CN112920249A - Novel industrial method for preparing stigmasterol - Google Patents
Novel industrial method for preparing stigmasterol Download PDFInfo
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- CN112920249A CN112920249A CN202110150205.8A CN202110150205A CN112920249A CN 112920249 A CN112920249 A CN 112920249A CN 202110150205 A CN202110150205 A CN 202110150205A CN 112920249 A CN112920249 A CN 112920249A
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- 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
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- 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
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Abstract
The invention provides a novel industrialized method for preparing stigmasterol by taking soybean oil leftovers as raw materials, which is characterized in that the soybean oil leftovers are subjected to the steps of dissolving, freezing, filtering, saponifying, acidifying, column chromatography, crystallizing and the like to prepare a high-purity stigmasterol product. The invention changes the soybean oil leftovers into valuable materials and recycles the resources to produce the stigmasterol with wide application, saves the resources, improves the comprehensive utilization rate of the resources and has great economic benefit and environmental benefit.
Description
Technical Field
The invention relates to an industrial new method for preparing stigmasterol, belonging to the field of pharmaceutical chemistry.
Background
Stigmasterol (stigmasterol), molecular formula C29H48O, with a molecular weight of 412, is also known as stigmasta-5, 22-dien-3 beta-ol or 24R-ethylcholest-5, 22-dien-3 beta-ol, is a phytosterol, widely found in various plants. Stigmasterol has obvious pharmacological activities of resisting oxidation, tumors, cardiovascular diseases and the like, is also a starting material for synthesizing steroid medicines, and has application in the industries of medicines, foods, chemical industry and the like. In recent years, with the discovery, development and scale-up of new steroid drugs, the amount of raw materials required is gradually increased; on the other hand, due to unreasonable mining, resource shortage is caused, the saponin content in the plant is reduced, so that the supply and demand of the international market are in conflict, and how to obtain the stigmasterol more widely is an important direction for stigmasterol research.
The soybean oil leftovers are byproducts generated in the process of producing the soybean oil by a hydration degumming process, so the soybean oil leftovers are often called hydrated oil residues, the yield of the hydrated oil residues accounts for 6-8% of the quality of the crude oil, the annual yield of the domestic soybean oil leftovers is over 10 ten thousand tons, if the domestic soybean oil leftovers cannot be well utilized, a large amount of resources are wasted, and the environmental pollution is serious because the domestic soybean oil leftovers are easy to ferment when being heated (over 20 ℃). Therefore, the reasonable utilization of the soybean oil leftover resources can generate great economic benefit and environmental benefit.
Disclosure of Invention
In order to solve the problems, the invention provides an industrialized new method for extracting stigmasterol from soybean oil leftovers, which has the advantages of few process steps, mild operation conditions, low solvent toxicity, safe production process, high extraction efficiency and high product purity of more than 98 percent.
The invention is realized by the following technical scheme:
a preparation method of stigmasterol takes soybean oil leftovers as raw materials.
Further, the preparation method of the stigmasterol comprises the following steps:
(1) dissolving: dissolving soybean oil leftovers with an organic solvent, and filtering to obtain a supernatant;
(2) freezing: freezing the supernatant at-30 to-10 ℃ for 10 to 15 hours, and quickly filtering out precipitated solids to obtain the supernatant;
(3) concentration: concentrating the supernatant obtained in the step (2) to remove the solvent to obtain crude product of the oily stigmasterol oleate;
(4) saponification: dissolving the oily stigmasterol oleate crude product obtained in the step (3) by using 8-15 times (v/w) of 0.5-2 wt% sodium hydroxide-methanol solution, and carrying out reflux reaction for 3-5 hours;
(5) acidifying: adjusting the pH value of the saponified solution to 5-6.5 by using acetic acid, and concentrating to remove methanol to obtain a paste crude product;
(6) and (3) column chromatography purification: performing chromatographic separation on the paste crude product obtained in the step (5) by a silica gel column, performing gradient elution by using a petroleum ether-ethyl acetate solvent system, collecting the stigmasterol section eluent, and concentrating to remove the solvent to obtain the stigmasterol crude product;
(7) and (3) crystallization: dissolving the crude stigmasterol product in methanol or ethanol, crystallizing, and filtering to obtain pure stigmasterol product.
Further, the organic solvent in the step (1) is selected from methanol, acetone or ethyl acetate.
