CN104447264A - Method for extracting and separating lupulone from lupulus - Google Patents
Method for extracting and separating lupulone from lupulus Download PDFInfo
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- CN104447264A CN104447264A CN201410650378.6A CN201410650378A CN104447264A CN 104447264 A CN104447264 A CN 104447264A CN 201410650378 A CN201410650378 A CN 201410650378A CN 104447264 A CN104447264 A CN 104447264A
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- lupulone
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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
- 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
- C07C45/80—Separation; Purification; Stabilisation; Use of additives by liquid-liquid treatment
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Abstract
The invention relates to a method for extracting and separating lupulone from lupulus. The method comprises the following specific steps: filling the compressed lupulus into a subcritical ultrasonic extractor, introducing an R134a mixed solvent into the extractor, dissolving the active ingredients of the extracted material in the R134a mixed solvent in a liquid state or a subcritical state, and pumping the filtrate into a separator; regulating the temperature and pressure so that R134a in the R134a mixed solvent is converted from liquid state into gas state, separating the R134a from the extracting solution, concentrating the methanol-containing extracting solution by virtue of a concentration evaporator so as to obtain the lupulus extract, and entering a crystallization section; adding a certain amount of lupulus extract into a reaction kettle, adding water, stirring, standing at room temperature, performing suction filtration, and collecting the insoluble substance; adding water to the insoluble substance, stirring, standing at room temperature, and performing suction filtration; and stirring and performing suction filtration, collecting the insoluble substance, thereby obtaining the crude lupulone. According to the method disclosed by the invention, a subcritical ultrasonic extraction technology is utilized, the R134a mixed solvent is taken as an extraction solvent, and the solvent can return to a high-purity state without being subjected to special treatment in production.
Description
Technical field
The present invention relates to lupulone separation field, particularly relate to a kind of method of extraction and isolation lupulone from hops.
Background technology
The female inflorescence that hops (Humulus lupulus L.) is Cannabaceae Humulus per nnial herb hops.There is cultivation on the ground such as China northeast, East China and Shandong, Shaanxi, Gansu.Its principle active component of hops is lupulone and humulone.In hops, lupulone has stronger female hormone, and its effect is mainly used in treatment women through closing and dysmenorrhoea, also can be used for suppressing the male sex to indulge in sensual pleasures.
From hops, the prior art of extraction and isolation lupulone is for getting hops constrictor 95% methyl alcohol (or ethanol) 50 DEG C of refluxing extraction 2h, coarse filtration, residue 95% methyl alcohol (or ethanol) extracts 2h, coarse filtration, residue uses 95% methyl alcohol (or ethanol) to extract 2h again, coarse filtration liquid merges, then fine filtering.Filtrate reduced in volume is to medicinal extract shape (also known as hop extract).Or use supercritical CO
2method is extracted and is obtained hop extract.Hop extract NaCl solution is dissolved, and filtrate petroleum ether extraction is also concentrated into paste.By water dissolution, be adjusted to different flat pH with NaOH, removing impurity, then be adjusted to certain pH with acid lupulone is separated out, then through recrystallization acquisition lupulone fine work.
But extracting method of the prior art, 95% and above methyl alcohol (or ethanol) must be used during extract by solvents, otherwise the separation of lupulone is had a strong impact on because extracting solution water-soluble impurity, therefore rectifying tower must be utilized aborning to carry out the purification of methanol concentration, like this because the loss of methyl alcohol causes the increase of production cost.For keeping higher extraction yield, Extracting temperature must remain on 80-85 DEG C, otherwise extraction yield will reduce greatly, the destruction of easily causing product because temperature is higher.Because of the restriction of extractor operation, it is meticulous that raw material is not easily pulverized, otherwise extracting solution flows out difficulty, can not pulverize so too carefully cause extraction yield to reduce because of raw material.Supercritical CO
2method is extracted because needing high pressure to cause device fabrication requirement strict, extracts volume little, has had a strong impact on large-scale production.During separation and purification, acid-alkali accommodation is wayward, and often cause removal of impurities not thorough, crystallization purity is not high.
In view of above-mentioned defect, creator of the present invention obtains this creation finally through research and practice.
Summary of the invention
The object of the present invention is to provide a kind of method of extraction and isolation lupulone from hops, in order to overcome above-mentioned technological deficiency.
For achieving the above object, the invention provides a kind of method of extraction and isolation lupulone from hops, this detailed process is:
Step a, hops constrictor is loaded in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, and filtrate pumps in separator;
Step b, regulates temperature and pressure to make R134a in R134a mixed solvent be gaseous state by liquid conversion, separates with extracting solution, and the extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section;
Step c, gets a certain amount of hop extract and is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, stirs 30min, left at room temperature 6h, suction filtration, collects insolubles;
Steps d, by insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 45 DEG C ~ 50 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stirs 30min, left at room temperature 6h, suction filtration;
Step e, filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain lupulone crude product; With normal hexane, recrystallization is carried out to lupulone crude product and obtain white pin state lupulone fine work.
