CN1616479A - Method for extracting stigmasterol from plant sterol - Google Patents
Method for extracting stigmasterol from plant sterol Download PDFInfo
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- CN1616479A CN1616479A CNA2003101087042A CN200310108704A CN1616479A CN 1616479 A CN1616479 A CN 1616479A CN A2003101087042 A CNA2003101087042 A CN A2003101087042A CN 200310108704 A CN200310108704 A CN 200310108704A CN 1616479 A CN1616479 A CN 1616479A
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Abstract
The process of separating and purifying stigmasterol from plant sterol includes: the first step of adding solvent absolute ethyl alcohol, n-propanol or n-butanol, heating to dissolve, slowly lowering temperature to crystallize, filtering, centrifugally separating and vacuum drying; and the second step of adding separating solvent into the product of the first step, heating to dissolve, slowly lowering temperature to crystallize and filtering; with the separation capable of being repeated for 2 or 3 times. The present invention has separate material concentration and separation refining steps, and has greatly raised stigmasterol purity and yield and no environmental pollution.
Description
Technical field
The invention belongs to field of fine chemical, relate to a kind ofly from plant sterol, separate, the method for purification Stigmasterol.
Background technology
The plant sterol that is contained among the plant mainly is the mixture of brassicasterol, campesterol, Stigmasterol and Sitosterol, and it can use greasy deodorizing technology industrial, obtains in large quantities in the deodorization distillate by by product.Stigmasterol is used for the pharmaceuticals of synthetic adrenocortical hormone and progestin, and Sitosterol in the plant sterol and campesterol are nugatory as the medical synthesis material of adrenocortical hormone and progestin, if do not remove these unworthy plant sterols in advance, Sitosterol, campesterol can have side effects and react obstacle, therefore they must be removed from plant sterol.
Because structural extreme is similar, from plant sterol, separate and remove Sitosterol and campesterol, obtaining the higher monomer Stigmasterol of purity is relatively a difficulty and a loaded down with trivial details job, the separation and purification Stigmasterol generally has three kinds of methods from plant sterol: the one, and utilize the two keys in the Stigmasterol structural formula after the bromination addition, to form Stigmasterol acetyl tetrabromide, can obtain pure Stigmasterol through a series of separating treatment again, but will use high temperature, hyperbaric environment in the reaction, running cost is higher; The 2nd, can utilize the chromatogram technology of preparing, carry out separated and collected according to the difference of each sterol component retention time or Rf value, but less with this method output, separating effect neither be very desirable; The 3rd, utilize organic solvent to carry out multistage fractional crystallization, obtain the higher Stigmasterol of purity at last.It is a kind of with the method for organic solvent from plant sterol separation and Extraction Stigmasterol that application number is that 02115645.X discloses, adopt the multistage Steppecd crystallization of solvent, selected organic solvent is the mixture of ethylene dichloride and n-heptane, in order from plant sterol, to obtain highly purified Stigmasterol, just carry out repeatedly simple refining separating treatment, so just reduced the extraction yield, Stigmasterol content and the yield that this kind method obtains all lower (content is about 85%, and yield is about 25%); And the ethylene dichloride that uses is the chlorine series solvent, and toxicity is big, and is big for environment pollution.
Summary of the invention
The technical assignment of technical problem to be solved by this invention and proposition is the defective that overcomes above-mentioned prior art, a kind of novel method of extracting Stigmasterol from plant sterol is provided, it concentrates and two steps of separation and purification by raw material, and specific nontoxicity organic solvent and suitable process conditions in each step, have been used, to improve the purity and the yield of Stigmasterol, environmentally safe.