In one embodiment, the method for preparing stigmasterol comprises the following steps:
(1) dissolving: dissolving soybean oil leftovers by using ethyl acetate in an amount which is 3-8 times (v/w), and filtering to obtain a supernatant;
(2) freezing: freezing the supernatant at-20 deg.C for 12 hr, and rapidly filtering to remove the precipitated solid to obtain supernatant;
(3) concentration: concentrating the supernatant obtained in the step (2) to remove the solvent to obtain crude product of the oily stigmasterol oleate;
(4) saponification: dissolving the oily stigmasterol oleate crude product obtained in the step (3) by using 10 times of the volume of 0.5-2 wt% of sodium hydroxide-methanol solution, and carrying out reflux reaction for 3-5 hours;
(5) acidifying: adjusting pH of the saponified solution to 6.0 with acetic acid, concentrating to remove methanol to obtain paste crude product;
(6) and (3) column chromatography purification: performing chromatographic separation on the paste crude product obtained in the step (5) by a silica gel column, performing gradient elution by using a petroleum ether-ethyl acetate solvent system, collecting the stigmasterol section eluent, and concentrating to remove the solvent to obtain the stigmasterol crude product;
(7) and (3) crystallization: dissolving the crude stigmasterol product in ethanol, crystallizing, and filtering to obtain pure stigmasterol product.
"v/w" in the present invention means the ratio of the volume of the added solvent to the weight of the intermediate material to be dissolved, L/Kg or mL/g, for example, the soybean oil offal is dissolved with 5 times (v/w) of ethyl acetate, that is, the soybean oil offal per Kg is dissolved with 5L of ethyl acetate.
The novel industrial method for preparing stigmasterol provided by the invention has the following advantages:
(1) the soybean oil leftovers are dissolved and then frozen, so that a large amount of solid impurities can be separated out, and can be removed by filtering, the operation is simple, the cost is low, the subsequent process is greatly simplified, and the extraction efficiency and the yield of the stigmasterol are improved;
(2) the saponification process is carried out in a sodium hydroxide-methanol solution, the saponification effect is good, and the product yield is high;
(3) the natural characteristics of the stigmasterol product can be maintained, the process steps are few, the operation condition is mild, the solvent toxicity is low, the production process is safe, the extraction efficiency is high, and the product purity can reach more than 98%;
(4) the soybean oil leftovers are used as raw materials, waste materials are changed into valuable materials, resources are recycled, the resources are saved, the comprehensive utilization rate of the resources is improved, and the ecological environment is protected.
Detailed Description
The present invention is described in further detail with reference to the following examples, but the present invention is not limited thereto, and any equivalent replacement in the field made in accordance with the present disclosure is included in the scope of the present invention.
EXAMPLE 1 Industrial preparation of Stigmasterol
Adding 100Kg of soybean oil leftovers into a 1000L enamel reaction kettle, and sucking 500L of ethyl acetate; heating with steam in the jacket to 60 deg.C, and stirring for dissolving; after the solution is dissolved and clear, the solution is filtered by a stainless steel plate frame while the solution is hot; the filtrate is divided into 50L stainless steel barrels with covers, and the stainless steel barrels are put into a refrigeration house for freezing and crystallizing;
after 12 hours, quickly filtering to remove the solid after no solid is separated out; recovering ethyl acetate from the solution at 60 deg.C and-0.08 Mpa; after the concentration is finished, 14.7kg of crude stigmasterol oleate is obtained;
adding 14.7kg of crude stigmasterol oleate into a 500L enamel reaction kettle, and sucking 150L of sodium hydroxide-methanol solution, wherein the concentration of sodium hydroxide is 1%; refluxing and reacting for 4 hours, and after the reaction is completed, dropwise adding acetic acid to adjust the pH value to 6.0; recovering methanol to dryness at 60 deg.C under-0.08 Mpa to obtain about 17Kg of paste;
adding 17Kg of paste into 170L of petroleum ether directly, heating to 40 ℃, stirring for dissolving, and cooling for precipitation after dissolving; pumping the supernatant into a silica gel column (50 Kg of silica gel pre-filled with 200 meshes) by using a 60L/h plunger pump; gradient eluting according to petroleum ether/ethyl acetate ratio of 1:0-20:1-10:1-5:1(v/v), collecting stigmasterol fraction eluate, and concentrating to dry to obtain white solid 7.87Kg with purity of 95%;
adding 7.87Kg of crude stigmasterol into 80L of ethanol, refluxing and dissolving at 80 deg.C to clear, filtering while hot, naturally cooling the filtrate to room temperature, and separating out 4.1Kg of stigmasterol white solid with purity of 98.1%.