In above-mentioned steps c, the mixture of hop extract and water, at 45 DEG C ~ 50 DEG C temperature, stirs with 10%NaOH adjust pH to 8.5 ~ 9.0 time.
In above-mentioned steps b, steam the de-solvent obtained, R134a, methyl alcohol reclaim through condenser system and turn back to extraction plant recycle.
Beneficial effect of the present invention is compared with prior art: 1, the present invention utilizes subcritical ultrasound assisted extraction technique, adopt R134a mixed solvent as Extraction solvent, in production, solvent does not need special processing can recover high purity state, 95% and above methyl alcohol (or ethanol) must be used when solving extract by solvents, otherwise have a strong impact on the problem of the separation of lupulone more because extracting solution water-soluble impurity.
2, the present invention utilizes subcritical ultrasound assisted extraction technique, and adopt R134a mixed solvent as Extraction solvent, Extracting temperature is only room temperature, and solve as keeping higher extraction yield, Extracting temperature must remain on 80-85 DEG C, otherwise the problem that extraction yield will reduce greatly.
3, the present invention utilizes subcritical ultrasound assisted extraction technique, and adopt R134a mixed solvent as Extraction solvent, raw material pulverizing is meticulous also can not affect production, and solve the restriction because of extractor operation, it is meticulous that raw material is not easily pulverized, otherwise extracting solution flows out the problem of difficulty.
4, the present invention utilizes subcritical ultrasound assisted extraction technique, and subcritical ultrasonic extraction device pressure is far below supercritical extraction equipment, and volume of equipment increases greatly, large-scale production is become a reality, solves supercritical CO
2method is extracted because needing high pressure to cause device fabrication requirement strict, extracts volume little, has had a strong impact on the problem of large-scale production.
5, the present invention utilizes subcritical ultrasound assisted extraction technique, adopt R134a mixed solvent as Extraction solvent, because not using 95% and above methyl alcohol (or ethanol), hop extract water-soluble impurity is reduced, make acid-alkali accommodation be easy to control, crystallization is comparatively thorough, and when solving separation and purification, acid-alkali accommodation is wayward, often cause removal of impurities not thorough, the problem that crystallization purity is not high.
Embodiment
Below, to above-mentioned being described in more detail with other technical characteristic and advantage of the present invention.
The process of the present invention's extraction and isolation lupulone from hops is:
Step a, hops constrictor is loaded in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, and filtrate pumps in separator.
Step b, regulates temperature and pressure to make R134a in R134a mixed solvent be gaseous state by liquid conversion, separates with extracting solution, and the extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section.
Steam the de-solvent (R134a, methyl alcohol) obtained and turn back to extraction plant recycle through condenser system recovery.
Step c, gets a certain amount of hop extract and is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at 45 DEG C ~ 50 DEG C temperature, with 10%NaOH adjust pH to 8.5 ~ 9.0, stirs 30min, left at room temperature 6h, suction filtration, collects insolubles.
Steps d, by insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 45 DEG C ~ 50 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stirs 30min, left at room temperature 6h, suction filtration.
Step e, filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain lupulone crude product; With normal hexane, recrystallization is carried out to lupulone crude product and obtain white pin state lupulone fine work.
Below by embodiment, aforesaid method is described.
Embodiment one:
Getting hops constrictor 50kg loads in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, filtrate pumps in separator, R134a is made in R134a mixed solvent to be gaseous state by liquid conversion by regulating temperature and pressure, separate with extracting solution, extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section.
Steam the de-solvent (R134a, ethanol) obtained and turn back to extraction plant recycle through condenser system recovery.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at 45 DEG C of temperature, with 10%NaOH adjust pH to 8.5 ~ 9.0, stirs 30min, left at room temperature 6h, suction filtration, collect insolubles.By insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 45 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stir 30min, left at room temperature 6h, suction filtration.Filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain 1.42kg lupulone crude product.With normal hexane, recrystallization is carried out to lupulone crude product and obtain 1.06kg white pin state lupulone fine work.
Embodiment two:
Getting hops constrictor 50kg loads in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, filtrate pumps in separator, R134a is made in R134a mixed solvent to be gaseous state by liquid conversion by regulating temperature and pressure, separate with extracting solution, extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section.
Steam the de-solvent (R134a, ethanol) obtained and turn back to extraction plant recycle through condenser system recovery.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at 50 DEG C of temperature, with 10%NaOH adjust pH to 8.5 ~ 9.0, stirs 30min, left at room temperature 6h, suction filtration, collect insolubles.By insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 50 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stir 30min, left at room temperature 6h, suction filtration.Filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain 1.46kg lupulone crude product.With normal hexane, recrystallization is carried out to lupulone crude product and obtain 1.09kg white pin state lupulone fine work.
