CN104447264B - A kind of method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) - Google Patents
A kind of method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) Download PDFInfo
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- CN104447264B CN104447264B CN201410650378.6A CN201410650378A CN104447264B CN 104447264 B CN104447264 B CN 104447264B CN 201410650378 A CN201410650378 A CN 201410650378A CN 104447264 B CN104447264 B CN 104447264B
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- lupuli
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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 present invention relates to a kind of method extracted from Flos lupuli (Flos Humuli Lupuli) and separate .beta.-bitter acid, this detailed process is: loaded by Flos lupuli (Flos Humuli Lupuli) compressor in subcritical ultrasonic extractor, R134a mixed solvent is passed through in extractor, the effective ingredient being extracted in material is dissolved in the R134a mixed solvent of liquid or subcritical state, and filtrate pumps in separator；Regulation temperature and pressure makes R134a in R134a mixed solvent be converted into gaseous state by liquid, separates with extracting solution, and the concentrated vaporizer of extracting solution containing methanol is concentrated to give hop extract, enters crystallize workshop section；Take a certain amount of hop extract to be placed in reactor, add water, stirring, left at room temperature, sucking filtration, collect insoluble matter；Insoluble matter is added water, stirring, left at room temperature, sucking filtration；Stirring sucking filtration, collects insoluble matter, obtains .beta.-bitter acid crude product.The present invention utilizes subcritical ultrasound assisted extraction technique, uses R134a mixed solvent as Extraction solvent, and in production, solvent is not required to special handling and can recover high-purity state.
Description
Technical field
The present invention relates to .beta.-bitter acid separation field, particularly relate to a kind of method extracted from Flos lupuli (Flos Humuli Lupuli) and separate .beta.-bitter acid.
Background technology
Flos lupuli (Flos Humuli Lupuli) (Humulus lupulus L.) is the female inflorescence that Cannabaceae grass belongs to herbaceos perennial Flos lupuli (Flos Humuli Lupuli).
There is cultivation on the ground such as China northeast, East China and Shandong, Shaanxi, Gansu.Its principle active component of Flos lupuli (Flos Humuli Lupuli) be .beta.-bitter acid and
Oxadiazon.In Flos lupuli (Flos Humuli Lupuli) .beta.-bitter acid has stronger estrogen, and its effect is mainly used in treating women's amenorrhea and dysmenorrhea,
Also can be used for suppressing male to indulge in sensual pleasures.
The prior art separating .beta.-bitter acid is extracted for taking Flos lupuli (Flos Humuli Lupuli) compressor 95% methanol (or second from Flos lupuli (Flos Humuli Lupuli)
Alcohol) 50 DEG C of reflux, extract, 2h, coarse filtration, residue 95% methanol (or ethanol) extracts 2h, and coarse filtration, residue is again with 95%
Methanol (or ethanol) extracts 2h, and coarse filtration liquid merges, then fine filtering.Filtrate reduced in volume is to extractum shape (also known as hop extract).
Or use supercritical CO2Method is extracted and is obtained hop extract.Hop extract NaCl solution is dissolved, and filtrate extracts with petroleum ether
Take and be concentrated into paste.With water dissolution, it is adjusted to different flat pH with NaOH, removes impurity, then be adjusted to necessarily with acid
PH makes .beta.-bitter acid separate out, then obtains .beta.-bitter acid fine work through recrystallization.
But extracting method of the prior art, must use 95% and above methanol (or ethanol) during extract by solvents,
Otherwise have a strong impact on the separation of .beta.-bitter acid because extracting solution water-solubility impurity more, rectifying column must be utilized the most aborning
Carry out the purification of methanol concentration, so cause the increase of production cost because of the loss of methanol.For keeping higher extraction ratio,
Extracting temperature preferably must be held in 80-85 DEG C, and otherwise extraction ratio will be substantially reduced, and easily causes product owing to temperature is higher
Destroy.Because of the restriction of extraction pot operation, it is meticulous that raw material is difficult to pulverize, and otherwise extracting solution flows out difficulty, so because of raw material
Can not pulverize and the most carefully cause extraction ratio to reduce.Supercritical CO2Method is extracted because needing high pressure to cause device fabrication requirement strict,
Extraction volume is little, has had a strong impact on large-scale production.Time isolated and purified, acid-alkali accommodation is wayward, often results in remove impurity
Not thorough, crystallize purity is the highest.