EXAMPLE 2 Industrial preparation of Stigmasterol
Adding 100Kg of soybean oil leftovers into a 1000L enamel reaction kettle, and sucking 800L of acetone; heating with steam in the jacket to 50 deg.C, and stirring for dissolving; after the solution is dissolved and clear, the solution is filtered by a stainless steel plate frame while the solution is hot; the filtrate is divided into 50L stainless steel barrels with covers, and the stainless steel barrels are put into a refrigeration house for freezing and crystallizing;
after 15 hours, quickly filtering to remove solids after no solids are separated out; recovering acetone from the solution at 50 deg.C and-0.08 MPa; after the concentration is finished, 15.2kg of crude stigmasterol oleate is obtained;
15.2kg of crude stigmasterol oleate is added into a 500L enamel reaction kettle, 225L of sodium hydroxide-methanol solution is absorbed, and the concentration of sodium hydroxide is 1%; refluxing and reacting for 5 hours, and after the reaction is completed, dropwise adding acetic acid to adjust the pH value to 6.5; recovering methanol to dryness at 60 deg.C under-0.08 MPa to obtain about 17.4Kg of paste;
adding 17.4Kg of paste into 180L of petroleum ether directly, heating to 40 ℃, stirring for dissolving, and cooling for precipitation after dissolving; pumping the supernatant into a silica gel column (50 Kg of silica gel pre-filled with 200 meshes) by using a 60L/h plunger pump; gradient eluting according to petroleum ether/ethyl acetate ratio of 1:0-20:1-10:1-5:1(v/v), collecting stigmasterol fraction eluate, and concentrating to dry to obtain white solid 8.03Kg, with purity of 94%;
adding 8.03Kg of crude stigmasterol into 80L of methanol, refluxing and dissolving at 70 ℃ until the solution is clear, filtering while the solution is hot, naturally cooling the filtrate to room temperature, and separating out 3.9Kg of stigmasterol white solid with the purity of 98.0%.
EXAMPLE 3 Industrial preparation of Stigmasterol
Adding 100Kg of soybean oil leftovers into a 1000L enamel reaction kettle, and sucking 300L of methanol; heating with steam in the jacket to 55 deg.C, and stirring for dissolving; after the solution is dissolved and clear, the solution is filtered by a stainless steel plate frame while the solution is hot; the filtrate is divided into 50L stainless steel barrels with covers, and the stainless steel barrels are put into a refrigeration house for freezing and crystallizing;
after 10 hours, quickly filtering to remove the solid after no solid is separated out; recovering methanol from the solution at 55 deg.C and-0.08 Mpa; after the concentration is finished, 14.9kg of crude stigmasterol oleate is obtained;
14.9kg of crude stigmasterol oleate is added into a 500L enamel reaction kettle, and 120L of sodium hydroxide-methanol solution is absorbed, wherein the concentration of sodium hydroxide is 1 percent; refluxing and reacting for 3 hours, and after the reaction is completed, dropwise adding acetic acid to adjust the pH value to 5.0; recovering methanol to dryness at 60 deg.C under-0.08 MPa to obtain 16.7Kg of paste;
adding 16.7Kg of paste into 170L of petroleum ether directly, heating to 40 ℃, stirring for dissolving, and cooling for precipitation after dissolving; pumping the supernatant into a silica gel column (50 Kg of silica gel pre-filled with 200 meshes) by using a 60L/h plunger pump; gradient eluting according to petroleum ether/ethyl acetate ratio of 1:0-20:1-10:1-5:1(v/v), collecting stigmasterol fraction eluate, and concentrating to dry to obtain white solid 7.90Kg with purity of 94%;
adding 7.90Kg of crude stigmasterol into 80L of methanol, refluxing and dissolving at 70 ℃ until the solution is clear, filtering while the solution is hot, naturally cooling the filtrate to room temperature, and separating out 3.7Kg of stigmasterol white solid with the purity of 98.6%.