Embodiment three:
Getting hops constrictor 100kg loads in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, filtrate pumps in separator, R134a is made in R134a mixed solvent to be gaseous state by liquid conversion by regulating temperature and pressure, separate with extracting solution, extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section.Steam the de-solvent (R134a, ethanol) obtained and turn back to extraction plant recycle through condenser system recovery.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at 45 DEG C of temperature, with 10%NaOH adjust pH to 8.5 ~ 9.0, stirs 30min, left at room temperature 6h, suction filtration, collect insolubles.By insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 50 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stir 30min, left at room temperature 6h, suction filtration.Filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain 2.83kg lupulone crude product.With normal hexane, recrystallization is carried out to lupulone crude product and obtain 2.08kg white pin state lupulone fine work.
The foregoing is only preferred embodiment of the present invention, is only illustrative for invention, and nonrestrictive.Those skilled in the art is understood, and can carry out many changes in the spirit and scope that invention claim limits to it, amendment, even equivalence, but all will fall within the scope of protection of the present invention.
Claims (3)
1. the method for extraction and isolation lupulone from hops, it is characterized in that, this detailed process is:
Step a, hops constrictor is loaded in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed in extractor, the effective constituent be extracted in material is dissolved in the R134a mixed solvent of liquid state or subcritical state, the extraction liquid of gained filters through filter, and filtrate pumps in separator;
Step b, regulates temperature and pressure to make R134a in R134a mixed solvent be gaseous state by liquid conversion, separates with extracting solution, and the extracting solution containing methyl alcohol concentrates to obtain hop extract through concentration evaporator, enters crystallization workshop section;
Step c, gets a certain amount of hop extract and is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, stirs 30min, left at room temperature 6h, suction filtration, collects insolubles;
Steps d, by insolubles by insolubles: water=1: the weight ratio of 10 adds water, at 45 DEG C ~ 50 DEG C, with 10%NaOH adjust pH 12.5 ~ 13.0, stirs 30min, left at room temperature 6h, suction filtration;
Step e, filtrate, with dilute phosphoric acid acid adjust pH to 8.5, is stirred 30min, suction filtration, is collected insolubles, obtain lupulone crude product; With normal hexane, recrystallization is carried out to lupulone crude product and obtain white pin state lupulone fine work.
2. the method for extraction and isolation lupulone from hops according to claim 1, is characterized in that, in above-mentioned steps c, the mixture of hop extract and water, at 45 DEG C ~ 50 DEG C temperature, stirs with 10%NaOH adjust pH to 8.5 ~ 9.0 time.
3. the method for extraction and isolation lupulone from hops according to claim 2, is characterized in that, in above-mentioned steps b, steam the de-solvent obtained, R134a, methyl alcohol reclaim through condenser system and turns back to extraction plant recycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410650378.6A CN104447264B (en) | 2014-11-08 | 2014-11-08 | A kind of method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410650378.6A CN104447264B (en) | 2014-11-08 | 2014-11-08 | A kind of method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) |
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| CN104447264A true CN104447264A (en) | 2015-03-25 |
| CN104447264B CN104447264B (en) | 2016-08-17 |
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| CN201410650378.6A Expired - Fee Related CN104447264B (en) | 2014-11-08 | 2014-11-08 | A kind of method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746284A (en) * | 2019-11-18 | 2020-02-04 | 新疆大学 | Extraction and separation method of β -acid homolog in hops |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3965188A (en) * | 1972-01-10 | 1976-06-22 | Miller Brewing Company | Hop extract process and product |
| CN101045678A (en) * | 2006-03-28 | 2007-10-03 | 新疆大学 | Method for producing hexahydrolupulicone |
| CN101376625A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for separating alpha and beta acid from hop extract |
| CN101905091A (en) * | 2010-07-12 | 2010-12-08 | 新疆大学 | Equipment and method for extracting biologically active ingredients from subcritical fluid |
-
2014
- 2014-11-08 CN CN201410650378.6A patent/CN104447264B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3965188A (en) * | 1972-01-10 | 1976-06-22 | Miller Brewing Company | Hop extract process and product |
| CN101045678A (en) * | 2006-03-28 | 2007-10-03 | 新疆大学 | Method for producing hexahydrolupulicone |
| CN101376625A (en) * | 2008-10-07 | 2009-03-04 | 浙江大学 | Method for separating alpha and beta acid from hop extract |
| CN101905091A (en) * | 2010-07-12 | 2010-12-08 | 新疆大学 | Equipment and method for extracting biologically active ingredients from subcritical fluid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746284A (en) * | 2019-11-18 | 2020-02-04 | 新疆大学 | Extraction and separation method of β -acid homolog in hops |
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