, preferably 25°C.
  • a method for the isolation of sterols from sulfate pulping process tall oil pitch comprising the steps of: (a) saponifying the tall oil pitch; (b) separating the neutral fraction from the saponified tall oil pitch;
  • the blended solution is allowed to cool to a final temperature from about 20 °C to about 40°C to produce sterol crystals
  • hydrocarbon solvent is selected from the group consisting of straight- and branched- chain hydrocarbons with from 5 to 10 carbons;
  • hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, iso-octane, and mixtures thereof;
  • the alcohol solvent is selected from the group of aliphatic alcohols consisting of methanol, ethanol, butanol, iso-propanol, and mixtures thereof;
  • step (a) is greater than 60 °C; (8) the method of claim 1 wherein the temperature in step (a) is greater than 70°C;

Abstract

Isolation of the sterol component of the neutrals fraction of saponified tall oil pitch is disclosed. Sterol isolation is accomplished by a liquid-liquid extraction from the tall oil pitch-derived neutrals, resulting in a hydrocarbon (preferably heptane) phase at a relatively high temperature (preferably greater than 50 °C) to which small amounts of an alcohol solvent, preferably methanol, is added. To the hydrocarbon/alcohol/neutrals solution is then added water of a higher temperature, preferably 60-70 °C to result in the formation of two separate phases. The blended solution is allowed to cool slowly, with agitation, to facilitate crystallization of sterols. The sterols are isolated by filtration and then washed with hydrocarbon solvent to result in high yield and high purity.