Technical scheme of the present invention is such: the method for extracting Stigmasterol from plant sterol, it is characterized in that reactions steps is as follows: the first step, solubilizing agent dehydrated alcohol, n-propyl alcohol or propyl carbinol in plant sterol, rising temperature for dissolving, slow then decrease temperature crystalline, filter, the crystallisate of gained repeats above-mentioned enrichment step 0～1 time, carries out centrifugation, vacuum-drying afterwards; Second step, bonus point exsolution agent in the plant sterol enriched material that obtains toward the first step, rising temperature for dissolving, slow decrease temperature crystalline then, filtration, the crystallisate of gained repeats above-mentioned separating step 2～3 times.From plant sterol, separate in two steps among the present invention, the purification Stigmasterol, plant sterol obtains tentatively concentratedly in the first step, this enriched product is transferred in the separation and purification operation of second step then.The concentration technology and the final separation and purification technology of raw material were separated in two steps, and by using specific organic solvent and suitable process conditions, be different from simple separation in the existing method fully, concentration technology can make the yield of Stigmasterol be greatly improved, and the extraction times of separating technology is obviously reduced.2～3 times the content of Stigmasterol is reached about 95% as long as extract in the separating technology of the present invention, 3～4 extractions can make the content of Stigmasterol reach about 98%, and existing method needs 6～7 extractions also can only reach about 85%, and the Stigmasterol content height that the present invention obtains and the efficient of sepn process significantly improve.
The described method of extracting Stigmasterol from plant sterol, the separation solvent is a kind of or wantonly two kinds of combinations in ethyl acetate, acetone, butanone, normal hexane, normal heptane, Virahol, isopropylcarbinol, the pimelinketone.
The described method of from plant sterol, extracting Stigmasterol, the plant sterol enriched material is 1: 5～12 with the mass volume ratio that separates solvent (g/ml), and solvent temperature is 60～85 ℃, and Tc is controlled at 25～45 ℃, and the insulation rearing crystal time is 10～16 hours.
The described method of extracting Stigmasterol from plant sterol, plant sterol enriched material be preferably 1: 6 with the mass volume ratio that separates solvent～and 10.
The described method of from plant sterol, extracting Stigmasterol, plant sterol in the first step and the mass volume ratio of solvent (g/ml) are 1: 5～10, solvent temperature is 60～110 ℃, Tc is controlled at 15～35 ℃, the insulation rearing crystal time is 10～16 hours, vacuum tightness is-0.08～-0.09Mpa, drying temperature is 40～60 ℃.
The described method of extracting Stigmasterol from plant sterol, the mass volume ratio of plant sterol and solvent be preferably 1: 6～and 8.
The described method of from plant sterol, extracting Stigmasterol, the filtrate of gained in the intermediate steps in the first step and second step, after measuring the content of Stigmasterol wherein, can mix back recrystallize (being mother liquid recycle) by the filter cake close with the Stigmasterol content that the reaction that feeds intake next time obtains, fully extract Stigmasterol, can further improve the yield of Stigmasterol like this, make yield more than 55%.
The described method of from plant sterol, extracting Stigmasterol, obtaining the lower filtrate of Stigmasterol content in the reaction directly handles through low temperature or distillation, at-8～-12 ℃ of other sterol and solvents that reclaim down wherein, solvent is reusable, reduce production costs, the Sitosterol content of final filtrate is used for fodder additives, cosmetic industry etc. after the recovery about 60%, make full use of resource.
The invention has the beneficial effects as follows: 1) concentrating and two steps of separating of separation and purification by raw material, and specific nontoxicity organic solvent and suitable process conditions in each step, have been used, the purity and the yield of Stigmasterol have been improved greatly, environmentally safe; 2) before separating step, plant sterol is concentrated, reduced the number of times of extraction and the yield of Stigmasterol is greatly improved; 3) recrystallize after the close filter cake of Stigmasterol content that obtains of the reaction filtrate that produces and the reaction that feeds intake next time mixes fully extracts Stigmasterol, has further improved the yield of Stigmasterol; 4) other sterol and solvent from plant sterol are reclaimed, make full use of resource, reduced production cost.
Embodiment
Ingredient requirement: the total content of being produced with soybean oil deodorizer distillate as the raw material that extracts Stigmasterol, requires wherein that Stigmasterol content is not less than 20% greater than 90% refined plant sterol, and solvent for use is all analytical pure.
