CN1058699C - Preparation of tetrahydroisoalpha acid from hops extract - Google Patents
Preparation of tetrahydroisoalpha acid from hops extract Download PDFInfo
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- CN1058699C CN1058699C CN98120079A CN98120079A CN1058699C CN 1058699 C CN1058699 C CN 1058699C CN 98120079 A CN98120079 A CN 98120079A CN 98120079 A CN98120079 A CN 98120079A CN 1058699 C CN1058699 C CN 1058699C
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Abstract
The present invention discloses a method for preparing tetrahydro iso-alpha and beta acid, which adopts hop extract as raw material. The method mainly comprises the following four steps: step 1, alpha acid and beta acid are simultaneously separated from extract by alkaline alcohol, and mixed solution of the alpha acid and the beta acid is prepared; step 2, the beta acid is separated from the mixed solution of the alpha acid and the beta acid by CO2 gas, the solution is acidified, and the alpha acid is separated; step 3, the alpha acid is catalyzed and hydrogenated in alkaline alcohol water solution, and a tetrahydro iso-alpha acid crude product is prepared; step 4, the tetrahydro iso-alpha acid crude product is prepared into solution which contains 5 to 10% of THIAA in an alkaline alcohol method. The operating steps of the present invention are simple. The conversion rate of the obtained THIAA is high.
Description
The present invention relates to the preparation method of the different α acid of tetrahydrochysene, refer to a kind of especially by liquid, subcritical or supercritical CO
2Hops Extract prepares the method for the different α acid of tetrahydrochysene.
Abroad, the method for preparing the different α acid of tetrahydrochysene early is to be raw material with natural α acid or β acid, through different α acid of method system tetrahydrochysene such as over hydrogenation and oxidation and lead salt precipitations, the shortcoming of this method maximum is easy lead compound (the US patent 3 of residual harmful in product, 552,925), also have with β acid be raw material earlier with its hydrogenation again with oxygen, air or superoxide with its oxidation, be isomerizated into the different α acid of tetrahydrochysene (USP.4,918,240; 4,644,084); Also having a kind of method is to be raw material with the hop extract, earlier the α acid in the medicinal extract is separated, and carry out isomerization, carry out hydrogenation again to make the different α acid of tetrahydrochysene (USP.5,013,571), have again α acid is carried out hydrogenation and isomerization simultaneously with preparation tetrahydrochysene different α acid (J.Agric.Foodchem.1991,39 in primary first-order equation, 1732-1734) or the like, these methods respectively have characteristics, but all exist flow process oversize, the shortcoming that transformation efficiency is lower.
Other has the name that flies two people invention by Zhou Minggui, Tang one to be called the Chinese invention patent application of " method that is prepared tetrahydro-iso-humulone by hop extract ", application number: 94100149.0, the disclosed method of this patent application is directly to isolate humulone (being α acid) from hop extract, after oxidation is isomerizated into tetrahydro-iso-humulone (being the different α acid of tetrahydrochysene).The advantage of this method is that flow process is shorter, but some step is difficult to finish, and raw material availability is not too high, only about 70%.
At the deficiencies in the prior art, it is the different α acid (Tetrahydroiso-α-acid of amaroid-tetrahydrochysene that raw material is made beer with the hop extract that main purpose of the present invention provides a kind of, THIAA) method uses this method to obtain higher productive rate with the step of more simplifying.
Method of the present invention is made up of following four steps:
1. from hop extract, isolate α acid and β acid with the alkaline ethanol method.
2. use CO
2Gas is isolated β acid and is used it for anything else in addition from α, β acid mixed solution, and souring soln, separates out α acid.
3. in alkaline ethanol-aqueous solution and in the presence of catalyzer, feed hydrogen, make α acid hydrogenation simultaneously and isomerization, make the different α acid crude of tetrahydrochysene.
4. the different α acid of tetrahydrochysene is made the different α acid solution of the tetrahydrochysene that contains THIAA 5～10% that can directly be used for modulating beer with the alkaline ethanol method.