In view of drawbacks described above, creator of the present invention obtains this creation finally through research and practice.
Summary of the invention
It is an object of the invention to provide a kind of method extracted from Flos lupuli (Flos Humuli Lupuli) and separate .beta.-bitter acid, in order to overcome above-mentioned skill
Art defect.
For achieving the above object, the present invention provides a kind of method extracted from Flos lupuli (Flos Humuli Lupuli) and separate .beta.-bitter acid, this concrete mistake
Cheng Wei:
Step a, loads Flos lupuli (Flos Humuli Lupuli) compressor in subcritical ultrasonic extractor, selects suitable temperature and pressure, will
R134a mixed solvent is passed through in extractor, and the effective ingredient being extracted in material is dissolved in liquid or subcritical state
In R134a mixed solvent, the extract of gained filters through filter, and filtrate pumps in separator；
Step b, regulation temperature and pressure makes R134a in R134a mixed solvent be converted into gaseous state by liquid, with extraction
Separately, the concentrated vaporizer of extracting solution containing methanol is concentrated to give hop extract to liquid, enters crystallize workshop section；
Step c, takes 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, sucking filtration, collects insoluble matter；
Step d, presses insoluble matter by insoluble matter: water=1: the weight ratio of 10 adds water, at 45 DEG C～50 DEG C, uses 10%NaOH
Adjust pH value 12.5～13.0, stir 30min, left at room temperature 6h, sucking filtration；
Step e, filtrate is adjusted pH value to 8.5 with phosphoric acid,diluted acid, is stirred 30min, sucking filtration, collect insoluble matter, to obtain final product
.beta.-bitter acid crude product；With normal hexane .beta.-bitter acid crude product is carried out recrystallization and obtain white pin state .beta.-bitter acid fine work.
In above-mentioned steps c, the mixture of hop extract and water, at a temperature of 45 DEG C～50 DEG C, is adjusted with 10%NaOH
PH value stirs to 8.5～9.0 times.
In above-mentioned steps b, steaming the de-solvent obtained, R134a, methanol reclaim through condenser system and return to extraction
Device recycles.
The beneficial effects of the present invention is compared with prior art: 1, the present invention utilizes subcritical ultrasound assisted extraction technique,
Using R134a mixed solvent as Extraction solvent, in production, solvent is not required to special handling and can recover high-purity state,
95% and above methanol (or ethanol) must be used when solving extract by solvents, otherwise miscellaneous because of extracting solution water solublity
The problem that matter is many and has a strong impact on the separation of .beta.-bitter acid.
2, the present invention utilizes subcritical ultrasound assisted extraction technique, uses R134a mixed solvent as Extraction solvent, extracts
Temperature is only room temperature, solves as keeping higher extraction ratio, and Extracting temperature preferably must be held in 80-85 DEG C, otherwise carries
Take the problem that rate will be substantially reduced.
3, the present invention utilizes subcritical ultrasound assisted extraction technique, uses R134a mixed solvent as Extraction solvent, raw material
Pulverizing and meticulous also do not interfere with production, solve because of the restriction of extraction pot operation, it is meticulous that raw material is difficult to pulverize, and otherwise carries
Take the problem that liquid stream goes out difficulty.
4, the present invention utilizes subcritical ultrasound assisted extraction technique, and subcritical ultrasonic extraction device pressure carries far below supercritical
Taking equipment, volume of equipment is greatly increased, and makes large-scale production become a reality, solves supercritical CO2Method is extracted because needing
High pressure causes device fabrication requirement strict, extracts volume little, the problem having had a strong impact on large-scale production.
5, the present invention utilizes subcritical ultrasound assisted extraction technique, and employing R134a mixed solvent is as Extraction solvent, because of not
Use 95% and above methanol (or ethanol), make hop extract water-solubility impurity reduce, and makes acid-alkali accommodation be prone to control
System, crystallize is more thorough, and when solving isolated and purified, acid-alkali accommodation is wayward, often results in remove impurity not thorough, analysis
The problem that brilliant purity is the highest.
Detailed description of the invention
Hereinafter, to the present invention, above-mentioned and other technical characteristic and advantage are described in more detail.