Embodiment 1
The first step: with plant sterol 100g (Stigmasterol content 23.2%), 75 ℃ of dissolving 1hr that reflux in n-propyl alcohol 750ml, cool off ℃ crystallization of this solution to 20, insulation growing the grain 15hr, after-filtration, with filter cake vacuum-drying (vacuum tightness-0.08～-0.09Mpa, 40 ℃ of temperature), behind the 5hr drying crystalline 48.5g (Stigmasterol content 35.7%).
Second step: the plant sterol enriched material 48.5g that the first step is obtained, heating for dissolving in the 245ml ethyl acetate, be cooled to 40 ℃ again behind this solution insulation growing the grain 14hr, the crystallization of filter deposition, crystallization to gained, carry out lock out operation 3 times with same refining separation condition, get Stigmasterol 3.5g (Stigmasterol content 95.3%), the ultimate yield behind mother liquid recycle is 57.4%.
Listed Stigmasterol Determination on content result in the following table, assay is to use gas chromatography.
| The first step | Second step | |||
| Crystallization for the first time | Crystallization for the second time | Crystallization for the third time | The 4th crystallization | |
| Stigmasterol content 35.7% | ????51.2％ | ????70.8％ | ????84.2％ | ????95.3％ |
Embodiment 2
The first step: plant sterol 100g (Stigmasterol 20.9%) 78 ℃ of heating for dissolving in dehydrated alcohol 800ml, the slow cooling of this solution is cooled to 25 ℃ of post crystallizations, growing the grain 12hr after-filtration, the vacuum-drying of gained filter cake must concentrate plant sterol 49.6g (Stigmasterol content 41.2%).
Second step: the concentrated plant sterol 49.6g heating for dissolving in the 250ml isopropylcarbinol with the first step obtains, again this solution is cooled to 40 ℃ of crystallizations, growing the grain 12hr, filtration obtains crystallization.To the crystallization that obtains, carry out lock out operation 2 times with same refining separation condition, thereby can obtain Stigmasterol 3.9g (Stigmasterol content 95.4%).
The filtrate of gained in the first step and the second step crystallization, after measuring the content of Stigmasterol wherein, can mix back recrystallize (being mother liquid recycle), obtain Stigmasterol 14.2g with the filter cake (Stigmasterol content is close) in the following batch of crystallization that obtains that feeds intake, its content reaches 95.4%, and yield reaches 64.0%.
The lower filtrate of Stigmasterol content that produces in the reaction, it can directly reclaim sterol and solvent in the time of-10 ℃, and solvent can reuse, and Sitosterol can be used for fodder additives, cosmetic industry etc.
Claims (8)
1, from plant sterol, extracts the method for Stigmasterol, it is characterized in that reactions steps is as follows: the first step, solubilizing agent dehydrated alcohol, n-propyl alcohol or propyl carbinol in plant sterol, rising temperature for dissolving, slow then decrease temperature crystalline, filter, the crystallisate of gained repeats above-mentioned enrichment step 0～1 time, carries out centrifugation, vacuum-drying afterwards; Second step, bonus point exsolution agent in the plant sterol enriched material that obtains toward the first step, rising temperature for dissolving, slow decrease temperature crystalline then, filtration, the crystallisate of gained repeats above-mentioned separating step 1～3 time.
2, the method for extracting Stigmasterol from plant sterol according to claim 1 is characterized in that described separation solvent is a kind of or wantonly two kinds of combinations in ethyl acetate, acetone, butanone, normal hexane, normal heptane, Virahol, isopropylcarbinol, the pimelinketone.
3, the method for from plant sterol, extracting Stigmasterol according to claim 2, it is characterized in that described plant sterol enriched material is 1: 5～12 with the mass volume ratio that separates solvent (g/ml), solvent temperature is 60～85 ℃, Tc is controlled at 25～45 ℃, and the insulation rearing crystal time is 10～16 hours.