It is as follows to describe each step of the present invention below in detail:
1. from medicinal extract, isolate α acid and β acid simultaneously with alkaline ethanol, make α, β mixing solutions.Its main process is: take by weighing a certain amount of medicinal extract, [weight ratio of medicinal extract and KOH ethanolic soln is 2: (0.5～1) it to be dissolved in potassium hydroxide (KOH) ethanolic soln (KOH can replace with NaOH) under 20～60 ℃.In the KOH-ethanolic soln moisture 5～20%.The ratio of the KOH mole number in the medicinal extract in α acid and β acid total mole number and the ethanol is 1: 1.1～1.8.] after dissolving finishes, left standstill 1～2 hour, in this solution, add 8～12 times water again.Stir, left standstill 3～4 hours, make the solution layering that [generally be divided into two-layerly, the upper strata is a water, wherein be dissolved with α acid and β acid potassium (sodium) salt, lower floor is a residue, is divided into three layers sometimes, and the upper strata is the lightweight oil reservoir, in a small amount of fragrant flower oil is arranged, the middle level is a water layer, lower floor is a residue].Water layer is separated, promptly got α, β acid mixing solutions, its pH value is about 9.5～11.0.α acid yield is 96～98%, and β acid yield is 85～90%.
2. in α, β acid mixing solutions, lead to CO
2Gas, the pH value of regulator solution is separated out β acid from solution, separate with α acid in the solution.Detailed process is: solution is put in the reactor, and solution is heated to 20～40 ℃, under agitation feeds CO
2When the pH value of solution value reduces to 8.0～9.0, stop ventilation, continue to stir 1～2 hour, when forming white molecule, β acid stops.Filter, isolate β acid, use 40%H afterwards again
2SO
4(or 6N HCl) transfers pH value to 1～2 of solution, makes α acid separate out (the thick thing of tawny) from solution, isolates water after leaving standstill, and α acid is handled for next step, and the rate of recovery of α acid is 90～95% in this step, and β acid is 80～85%.
3. catalysis in the alkaline ethanol aqueous solution, hydrogenation and isomerized alpha acid are made the different α acid crude of tetrahydrochysene, and detailed process is: the prepared α acid of second step is dissolved in the aqueous ethanolic solution [ethanol: water=(1.5～3): 1, volume ratio].Extraordinarily go into sal epsom or magnesium chloride by 0.1～0.5 of α acid mole number, press 6%～8% of α acid weight and add salt of wormwood, press 5%～15% of α acid weight and add catalyzer, transfer pH value of solution value to 7～12 with 40%NaOH again.Be placed in the hydrogenation reactor logical H
2Gas is to 0-10Kg/cm
2, under 40～100 ℃ and violent stirring, reacted 5～10 hours, after reaction is finished, put coldly, filter, remove catalyzer, gained solution is orange, uses 40%H
2SO
4Adjust pH is 1～2, promptly has the orange oily liquids to separate out.Standing demix, the isolated for disposal water is used 1% rare H again
2SO
4(or 0.1HCl) promptly gets the different α acid crude of tetrahydrochysene with orange oily matter washing 2～3 times, and wherein THIAA content is 60～80%, and the hydrogenation rate of recovery is 76～89%.
4. with the alkaline ethanol method the different α acid crude of tetrahydrochysene is made 5%～10% the different α acid solution of tetrahydrochysene, process is as follows: the different α acid crude of tetrahydrochysene is dissolved in [95% ethanol: water=1: 0.05～0.1] in the KOH ethanolic soln, fully stir, crude product is dissolved fully, add 8～10 times water of liquor capacity again, stir, placed 1～2 hour, insolubles in the elimination water promptly gets 5～10% THIAA solution.The consumption of alkaline ethanol is 0.5～2 times of THIAA weight in the crude product.Mole such as THIAA in alkali (KOH or NaOH) consumption and the crude product.
Compare with application number 94100149.0 disclosed technology (hereinafter to be referred as prior art), the present invention has own exclusive characteristics:
1. the present invention extracts α acid and β acid in the hop extract simultaneously with the alkaline ethanol method, make α, β acid mixing solutions, then with α acid and β acid in the alkaline aqueous solution extraction cream, α provided by the invention, β acid extraction method there is no report both at home and abroad to prior art at present.α of the present invention, β extraction yield are up to 96-98%, and the extraction yield of prior art is up to 90%.
2. the present invention tells the β acid in the medicinal extract separately, and as second kind of product, other has purposes, as makes β acid fragrant flower oil.
3. the present invention carries out hydrogenation, isomerization separately to α acid in the alkaline ethanol aqueous solution: and prior art is under acidic conditions hydrogenation to be carried out in α, β acid simultaneously, under alkaline condition, carry out isomerization in addition, the two has difference in essence, and the technical process of prior art is obviously long than technical process of the present invention.
4. α of the present invention, β acid total yield can reach 80%, exceeds about 5-10 percentage point than prior art.
Further elaborate manufacturing processed of the present invention below by specific embodiment.
