CN105693488A - Clean production process for high purity gossypol - Google Patents
Clean production process for high purity gossypol Download PDFInfo
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- CN105693488A CN105693488A CN201610157566.4A CN201610157566A CN105693488A CN 105693488 A CN105693488 A CN 105693488A CN 201610157566 A CN201610157566 A CN 201610157566A CN 105693488 A CN105693488 A CN 105693488A
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- gossypol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
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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
- C11B13/00—Recovery of fats, fatty oils or fatty acids from waste materials
- C11B13/02—Recovery of fats, fatty oils or fatty acids from waste materials from soap stock
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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
Abstract
The invention belongs to the technical field of oil crop processing, particularly relates to a clean production process for high-purity gossypol, and provides a simple, cheap and efficient clean production process for obtaining high purity free gossypol in order to realize large-scale industrial preparation of free gossypol. Compared with the conventional process, the present process has the advantages that high purity gossypol having a purity of over 98 percent is directly obtained through a simulated moving bed chromatographic continuous separation technology on the premise of not transforming gossypol into gossypol acetate with acetic acid and transforming the gossypol acetate into the gossypol, so that waste water, waste residues and waste solvents containing acetic acid associated with processing of acid oil from cottonseed oil dregs and preparation of the gossypol are removed from the source, so that green and clean processing and utilization of the cottonseed oil dregs are realized, and a major source of pollution in the cottonseed oil processing industry is eliminated; meanwhile, the quality and yield of the gossypol and co-generated cottonseed oil fatty acid are enhanced greatly, the added value of the cottonseed oil dregs is increased significantly, and the process has a wide application prospect in the cottonseed processing industry.
Description
Technical field
The invention belongs to the processing technique field of oil crop, be belonging to the process for cleanly preparing of a kind of high-purity gossypol specifically。
Background technology
Semen Gossypii is the seed of Cotton Gossypii, can be used for extracting oil, sows, as animal feed and process other products。Containing colory Semen Gossypii oils and fats and albumen in Semen Gossypii, and the gossypol as medicinal raw material。Semen Gossypii is except a part is for except seed, and all the other, all by traditional cottonseed processing technique, namely produce oils and fats by the method such as screw press, prepressing extraction, and its product is: Oleum Gossypii semen, cottonseed cake (cottonseed meal), cotton seed hulls, soap stock。
Gossypol is Polyhydroxy phenol, is the coloured noxious substance of distinctive one in Semen Gossypii, accounts for the 0.7～4.8% of Semen Gossypii, can cause that human body redness is hemorrhage, inappetence, off one's dot and affect male fertility。Additionally, gossypol also has use value widely, as antioxidant, anti-polymerizer, stabilizer etc. can be done on chemical industry；Agricultural can be done insecticide；For the analysis etc. of wastewater treatment and metallic element in environmental science, medicine is used as anticancer, antiviral drugs。
Edible causing poisoning containing the hair cotton oil that gossypol is more, patient skin has a violent burning sensation, and with dizzy, asthma, the symptom such as nervous and unable。Therefore, the hair cotton oil without special handling is inedible, it is necessary to first carries out alkali refining, removes gossypol therein。Can being converted into edible Oleum Gossypii semen after crude cotton seed oil carries out alkali refining, decolouring, deodorize process, wherein the Main Function of alkali refining removes distinctive gossypol in Oleum Gossypii semen exactly。Soap stock is the by-product that crude cotton seed oil is formed in alkali refining process, and the gossypol contained in crude cotton seed oil has focused largely in the soap stock after alkali refining。