The present invention extracts the process of separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli):
Step a, loads Flos lupuli (Flos Humuli Lupuli) compressor in subcritical ultrasonic extractor, selects suitable temperature and pressure, will
R134a mixed solvent is passed through in extractor, and the effective ingredient being extracted in material is dissolved in liquid or subcritical state
In R134a mixed solvent, the extract of gained filters through filter, and filtrate pumps in separator.
Step b, regulation temperature and pressure makes R134a in R134a mixed solvent be converted into gaseous state by liquid, with extraction
Separately, the concentrated vaporizer of extracting solution containing methanol is concentrated to give hop extract to liquid, enters crystallize workshop section.
The de-solvent (R134a, methanol) obtained of steaming returns to extraction equipment through condenser system recovery and recycles.
Step c, takes a certain amount of hop extract and is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds
Water, at a temperature of 45 DEG C～50 DEG C, adjusts pH value to 8.5～9.0 with 10%NaOH, stirs 30min, quiet under room temperature
Put 6h, sucking filtration, collect insoluble matter.
Step d, presses insoluble matter by insoluble matter: water=1: the weight ratio of 10 adds water, at 45 DEG C～50 DEG C, uses 10%NaOH
Adjust pH value 12.5～13.0, stir 30min, left at room temperature 6h, sucking filtration.
Step e, filtrate is adjusted pH value to 8.5 with phosphoric acid,diluted acid, is stirred 30min, sucking filtration, collect insoluble matter, to obtain final product
.beta.-bitter acid crude product；With normal hexane .beta.-bitter acid crude product is carried out recrystallization and obtain white pin state .beta.-bitter acid fine work.
Below by embodiment, said method is illustrated.
Embodiment one:
Take Flos lupuli (Flos Humuli Lupuli) compressor 50kg to load in subcritical ultrasonic extractor, select suitable temperature and pressure, will
R134a mixed solvent is passed through in extractor, and the effective ingredient being extracted in material is dissolved in liquid or subcritical state
In R134a mixed solvent, the extract of gained filters through filter, and filtrate pumps in separator, by regulation temperature
Degree and pressure make R134a in R134a mixed solvent be converted into gaseous state by liquid, separate with extracting solution, carrying containing methanol
Take the concentrated vaporizer of liquid and be concentrated to give hop extract, enter crystallize workshop section.
The de-solvent (R134a, ethanol) obtained of steaming returns to extraction equipment through condenser system recovery and recycles.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at a temperature of 45 DEG C,
Adjust pH value to 8.5～9.0 with 10%NaOH, stir 30min, left at room temperature 6h, sucking filtration, collect insoluble matter.
Insoluble matter is pressed insoluble matter: water=1: the weight ratio of 10 adds water, at 45 DEG C, adjust pH value 12.5 with 10%NaOH～
13.0, stir 30min, left at room temperature 6h, sucking filtration.Filtrate adjusts pH value to 8.5 with phosphoric acid,diluted acid, stirs 30min,
Sucking filtration, collects insoluble matter, obtains 1.42kg .beta.-bitter acid crude product.With normal hexane .beta.-bitter acid crude product is carried out recrystallization to obtain
1.06kg white pin state .beta.-bitter acid fine work.
Embodiment two:
Take Flos lupuli (Flos Humuli Lupuli) compressor 50kg to load in subcritical ultrasonic extractor, select suitable temperature and pressure, will
R134a mixed solvent is passed through in extractor, and the effective ingredient being extracted in material is dissolved in liquid or subcritical state
In R134a mixed solvent, the extract of gained filters through filter, and filtrate pumps in separator, by regulation temperature
Degree and pressure make R134a in R134a mixed solvent be converted into gaseous state by liquid, separate with extracting solution, carrying containing methanol
Take the concentrated vaporizer of liquid and be concentrated to give hop extract, enter crystallize workshop section.
The de-solvent (R134a, ethanol) obtained of steaming returns to extraction equipment through condenser system recovery and recycles.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at a temperature of 50 DEG C,
Adjust pH value to 8.5～9.0 with 10%NaOH, stir 30min, left at room temperature 6h, sucking filtration, collect insoluble matter.