Description

ISOLATION AND PURIFICATION OF STEROLS FROM
NEUTRALS FRACTION OF TALL OIL PITCH
BY DIRECT CRYSTALLIZATION, DUAL PHASE
BACKGROUND OF THE INVENTION
Field of the Invention
The present invention is related to methods of isolating and purifying the valuable constituents from Crude Tall Oil (CTO) recovered from the black liquor residue of wood pulping processes, primarily used in making paper. More particularly, the present invention is related to methods of extraction of valuable constituents from the bottoms, or pitch, fraction of distilled CTO. Most particularly, the present invention is related to methods of isolation and purification of extracted or distilled constituents of the neutrals fraction of CTO pitch which, upon said purification and subsequent modification, are useful as a dietary supplement in foods to reduce cholesterol levels in humans. Description of Related Art
CTO and Crude Sulfate Turpentine (CST) are major, renewable, chemical raw materials obtained from the kraft (sulfate) pulping of various coniferous trees. Coniferous trees, especially pine, contain resin acids in the free form, long chain fatty acids, and volatile terpenes . These materials, which are a major part of the wood extractives, are released from the wood during the kraft pulping process.
It has long been appreciated that the black liquor residue from wood pulping contains valuable chemicals, which make up the CTO, with various industrial applications. The black liquor contains the soaps of rosin and fatty acids, as well as sodium lignate and the spent cooking chemicals for reuse. On concentration of the spent pulping liquor, the sodium soap of these mixed acids rise to the surface and can be skimmed off. This material is referred to as "soap skimmings" or "tall oil soap." The soap skimmings are converted to CTO by reaction with sulfuric acid and then separated from the simultaneously- formed spent acid by batch cooking, continuous centrifuging, or continuous decanting. The CTO is normally divided into various fractions by distillation, which first extracts the pitch fraction. The de-pitched CTO is then separated into fractions of heads, tall oil rosin (TOR) , tall oil fatty acids (TOFA) , and distilled tall oil (DTO) .
Concentrated in the pitch fraction of CTO is a neutral fraction thereof. A major ingredient of the neutral fraction of CTO pitch is a class of commercially significant compounds known as sterols, including sitosterol. It is commonly known, however, that a typical method to obtain these sterols is via solvent extraction of tall oil soap, which is practiced commercially in Scandinavia. Recently, U.S. Patent No. 5,502,045 disclosed the use (by ingestion) of a β-sitostanol fatty acid ester for reducing serum cholesterol level. The patent's assignee, Raisio, a Finnish manufacturer of foodstuffs, grain, and specialty chemicals, has developed a cholesterol -reducing margarine called Benecol*. The active ingredient (in cholesterol reduction) in Benecol* is the claimed fat-soluble stanol ester which prevents cholesterol from being absorbed into the human digestive system. The stanol ester is produced from plant-derived sterols (phytosterols) via hydrogenation and trans-esterification reactions. Cholesterol reductions (LDL and HDL) of 10-15% are common for individuals with diets containing Benecol*.
Therefore, the value of recovering plant-derived sterols has become enhanced and the particular problems associated with recovering sitosterol from tall oil pitch worthy of investigation. A viable commercial process must achieve a high percent recovery of neutrals and/or sterols (greater than 70% recovery is preferable) and achieve high final sterol purity (higher than 95% is desirable) . Past attempts to extract neutrals/sterols from one or more fractions of CTO are reported in the following patents:
U.S. Patent Inventor Title Nos .
2,499,430 Vogel et al "Obtaining Sterols of High Purity"
2,530,809 Christenson et al " Fractionation of Tall Oil"
2,530,810 Christensen, et al " Separation of Unsaponifiable Matter from Tall Oil Residue"
2,547,208 Hasselstrom et al "Method for the Refining of Tall Oil Residue"
2,715,638 Albrecht et al " Production of Sterols from Tall Oil Pitch" ,835,682 Steiner et al " Sterol Recovery Process* ,866,781 Chase et al " Separating Non-acids from Soap Stocks" ,866,797 Berry et al " Improved Process of Isolating ,840,570 Julian et al "Process for Preparing Sterols from Tall Oil Pitch" ,879,431 Clark et al " Purification of Sterols by Distillation" ,965,085 Holmbom et al "Method for Refining of Soaps Soaps Using Solvent Extraction" ,044,031 Johansson et al " Process for the Separation of Sterols" ,124,607 Beaton et al " Preparation of Sterol Substates for Bioconversion" ,153,622 Lamminkari et al " Process for the Recovery of Beta-Sitosterol" ,420,427 Hamunen "Process for the Separation of Sterols or Mixtures of Sterols" ,422,974 Hamunen "Process for the Purification of Beta- Isolated from the Unsapon- ifiables in Crude Soap from the Sulphate Cellulose Process" ,422, 966 Ame " Separation of Neutrals from Tall Oil Soaps" ,496,478 Kulkarni et al " Process for Separating Unsaponifiables from Fatty and Rosin Acids" ,524,024 Hughes " Processes of Recovering Fatty Acids Sterols from Tall Oil Pitch" ,849,112 Barder et al "Adsorption Separation of Sterols from Tall Oil Pitch with Carbon Adsorbent" ,935,168 Sjόberg et al " Process for the Preparation of Alcohols" ,097,012 Thies et al " Solvent Extraction of Fatty Acid Stream with Liquid Water and Elevated Temperatures and Pressures" These approaches, however, have failed to provide both a high percent recovery of neutrals and/or sterols and a high final sterol purity. It is an object of this invention, therefore, to provide a method for recovering the neutral fraction of saponified tall oil pitch and isolating a high percentage of the sterol component thereof. It is a further object of this invention to obtain the isolated sterols at a high purity.
SUMMARY OF THE INVENTION
The above-stated objects of the invention are ultimately achieved by isolating the sterol component of the neutrals fraction of saponified tall oil pitch in the manner disclosed and claimed herein. The first step in the invention sterol isolation process is accomplished by extracting the neutrals from saponified tall oil pitch. Then the extracted neutrals phase in a hydrocarbon, preferably heptane, is mixed with an alcohol solvent, preferably methanol, at a relatively high temperature (preferably greater than 50°C) . To this hydrocarbon/neutrals/alcohol solution is then added small amounts of water of a temperature higher than that of the hydrocarbon/neutrals/alcohol solution to result in two phases. The hydrocarbon/alcohol/neutrals/ water solution is allowed to cool slowly, with agitation, to facilitate crystallization of sterols. The sterol crystals are isolated and washed with hydrocarbon solvent . BRIEF DESCRIPTION OF THE DRAWING (S.