In the existing technique preparing fatty acid with cotton oil distillation residues for raw material, soap stock is carried out direct acidifying, hydrolysis by multiplex concentrated sulphuric acid, make in cotton oil distillation residues that contained gossypol is substantially all oxidized to be destroyed, thus form a large amount of waste water and the very deep plant asphalt of color and luster, constitute a big polluter of vegetable oil processing industry, so far there are no the relevant report with cotton oil distillation residues for raw material separation and Extraction gossypol。
At present, gossypol extraction aspect mainly has: alkali-soluble acid analysis method, dianiline gossypol method, method of acetic acid, ion exchange etc., and methanol phase two-phase solvent abstraction technique processed in the processing technique of Semen Gossypii is used, it is possible to extract gossypol therein。These methods respectively have pluses and minuses。The method that simulated moving bed chromatography separates is adopted to extract the relevant report of gossypol there are no with cotton oil distillation residues for raw material so far。
Summary of the invention
The invention process for cleanly preparing of a kind of high-purity gossypol, relates to a kind of eco-friendly, carries out in the way of the coupling simulated moving bed chromatographic isolation of solvent extraction, relatively inexpensive, high efficiency, cotton oil distillation residues processing and utilization new technology。Comparatively uniqueness is, it relates to a kind of improved technique, this technique is with cotton oil distillation residues, rather than crude cotton seed oil, cottonseed meal or other cottonseed processing products, for raw material, adopt phosphoric acid, rather than concentrated sulphuric acid, neutralization, acidifying cotton oil distillation residues, with fatty acid contained in the method separation and Extraction gossypol of the coupling simulated moving bed chromatographic isolation of solvent extraction and cotton oil distillation residues, the free gossypol of co-producing high-purity and fatty acid, and no longer produce soap stock acidified waste water, also not in use by acetic acid, gossypol is converted into gossypol acetate。It is operated according to this patent, compared with traditional method before this, can under the premise not reducing cotton oil fatty acid quality, the products such as the acquisition free gossypol of high-quality high yield, production cost is made to be greatly lowered, from source, eradicated cotton oil distillation residues processing acidification oil simultaneously, prepare the waste water of gossypol institute association, waste residue and containing acetic acid solvent slop, the green achieving cotton oil distillation residues processing and utilization cleans, eliminate a big polluter of cotton oil processing industry, also substantially increase the quality of the cotton oil fatty acid of gossypol and coproduction simultaneously and go out rate, the added value making cotton oil distillation residues is substantially improved, this improvement for the comprehensive utilization of this large oil crop resource with a very important position in national economy of Semen Gossypii it is critical that。
One of most important purpose of the present invention, it is simply that will obtain the medicinal raw material free gossypol of high-purity high-quality, reduces production cost, it is ensured that product quality。
As a result along band, another object of the present invention, be to realize the cleaning of separation and Extraction fatty acid in cotton oil distillation residues, environmental friendlinessization produces, and solves the problem of environmental pollution of Oleum Gossypii semen processing industry from source。
Specifically, first, it has been found that use phosphoric acid cotton oil distillation residues, the mixture being subsequently adding cotton oil fatty acid obtained after extractant is thoroughly hydrolyzed and gossypol can be separated into cotton oil fatty acid and two kinds of components of gossypol on simulation moving bed。Thus establish the basis of the gossypol preparation technology of the extractant extracting of the cotton oil distillation residues after acidification hydrolization, simulation moving bed separation。