EXAMPLE 4 Industrial preparation of Stigmasterol
Adding 100Kg of soybean oil leftovers into a 1000L enamel reaction kettle, and sucking 600L of ethyl acetate; heating with steam in the jacket to 60 deg.C, and stirring for dissolving; after the solution is dissolved and clear, the solution is filtered by a stainless steel plate frame while the solution is hot; the filtrate is divided into 50L stainless steel barrels with covers, and the stainless steel barrels are put into a refrigeration house for freezing and crystallizing;
after 15 hours, quickly filtering to remove solids after no solids are separated out; recovering ethyl acetate from the solution at 60 deg.C and-0.08 Mpa; after the concentration is finished, 15.1kg of crude stigmasterol oleate is obtained;
15.1kg of crude stigmasterol oleate is added into a 500L enamel reaction kettle, and 180L of sodium hydroxide-methanol solution is absorbed, wherein the concentration of sodium hydroxide is 1%; refluxing and reacting for 4 hours, and after the reaction is completed, dropwise adding acetic acid to adjust the pH value to 6.0; recovering methanol to dryness at 60 deg.C under-0.08 MPa to obtain about 17.2Kg of paste;
adding 17.2Kg of paste into 170L of petroleum ether directly, heating to 40 ℃, stirring for dissolving, and cooling for precipitation after dissolving; pumping the supernatant into a silica gel column (50 Kg of silica gel pre-filled with 200 meshes) by using a 60L/h plunger pump; gradient eluting according to petroleum ether/ethyl acetate ratio of 1:0-20:1-10:1-5:1(v/v), collecting stigmasterol fraction eluate, and concentrating to dry to obtain white solid 8.06Kg, purity 95%;
adding 8.06Kg of crude stigmasterol into 100L of ethanol, refluxing and dissolving at 80 ℃ until the solution is clear, filtering while the solution is hot, naturally cooling the filtrate to room temperature, and separating out 4.0Kg of stigmasterol white solid with the purity of 98.8%.
EXAMPLE 5 Industrial preparation of Stigmasterol
Adding 100Kg of soybean oil leftovers into a 1000L enamel reaction kettle, and sucking 500L of methanol; heating with steam in the jacket to 55 deg.C, and stirring for dissolving; after the solution is dissolved and clear, the solution is filtered by a stainless steel plate frame while the solution is hot; the filtrate is divided into 50L stainless steel barrels with covers, and the stainless steel barrels are put into a refrigeration house for freezing and crystallizing;
after 12 hours, quickly filtering to remove the solid after no solid is separated out; recovering methanol from the solution at 55 deg.C and-0.08 Mpa; after the concentration is finished, 14.5kg of crude stigmasterol oleate is obtained;
14.5kg of crude stigmasterol oleate is added into a 500L enamel reaction kettle, 150L of sodium hydroxide-methanol solution is absorbed, and the concentration of sodium hydroxide is 1%; refluxing and reacting for 4 hours, and after the reaction is completed, dropwise adding acetic acid to adjust the pH value to 6.0; recovering methanol to dryness at 60 deg.C under-0.08 MPa to obtain 16.7Kg of paste;
adding 16.7Kg of paste into 160L of petroleum ether directly, heating to 40 ℃, stirring for dissolving, and cooling for precipitation after dissolving; pumping the supernatant into a silica gel column (50 Kg of silica gel pre-filled with 200 meshes) by using a 60L/h plunger pump; gradient eluting according to petroleum ether/ethyl acetate ratio of 1:0-20:1-10:1-5:1(v/v), collecting stigmasterol fraction eluate, and concentrating to dry to obtain white solid 7.83Kg, with purity of 96%;
adding 7.83Kg of crude stigmasterol into 80L of ethanol, refluxing and dissolving at 80 ℃ until the solution is clear, filtering while the solution is hot, naturally cooling the filtrate to room temperature, and separating out 3.7Kg of stigmasterol white solid with the purity of 99.2%.
Claims (4)
1. A preparation method of stigmasterol is characterized in that the stigmasterol is prepared by taking soybean oil leftovers as raw materials.
2. The method of claim 1, comprising the steps of:
(1) dissolving: dissolving soybean oil leftovers with an organic solvent, and filtering to obtain a supernatant;
(2) freezing: freezing the supernatant at-30 to-10 ℃ for 10 to 15 hours, and quickly filtering out precipitated solids to obtain the supernatant;
(3) concentration: concentrating the supernatant obtained in the step (2) to remove the solvent to obtain crude product of the oily stigmasterol oleate;
(4) saponification: dissolving the oily stigmasterol oleate crude product obtained in the step (3) by using 8-15 times (v/w) of 0.5-2 wt% sodium hydroxide-methanol solution, and carrying out reflux reaction for 3-5 hours;
(5) acidifying: adjusting the pH value of the saponified solution to 5-6.5 by using acetic acid, and concentrating to remove methanol to obtain a paste crude product;
(6) and (3) column chromatography purification: performing chromatographic separation on the paste crude product obtained in the step (5) by a silica gel column, performing gradient elution by using a petroleum ether-ethyl acetate solvent system, collecting the stigmasterol section eluent, and concentrating to remove the solvent to obtain the stigmasterol crude product;
(7) and (3) crystallization: dissolving the crude stigmasterol product in methanol or ethanol, crystallizing, and filtering to obtain pure stigmasterol product.