The Figure represents a flow diagram of the claimed process of isolation and purification of sterols from single-solvent extraction neutrals of tall oil pitch by direct crystallization—dual phase.
DESCRIPTION OF THE PREFERRED EMBODIMENT (S)
Generally, the invention direct crystallization, dual phase, process involves controlling the growth of sterol crystals from a solution of extracted, or distilled, tall oil pitch neutrals in a hydrocarbon solvent, preferably heptane. To the solvent solution of extracted neutrals an alcohol solvent, preferably methanol, is added at a temperature greater than 50°C, to result in a hydrocarbon/methanol/neutrals solution. Water, also of a relatively higher temperature (preferably greater than 60°C, more preferably greater than 70°C) is then added to the hydrocarbon/methanol/neutrals solution to produce two liquid phases. The mixture of the two liquid phases is cooled slowly, resulting in the crystallization of the sterols from the neutrals portion of the hydrocarbon/neutrals phase. The two liquid phases are filtered to recover the sterol crystals. Sterol yields up to 80.3%, based on the weight of sterols recovered divided by the available sterols in the neutrals, were achieved. Also, purities of up to 98.4% were achieved, with negligible contamination .
With reference to the Figure, the direct crystallization, dual phase, process is seen to involve adding water to the relatively high temperature hydrocarbon/alcohol/neutrals solution to result in two liquid phases. The mixture is allowed to cool slowly, during which time the sterols crystallize. The mixture is then filtered to recover the sterol crystals.
In a preferred embodiment of the invention process, the sterols are recovered from a hydrocarbon solution of the pitch- extracted neutrals of tall oil processing. The neutrals may be derived from various sources, such as tall oil soaps or tall oil pitch. Also, such neutrals may be recovered by various means, the more obvious of which include distillation or solvent extraction. The hydrocarbon employed, likewise, may be one (or a mixture) of several organic solvents. A preferred hydrocarbon solvent is heptane. (For the purposes of the following examples, extraction neutrals are prepared and concentrated in the laboratory, but the neutrals could remain in residual heptane from the solvent extraction operation.) A temperature of 50-60°C is sufficient to dissolve the neutrals in the lab; however, optimization of the invention process involves raising the temperature of the heptane stream phase to a higher temperature. To the heptane stream phase is added an alcohol, preferably methanol, at the same or higher temperature, to create a heptane/sterol/methanol phase. Then, water at a higher temperature, preferably greater than 60°C, more preferably greater than 70°C, is added to result in two separate liquid phases .
The dual-phase solution is allowed to cool slowly, preferably with sufficient agitation to keep the slurry well stirred throughout. Finally, the sterol crystals are filtered using a jacketed Buchner funnel, and the resulting filter cake is washed with copious amounts of heptane. The jacketed Buchner funnel is kept at near 40°C using a water bath. This keeps the temperature of the filter cake from cooling excessively during filtration, which can lead to contamination. Final crystallization temperature is from 20-30°C, preferably 25°C.
The following examples are representative of the invention process :
Multiple experiments were conducted according to the description of the invention process set forth above, and data were tabulated for various combinations of high and low values for three variables in the Table.
Table
Figure imgf000010_0001
The data from Table I show that sterol yields ranged from 71.1-80.3% and sterol purities ranged from 85.4- 98.4%.
The subject matter of the invention is:
(1) A method for the isolation of sterols from sulfate pulping process tall oil pitch comprising the steps of: (a) saponifying the tall oil pitch; (b) separating the neutral fraction from the saponified tall oil pitch;
(c) blending a hydrocarbon solution of the neutrals with an alcohol solvent at a temperature greater than the crystallization temperature of sterol to produce a hydrocarbon/ neutrals/alcohol solution;
(d) adding water of a temperature higher than that of the hydrocarbon/neutrals/ alcohol solution to result in two phases;
(e) the blended solution is allowed to cool to a final temperature from about 20 °C to about 40°C to produce sterol crystals; and
(f) the sterol crystals are recovered from the cooled solution.
(2) the method of (1) wherein the extraction neutrals of tall oil pitch are derived by a process selected from the group consisting of solvent extraction and distillation;
(3) the method of (1) wherein the hydrocarbon solvent is selected from the group consisting of straight- and branched- chain hydrocarbons with from 5 to 10 carbons;
(4) the method of (3) wherein the hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, iso-octane, and mixtures thereof;
(5) the method of (1) wherein the alcohol solvent is an aliphatic alcohol;
(6) the method of claim 5 wherein the alcohol solvent is selected from the group of aliphatic alcohols consisting of methanol, ethanol, butanol, iso-propanol, and mixtures thereof;
(7) the method of claim 1 wherein the temperature in step (a) is greater than 60 °C; (8) the method of claim 1 wherein the temperature in step (a) is greater than 70°C;
(9) the method of claim 1 further comprising washing the recovered sterol crystals with a hydrocarbon solvent to obtain a high yield of sterols of high purity; and
(10) the method of claim 9 wherein the sterol yield is at least 70% and the sterol purity is at least 95%.
Modifications to this invention will occur to those skilled in the art. Therefore, it is to be understood that this invention is not necessarily limited to the particular embodiments disclosed; rather, it is intended to cover all modifications which are within the true spirit and scope of this invention, as disclosed and claimed herein.