Secondly, it has been found that simulation moving bed separates the gossypol obtained, and can directly obtain the free gossypol of high purity more than 98% in acetone after recrystallization。Thus establish the basis of the simulation moving bed separation product free gossypol preparation technology of direct recrystallization in acetone。
It was found that gossypol and cotton oil fatty acid can be extracted by the technique being made up of the following step and obtain:
1) with phosphoric acid, cotton oil distillation residues is neutralized, by the pH regulator of cotton oil distillation residues to pH≤7.0；
2) add extractant, under the premise having extractant to exist, cotton oil distillation residues is thoroughly hydrolyzed, then carries out liquid-liquid separation, obtain organic facies and aqueous phase；
3) with extractant, aqueous phase being extracted, gained extract merges with organic facies, then concentration, recovery extractant, obtains extract, reclaims the extractant obtained and recycles。Regulating the pH value of raffinate alkali to neutral, then concentration, recovery extractant, reclaim the extractant obtained and recycle, enriched product is sold as liquid fertilizer；
4) extract simulation moving bed carries out chromatographic isolation, obtains eluent (free fatty containing in extract) and scrub raffinate (gossypol containing in extract)。Cottonseed oil fatty acid is obtained, it is possible to sell, it is also possible to obtain Palmic acid, oleic acid and plant asphalt through negative pressure rectification, sell as product after eluent elimination eluant。Eluant reclaims, and recycles；
5), after scrub raffinate elimination eluant, coarse cotton phenol is obtained。Eluant reclaims, and recycles；
6) coarse cotton phenol recrystallization in acetone, then filtration, vacuum drying, obtain content and reach the high-purity gossypol of more than 98%。Disposing mother liquor, recycles。
Extractant therein can be the mixture of one or more compositions in benzene,toluene,xylene, hexane, hexamethylene, dichloromethane, chloroform, isopropanol, n-butyl alcohol, the tert-butyl alcohol, tert-pentyl alcohol, butanone, ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), ethyl acetate or other any organic solvents not miscible with water。The addition of extractant is 0.1～10 times of cotton oil distillation residues weight。Hydrolysis can be made catalyst with acid and carry out, it is also possible to carry out with phospholipase or lipase as catalyst。When with acid do catalyst be hydrolyzed time, hydrolysis in pH≤2,80～180 DEG C, it is preferred to 100～148 DEG C, 0.1～1.0MPa, when carry out 0.5～10 hour。When being hydrolyzed with phospholipase or lipase as catalyst, hydrolysis carries out 0.5～10 hour under the optimum pH of enzyme used, optimum temperature, normal pressure。Liquid-liquid separation can be settlement separate or centrifugation, carries out at normal pressure 0-50 DEG C。Extracting at 0～78 DEG C, it is preferred to 4～38 DEG C, 0.01～1.0MPa, when, carries out 1-10 time, extracts 80%～120% (v/v) that amount is aqueous phase amount of required extractant every time, and extraction time is 0.15～12hr time-1。Extractant be recovered in 10～180 DEG C, it is preferred to 30～150 DEG C, 0.0001～1.0MPa, when, carries out。Regulating the alkali used by raffinate pH can be ammonia, it is also possible to be potassium carbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium carbonate, quick lime, Calx or any material being adjusted to pH=6.5～7.0。The eluant that separation system of simulated moving bed chromatography uses can be dichloromethane, chloroform, hexane, hexamethylene, diisopropyl ether, ether, methyl tertiary butyl ether(MTBE), acetone, butanone, methanol, ethanol, water, toluene and the mixed solvent being made up of in any proportion two or more in them。The adsorbent used can be activated carbon, silica gel, microcrystalline Cellulose, activated alumina, polyacrylamide, ion exchange resin or other any adsorbing materials that can be separated with free fatty by gossypol in extract with particular eluent cooperation。It is 0～100 DEG C that simulated moving bed chromatography separates in temperature, it is preferred to 10～60 DEG C, carry out when pressure is 0.1～3.5MPa。Eluant be recovered in 10～180 DEG C, it is preferred to 30～150 DEG C, 0.0001～1.0MPa, when, carries out。Recrystallization means the process that gossypol saturated solution cooling relief gossypol in heat (50 DEG C) acetone precipitates out, and at 0～14 DEG C, 0.01～1.0MPa, when carries out。Filtering and carry out under 0～14 DEG C of normal pressure, vacuum drying, at 30～60 DEG C, carries out 6-40 hour when 0.0001～0.01MPa。Mother solution be recovered in 30～50 DEG C, carry out when 0.0001～0.01MPa。