4, the method for from plant sterol, extracting Stigmasterol according to claim 3, it is characterized in that described plant sterol enriched material be preferably 1: 6 with the mass volume ratio that separates solvent～10.
5, the method for from plant sterol, extracting Stigmasterol according to claim 1, it is characterized in that the plant sterol in the described the first step and the mass volume ratio (g/ml) of solvent are 1: 5～10, solvent temperature is 60～110 ℃, Tc is controlled at 15～35 ℃, the insulation rearing crystal time is 10～16 hours, vacuum tightness is-0.08～-0.09Mpa, drying temperature is 40～60 ℃.
6, the method for from plant sterol, extracting Stigmasterol according to claim 5, it is characterized in that the mass volume ratio of described plant sterol and solvent is preferably 1: 6～8.
7, the method for from plant sterol, extracting Stigmasterol according to claim 1, the filtrate that it is characterized in that gained in the described the first step and the intermediate steps in second step, after measuring the content of Stigmasterol wherein, can mix recrystallize afterwards by the filter cake close with the Stigmasterol content that the reaction that feeds intake next time obtains.
8, the method for extracting Stigmasterol from plant sterol according to claim 1 obtains the lower filtrate of Stigmasterol content and directly handles through low temperature or distillation in it is characterized in that reacting, at-8～-12 ℃ of other sterol and solvents that reclaim down wherein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101087042A CN1295244C (en) | 2003-11-15 | 2003-11-15 | Method for extracting stigmasterol from plant sterol |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101087042A CN1295244C (en) | 2003-11-15 | 2003-11-15 | Method for extracting stigmasterol from plant sterol |
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| CN1616479A true CN1616479A (en) | 2005-05-18 |
| CN1295244C CN1295244C (en) | 2007-01-17 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250182A (en) * | 2011-05-17 | 2011-11-23 | 李雪松 | Stigmaster-8(14)22,-diene-7alpha-methoxy-3beta-ol in cucumber roots and use thereof |
| 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 |
| CN108690113A (en) * | 2018-07-04 | 2018-10-23 | 江南大学 | A kind of method that ultrasonic wave added fractional crystallization prepares high-purity stigmasterol |
| CN108707176A (en) * | 2018-03-15 | 2018-10-26 | 武汉藤欣生物工程有限公司 | A kind of preparation method of high-purity stigmasterol monomer |
| CN108796023A (en) * | 2018-07-04 | 2018-11-13 | 江南大学 | A kind of preparation method of high-purity vegetable sterol monomeric ester |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5233699A (en) * | 1975-09-05 | 1977-03-14 | Tama Seikagaku Kk | Separation and purification of stigmasterol and brassicasterol from ph ytosterol |
-
2003
- 2003-11-15 CN CNB2003101087042A patent/CN1295244C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102250182A (en) * | 2011-05-17 | 2011-11-23 | 李雪松 | Stigmaster-8(14)22,-diene-7alpha-methoxy-3beta-ol in cucumber roots and use thereof |
| CN102250182B (en) * | 2011-05-17 | 2012-11-07 | 李雪松 | Stigmaster-8(14)22,-diene-7alpha-methoxy-3beta-ol in cucumber roots and use thereof |
| 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 |
| CN107722099B (en) * | 2017-11-21 | 2019-08-09 | 西安海斯夫生物科技有限公司 | A method of high-purity stigmasterol is prepared from phytosterols oletate |
| CN108707176A (en) * | 2018-03-15 | 2018-10-26 | 武汉藤欣生物工程有限公司 | A kind of preparation method of high-purity stigmasterol monomer |
| CN108690113A (en) * | 2018-07-04 | 2018-10-23 | 江南大学 | A kind of method that ultrasonic wave added fractional crystallization prepares high-purity stigmasterol |
| CN108796023A (en) * | 2018-07-04 | 2018-11-13 | 江南大学 | A kind of preparation method of high-purity vegetable sterol monomeric ester |
| 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 |
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| CN1295244C (en) | 2007-01-17 |
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