3. The method according to claim 2, wherein the organic solvent in step (1) is selected from methanol, acetone and ethyl acetate.
4. The method of claim 2, comprising the steps of:
(1) dissolving: dissolving soybean oil leftovers by using ethyl acetate in an amount which is 3-8 times (v/w), and filtering to obtain a supernatant;
(2) freezing: freezing the supernatant at-20 deg.C for 12 hr, and rapidly filtering to remove the precipitated solid to obtain supernatant;
(3) concentration: concentrating the supernatant obtained in the step (2) to remove the solvent to obtain crude product of the oily stigmasterol oleate;
(4) saponification: dissolving the oily stigmasterol oleate crude product obtained in the step (3) by using 10 times of the volume of 0.5-2 wt% of sodium hydroxide-methanol solution, and carrying out reflux reaction for 3-5 hours;
(5) acidifying: adjusting pH of the saponified solution to 6.0 with acetic acid, concentrating to remove methanol to obtain paste crude product;
(6) and (3) column chromatography purification: performing chromatographic separation on the paste crude product obtained in the step (5) by a silica gel column, performing gradient elution by using a petroleum ether-ethyl acetate solvent system, collecting the stigmasterol section eluent, and concentrating to remove the solvent to obtain the stigmasterol crude product;
(7) and (3) crystallization: dissolving the crude stigmasterol product in ethanol, crystallizing, and filtering to obtain pure stigmasterol product.
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Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB775835A (en) * | 1954-10-07 | 1957-05-29 | Eastman Kodak Co | Preparation of stigmasterol material |
FR1260564A (en) * | 1955-10-24 | 1961-05-12 | Eastman Kodak Co | Process for preparing a substance based on stigmasterol and product obtained |
US5117016A (en) * | 1991-05-13 | 1992-05-26 | Eastman Kodak Company | Method for obtaining a stigmasterol enriched product from deodorizer distillate |
WO2010097810A2 (en) * | 2009-02-25 | 2010-09-02 | Council Of Scientific & Industrial Research | A process for the preparation of phytosteryl ferulate |
CN107722099A (en) * | 2017-11-21 | 2018-02-23 | 西安海斯夫生物科技有限公司 | A kind of method that high-purity stigmasterol is prepared from phytosterols oletate |
CN111253458A (en) * | 2020-02-14 | 2020-06-09 | 湖南华诚生物资源股份有限公司 | Method for extracting stigmasterol from waste residues generated in natural ferulic acid production process |
-
2021
- 2021-02-03 CN CN202110150205.8A patent/CN112920249B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB775835A (en) * | 1954-10-07 | 1957-05-29 | Eastman Kodak Co | Preparation of stigmasterol material |
FR1260564A (en) * | 1955-10-24 | 1961-05-12 | Eastman Kodak Co | Process for preparing a substance based on stigmasterol and product obtained |
US5117016A (en) * | 1991-05-13 | 1992-05-26 | Eastman Kodak Company | Method for obtaining a stigmasterol enriched product from deodorizer distillate |
WO2010097810A2 (en) * | 2009-02-25 | 2010-09-02 | Council Of Scientific & Industrial Research | A process for the preparation of phytosteryl ferulate |
CN107722099A (en) * | 2017-11-21 | 2018-02-23 | 西安海斯夫生物科技有限公司 | A kind of method that high-purity stigmasterol is prepared from phytosterols oletate |
CN111253458A (en) * | 2020-02-14 | 2020-06-09 | 湖南华诚生物资源股份有限公司 | Method for extracting stigmasterol from waste residues generated in natural ferulic acid production process |
Non-Patent Citations (4)
Title |
---|
CLAUDIA APARECIDA SILVA ALMEIDA,等: "One-step rapid extraction of phytosterols from vegetable oils", 《FOOD RESEARCH INTERNATIONAL》 * |
CLAUDIA APARECIDA SILVA ALMEIDA,等: "One-step rapid extraction of phytosterols from vegetable oils", 《FOOD RESEARCH INTERNATIONAL》, 15 December 2019 (2019-12-15), pages 1 - 8 * |
朱向东,等: "豆甾醇提取纯化工艺研究", 《西南林学院学报》 * |
朱向东,等: "豆甾醇提取纯化工艺研究", 《西南林学院学报》, 31 December 2002 (2002-12-31), pages 41 * |
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