After the whole optimization of all important parameters mentioned in the present invention, the yield of gossypol is up to 3-5%, and the purity of gained gossypol product is up to more than 98%, and the yield of fatty acid product is all unaffected with purity。
Detailed description of the invention
Example below will be explained in detail the operational approach of the present invention, but cannot function as limitation of the invention。
Example one
The phosphoric acid that cotton oil distillation residues concentration is 85% that 1000g water content is 50% is adjusted pH to 6.5, is subsequently adding 1g phospholipase, 500ml ether, at 34.6 DEG C, be stirred at reflux hydrolysis 3h。Stratification 3h at 4 DEG C put by reactant mixture, then separatory at 4 DEG C, collects upper organic phase。Lower floor's aqueous phase repeats to extract 2 times (each 500ml) with the ether that temperature is 4 DEG C again, gained ether phase is merged with organic facies and obtains extracting solution。Extracting solution is put concentration in 50 DEG C of water-baths on distilling apparatus, reclaims ether, obtain extract。The lower aqueous layer of raffinate removes Distillation recovery ether, obtains 480ml and distills residual night, sells as liquid fertilizer。Reclaim the ether circulating and recovering obtained。
Then mixture is put with silica gel for adsorbent, the separation system of simulated moving bed chromatography constituted with hexane: ethanol=6:1 (v/v) for eluant separates, respectively obtain only containing the component of cotton oil fatty acid and only component containing gossypol。Only put on Rotary Evaporators containing the component of cotton oil fatty acid, under 60,0.0001MPa, reclaim elimination eluant, obtain cotton oil fatty acid 480g。Only the component containing gossypol is put on Rotary Evaporators, reclaims elimination eluant, obtain coarse cotton phenol 55g under 60,0.0001MPa。Reclaim the eluant circulation reuse obtained。
Being dissolved in acetone by coarse cotton phenol, be configured to the gossypol at 50 DEG C-acetone saturated solution, then put and stand overnight in 4 DEG C of refrigerators, then filter, be placed in vacuum drying oven 60 DEG C by gained filter cake, under 0.0001MPa, dry 14h, obtains 50.1g yellow crystals。
Checking through efficient liquid phase, yellow crystals is gossypol product, and purity has reached 98%。
Recycling Mother Solution reuse。
Cotton oil fatty acid, through rectification under vacuum, obtains Palmic acid 150g, oleic acid 300g and plant asphalt 30g。Checking through gas chromatogram, the purity of Palmic acid and oleic acid has respectively reached 98% and 99%。
Example two
The phosphoric acid that cotton oil distillation residues concentration is 85% that 1000g water content is 45% is adjusted pH to 2, is subsequently adding 500ml butanone, is warming up to reflux temperature, be stirred at reflux hydrolysis 5h。Reactant mixture puts left at room temperature layering 3h, then separatory at 24 DEG C, collects upper organic phase。Lower floor's aqueous phase repeats to extract 2 times (each 500ml) with the butanone that temperature is room temperature again, gained butanone phase is merged with organic facies and obtains extracting solution。Extracting solution is put rotation steam on instrument at 60 DEG C, concentrate under 0.0001MPa, reclaim butanone, obtain extract。The lower aqueous layer potassium carbonate of raffinate is neutralized to neutrality, then removes Distillation recovery butanone, obtains 300ml and distills residual night, sells as liquid fertilizer。Reclaim the butanone circulating and recovering obtained。
Then mixture is put with microcrystalline Cellulose for adsorbent, the separation system of simulated moving bed chromatography constituted with saturated butanone aqueous solution for eluant separates, respectively obtain only containing the component of cotton oil fatty acid and only component containing gossypol。Only put on Rotary Evaporators containing the component of cotton oil fatty acid, under 60,0.0001MPa, reclaim elimination eluant, obtain cotton oil fatty acid 420g。Only the component containing gossypol is put on Rotary Evaporators, reclaims elimination eluant, obtain coarse cotton phenol 43.8g under 60,0.0001MPa。Reclaim the eluant circulation reuse obtained。