Insoluble matter is pressed insoluble matter: water=1: the weight ratio of 10 adds water, at 50 DEG C, adjust pH value 12.5 with 10%NaOH～
13.0, stir 30min, left at room temperature 6h, sucking filtration.Filtrate adjusts pH value to 8.5 with phosphoric acid,diluted acid, stirs 30min,
Sucking filtration, collects insoluble matter, obtains 1.46kg .beta.-bitter acid crude product.With normal hexane .beta.-bitter acid crude product is carried out recrystallization to obtain
1.09kg white pin state .beta.-bitter acid fine work.
Embodiment three:
Take Flos lupuli (Flos Humuli Lupuli) compressor 100kg to load in subcritical ultrasonic extractor, select suitable temperature and pressure, will
R134a mixed solvent is passed through in extractor, and the effective ingredient being extracted in material is dissolved in liquid or subcritical state
In R134a mixed solvent, the extract of gained filters through filter, and filtrate pumps in separator, by regulation temperature
Degree and pressure make R134a in R134a mixed solvent be converted into gaseous state by liquid, separate with extracting solution, carrying containing methanol
Take the concentrated vaporizer of liquid and be concentrated to give hop extract, enter crystallize workshop section.Steam the de-solvent (R134a, ethanol) obtained
Return to extraction equipment through condenser system recovery recycle.
Hop extract is placed in reactor, by hop extract: water=1: the weight ratio of 2 adds water, at a temperature of 45 DEG C,
Adjust pH value to 8.5～9.0 with 10%NaOH, stir 30min, left at room temperature 6h, sucking filtration, collect insoluble matter.
Insoluble matter is pressed insoluble matter: water=1: the weight ratio of 10 adds water, at 50 DEG C, adjust pH value 12.5 with 10%NaOH～
13.0, stir 30min, left at room temperature 6h, sucking filtration.Filtrate adjusts pH value to 8.5 with phosphoric acid,diluted acid, stirs 30min,
Sucking filtration, collects insoluble matter, obtains 2.83kg .beta.-bitter acid crude product.With normal hexane .beta.-bitter acid crude product is carried out recrystallization to obtain
2.08kg white pin state .beta.-bitter acid fine work.
The foregoing is only presently preferred embodiments of the present invention, be merely illustrative for invention, and nonrestrictive.
Those skilled in the art understands, it can be carried out many changes in the spirit and scope that invention claim is limited,
Amendment, even equivalence, but fall within protection scope of the present invention.
Claims (2)
1. one kind is extracted the method separating .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli), it is characterised in that this detailed process is:
Step a, Flos lupuli (Flos Humuli Lupuli) compressor is loaded in subcritical ultrasonic extractor, select suitable temperature and pressure, R134a mixed solvent is passed through in extractor, the effective ingredient being extracted in material is dissolved in the R134a mixed solvent of liquid or subcritical state, the extract of gained filters through filter, and filtrate pumps in separator；
Step b, regulation temperature and pressure makes R134a in R134a mixed solvent be converted into gaseous state by liquid, separates with extracting solution, and the concentrated vaporizer of extracting solution containing methanol is concentrated to give hop extract, enters crystallize workshop section；
Step c, takes 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, sucking filtration, collects insoluble matter；
Step d, presses insoluble matter by insoluble matter: water=1: the weight ratio of 10 adds water, at 45 DEG C～50 DEG C, adjusts pH value 12.5～13.0 with 10%NaOH, stirs 30min, left at room temperature 6h, sucking filtration；
Step e, filtrate is adjusted pH value to 8.5 with phosphoric acid,diluted, is stirred 30min, sucking filtration, collect insoluble matter, obtain .beta.-bitter acid crude product；With n-hexane .beta.-bitter acid crude product is carried out recrystallization and obtain white pin state .beta.-bitter acid fine work；
In above-mentioned steps c, the mixture of hop extract and water, at a temperature of 45 DEG C～50 DEG C, adjusts pH value to stir to 8.5～9.0 times with 10%NaOH.
The method extracting separation .beta.-bitter acid from Flos lupuli (Flos Humuli Lupuli) the most according to claim 1, it is characterised in that in above-mentioned steps b, steams the de-solvent obtained, and R134a, methanol return to extraction equipment through condenser system recovery and recycles.
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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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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 |
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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 |
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