Claims

What is claimed is:
1. A method for the isolation of sterols from sulfate pulping process tall oil pitch comprising the steps of:
(a) saponifying the tall oil pitch;
(b) separating the neutral fraction from the saponified tall oil pitch;
(c) blending a hydrocarbon solution of the neutrals with an alcohol solvent at a temperature greater than the crystallization temperature of sterol to produce a hydrocarbon/ neutrals/alcohol solution;
(d) adding water of a temperature higher than that of the hydrocarbon/neutrals/ alcohol solution to result in two phases;
(e) the blended solution is allowed to cool to a final temperature from about 20 ┬░C to about 40 ┬░C to produce sterol crystals; and
(f) the sterol crystals are recovered from the cooled solution.
2. The method of claim 1 wherein the extraction neutrals of tall oil pitch are derived by a process selected from the group consisting of solvent extraction and distillation.
3. The method of claim 1 wherein the hydrocarbon solvent is selected from the group consisting of straight- and branched- chain hydrocarbons with from 5 to 10 carbons.
. The method of claim 3 wherein the hydrocarbon solvent is selected from the group consisting of pentane, hexane, heptane, iso-octane, and mixtures thereof.
5. The method of claim 1 wherein the alcohol solvent is an aliphatic alcohol.
6. The method of claim 5 wherein the alcohol solvent is selected from the group of aliphatic alcohols consisting of methanol, ethanol, butanol, iso-propanol, and mixtures thereof.
7. The method of claim 1 wherein the temperature in step (a) is greater than 60┬░C.
8. The method of claim 1 wherein the temperature in step (a) is greater than 70┬░C.
9. The method of claim 1 further comprising washing the recovered sterol crystals with a hydrocarbon solvent to obtain a high yield of sterols of high purity.
10. The method of claim 9 wherein the sterol yield is at least 70% and the sterol purity is at least 95%.
PCT/US1999/014135 1998-08-27 1999-07-12 Isolation and purification of sterols from neutrals fraction of tall oil pitch by direct crystallization, dual phase WO2000012533A1 (en)

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CN105037473A (en) * 2015-07-20 2015-11-11 宜春大海龟生命科学有限公司 Purification and refining method of sterol from tall oil
CN111875659A (en) * 2020-08-21 2020-11-03 宜春大海龟生命科学有限公司 Method for purifying phytosterol

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105037473A (en) * 2015-07-20 2015-11-11 宜春大海龟生命科学有限公司 Purification and refining method of sterol from tall oil
CN111875659A (en) * 2020-08-21 2020-11-03 宜春大海龟生命科学有限公司 Method for purifying phytosterol
CN111875659B (en) * 2020-08-21 2021-10-08 宜春大海龟生命科学有限公司 Method for purifying phytosterol

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