Being dissolved in acetone by coarse cotton phenol, be configured to the gossypol at 50 DEG C-acetone saturated solution, then put and stand overnight in 4 DEG C of refrigerators, then filter, be placed in vacuum drying oven 60 DEG C by gained filter cake, under 0.0001MPa, dry 24h, obtains 40.1g yellow crystals。
Checking through efficient liquid phase, yellow crystals is gossypol product, and purity has reached 98%。
Recycling Mother Solution reuse。
Claims (10)
1. the process for cleanly preparing of a high-purity gossypol。This technique is made up of the following step:
1) with phosphoric acid, cotton oil distillation residues is neutralized, by the pH regulator of cotton oil distillation residues to pH≤7.0；
2) add extractant, under the premise having extractant to exist, cotton oil distillation residues is thoroughly hydrolyzed, then carries out liquid-liquid separation, obtain organic facies and aqueous phase；
3) with extractant, aqueous phase being extracted, gained extract merges with organic facies, then concentration, recovery extractant, obtains extract, reclaims the extractant obtained and recycles。Regulating the pH value of raffinate alkali to neutral, then concentration, recovery extractant, reclaim the extractant obtained and recycle, enriched product is sold as liquid fertilizer；
4) extract simulation moving bed carries out chromatographic isolation, obtains eluent (free fatty containing in extract) and scrub raffinate (gossypol containing in extract)。Cottonseed oil fatty acid is obtained, it is possible to sell, it is also possible to obtain Palmic acid, oleic acid and plant asphalt through negative pressure rectification, sell as product after eluent elimination eluant。Eluant reclaims, and recycles；
5), after scrub raffinate elimination eluant, coarse cotton phenol is obtained。Eluant reclaims, and recycles；
6) coarse cotton phenol recrystallization in acetone, then filtration, vacuum drying, obtain content and reach the high-purity gossypol of more than 98%。Disposing mother liquor, recycles。
2. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that described extractant can be the mixture of one or more compositions in benzene,toluene,xylene, hexane, hexamethylene, dichloromethane, chloroform, isopropanol, n-butyl alcohol, the tert-butyl alcohol, tert-pentyl alcohol, butanone, ether, diisopropyl ether, methyl tertiary butyl ether(MTBE), ethyl acetate or other any organic solvents not miscible with water。The addition of extractant is 0.1～10 times of cotton oil distillation residues weight。
3. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that described hydrolysis can be made catalyst with acid and carry out, it is also possible to carry out with phospholipase or lipase as catalyst。When with acid do catalyst be hydrolyzed time, described hydrolysis in pH≤2,80～180 DEG C, it is preferred to 100～148 DEG C, 0.1～1.0MPa, when carry out 0.5～10 hour。When being hydrolyzed with phospholipase or lipase as catalyst, described hydrolysis carries out 0.5～10 hour under the optimum pH of enzyme used, optimum temperature, normal pressure。
4. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that described liquid-liquid separation can be settlement separate or centrifugation, at normal pressure, carries out at 0～50 DEG C。
5. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterized in that described extraction is at 0～78 DEG C, preferably 4～38 DEG C, 0.01～1.0MPa, when carry out 1-10 time, extracting 80%～120% (v/v) that amount is aqueous phase amount of required extractant, extraction time is 0.15～12hr time every time-1。Extractant be recovered in 10～180 DEG C, it is preferred to 30～150 DEG C, 0.0001～1.0MPa, when, carries out。
6. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterized in that the described alkali used by raffinate pH that regulates can be ammonia, it is also possible to be potassium carbonate, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium hydroxide, calcium carbonate, quick lime, Calx or any material being adjusted to pH=6.5～7.0。
7. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that the eluant that described separation system of simulated moving bed chromatography uses can be dichloromethane, chloroform, hexane, hexamethylene, diisopropyl ether, ether, methyl tertiary butyl ether(MTBE), acetone, butanone, methanol, ethanol, water, toluene and the mixed solvent being made up of in any proportion two or more in them。The adsorbent used can be activated carbon, silica gel, microcrystalline Cellulose, activated alumina, polyacrylamide, ion exchange resin or other any adsorbing materials that can be separated with free fatty by gossypol in extract with particular eluent cooperation。
8. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that it is 0～100 DEG C that simulated moving bed chromatography separates in temperature, it is preferred to 10～60 DEG C, carry out when pressure is 0.1～3.5MPa。Eluant be recovered in 10～180 DEG C, it is preferred to 30～150 DEG C, 0.0001～1.0MPa, when, carries out。
9. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterized in that described recrystallization means the process that gossypol saturated solution cooling relief gossypol in heat (50 DEG C) acetone precipitates out, at 0～14 DEG C, 0.01～1.0MPa, when, carries out。Filtering and carry out under 0～14 DEG C of normal pressure, vacuum drying, at 30～60 DEG C, carries out 6-40 hour when 0.0001～0.01MPa。
10. the process for cleanly preparing of high-purity gossypol as claimed in claim 1, it is characterised in that described mother solution be recovered in 30～50 DEG C, carry out when 0.0001～0.01MPa。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298641A (en) * | 2017-06-07 | 2017-10-27 | 新疆维吾尔自治区中药民族药研究所 | The preparation method of gossypol and the preparation method of gossypol acetate |
| CN108276263A (en) * | 2018-04-09 | 2018-07-13 | 中国科学院新疆理化技术研究所 | A method of preparing free gossypol by raw material of gossypol acetate |
| CN113214065A (en) * | 2020-02-04 | 2021-08-06 | 中国医学科学院药物研究所 | Gossypol crystal III type substance, preparation method, composition and application thereof |
| CN113214065B (en) * | 2020-02-04 | 2024-05-14 | 中国医学科学院药物研究所 | Gossypol crystal III substance, preparation method, composition and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112637A (en) * | 1990-11-05 | 1992-05-12 | The United States Of America As Represented By The Secretary Of Agriculture | Extraction of gossypol from cottonseed |
| CN102936534A (en) * | 2012-12-07 | 2013-02-20 | 江南大学 | Process for simultaneously extracting phosphatide, gossypol and pigments from cottonseed oil |
| CN102942992A (en) * | 2012-12-07 | 2013-02-27 | 江南大学 | Technique for simultaneously extracting lipid and gossypol from cotton seed |
| CN103725421A (en) * | 2013-09-25 | 2014-04-16 | 山东渤海实业股份有限公司 | Method for increasing utilization rate of cottonseed oil mixture refining by-products |
| CN104450204A (en) * | 2014-12-24 | 2015-03-25 | 江南大学 | Cleaner production process for synchronously extracting gossypol and fatty acid from cottonseed oil soap |
-
2016
- 2016-03-18 CN CN201610157566.4A patent/CN105693488A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112637A (en) * | 1990-11-05 | 1992-05-12 | The United States Of America As Represented By The Secretary Of Agriculture | Extraction of gossypol from cottonseed |
| CN102936534A (en) * | 2012-12-07 | 2013-02-20 | 江南大学 | Process for simultaneously extracting phosphatide, gossypol and pigments from cottonseed oil |
| CN102942992A (en) * | 2012-12-07 | 2013-02-27 | 江南大学 | Technique for simultaneously extracting lipid and gossypol from cotton seed |
| CN103725421A (en) * | 2013-09-25 | 2014-04-16 | 山东渤海实业股份有限公司 | Method for increasing utilization rate of cottonseed oil mixture refining by-products |
| CN104450204A (en) * | 2014-12-24 | 2015-03-25 | 江南大学 | Cleaner production process for synchronously extracting gossypol and fatty acid from cottonseed oil soap |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107298641A (en) * | 2017-06-07 | 2017-10-27 | 新疆维吾尔自治区中药民族药研究所 | The preparation method of gossypol and the preparation method of gossypol acetate |
| CN108276263A (en) * | 2018-04-09 | 2018-07-13 | 中国科学院新疆理化技术研究所 | A method of preparing free gossypol by raw material of gossypol acetate |
| CN108276263B (en) * | 2018-04-09 | 2021-03-09 | 中国科学院新疆理化技术研究所 | Method for preparing free gossypol by using gossypol acetate as raw material |
| CN113214065A (en) * | 2020-02-04 | 2021-08-06 | 中国医学科学院药物研究所 | Gossypol crystal III type substance, preparation method, composition and application thereof |
| CN113214065B (en) * | 2020-02-04 | 2024-05-14 | 中国医学科学院药物研究所 | Gossypol crystal III substance, preparation method, composition and application thereof |
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