(1) takes by weighing subcritical CO
2Hop extract 534g (wherein containing α acid 42.01%, β acid 37.92%) is dissolved in (ethanol is 95% ethanol in the alkaline ethanol solution, wherein is dissolved with the KOH of 68g) in the 260ml alkaline ethanol solution.After stirring, placed 1 hour, heat release during the medicinal extract dissolving, top temperature can reach 56 ℃, so need not heat.
(2) in above-mentioned medicinal extract solution, add water 2080ml, stir after 30 minutes, left standstill 4 hours, system is divided into two-layer, supernatant liquid is the aqueous solution of α, β acid potassium salt, and lower floor is a clay shape residue, and inclining earlier with gradient method supernatant liquid, again with lower floor's residue suction filtration, gained filtrate and supernatant liquor merge solution 2500ml, pH value 9.67, residue 230.8g, sampling is analyzed on HPLC, and the result is:
In the solution: α acid content 86.64mg/ml
β acid content 72.23mg/ml
In the residue: α acid content 13.0mg/g
β acid content 53.6mg/g
α acid recovering rate 96.7%, β acid recovering rate 89.3%.
The α that above-mentioned steps is obtained, the 5000m Erlenmeyer flask that the β mixed aqueous solution places belt stirrer under agitation slowly feed CO
2, generating white fine precipitation in the solution immediately, the pH value of solution value descends gradually, when the pH value reduces to 8.0～8.6, stops logical CO
2, continuing to stir 1.5 hours, β acid forms the fine particle of white (or slightly yellow), stops to stir.Filter, separate β acid 186g, filtrate is orange.Use 40%H
2SO
4PH value of filtrate is transferred to 1～2, α acid (isabelline) is promptly separated out with thick solid substance, separate with gradient method, get α acid 242g, supernatant liquor discards, and analyzes through HPLC, contain pure α acid 86.76% in the solid substance, the α acid recovering rate is 96.98%, contains β acid 82.85% in the β acid crude, and the β acid recovering rate is 85.20%.
(3) earlier by 95% ethanol: the ratio preparation alcohol solution 2000ml of water=2: 1,242g α acid (crude product) is dropped in the aqueous ethanolic solution, stirring makes whole dissolvings, adds MgSO then while stirring
47H
2O16.66g, K
2CO
314.50g, catalyzer (Pd-C, 10%) 24g, with 40%NaOH the pH of system is transferred to 10.0～10.5 again, this reaction mixture is put into 5 liters of reactors, use N earlier
2Gas is driven air in the still away, feeds H again
2Gas makes H in the still
2Atmospheric pressure reaches 10Kg/cm
2, starting agitator and stir, heating makes temperature in the kettle progressively rise to 95～100 ℃ simultaneously, and keep this temperature as far as possible, after the reaction beginning, stop heating, if temperature is above 100 ℃, then need lead to water coolant, adjust temperature and make it in span of control, along with H in the still is carried out in reaction
2Atmospheric pressure descends, when reducing to 1Kg/cm
2About, in still, lead to a hydrogen again, air pressure is reached to 8.0Kg/cm
2, proceed reaction, reaction was to 7 hours, and hydrogen pressure is reduced to 1Kg/cm
2About, stopped reaction, logical water coolant makes system temperature drop to room temperature, emits reaction mass, and filters, and removes catalyzer.Gained filtrate gradually is burgundy after placing.Use 40% H
2SO
4Filtrate pH value is transferred to 1～2, have the oily glop to separate out.Leave standstill and make layering, emit supernatant liquor, use 1% H again with gradient method
2SO
4With oily liquid washing 2～3 times, get oily liquids 208g, analyze through HPLC, wherein contain THIAA88.85%, the THIAA rate of recovery is 88.02%.
(4) in 95% ethanol: the ratio preparation aqueous ethanolic solution 170g of water=1: 0.1 toward wherein adding 25.7gKOH, is made into alkaline ethanol solution.The different α acid crude of 208g oily tetrahydrochysene of third step gained is dissolved in this basic solution.After the dissolving fully, add water 1360ml.Stir, standing demix, insolubles sinks to lower floor in the water, and inclining with gradient method supernatant liquor, and with insolubles filtration in the water, filtrate and supernatant liquor merge, and get solution 1700ml, analyze through HPLC, contain THIAA9.68% in the solution, the different α acid recovering rate of tetrahydrochysene is 97.95%.
Claims (10)
1, a kind of is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that the main operational steps of this method is:
(1) from medicinal extract, isolates α acid and β acid simultaneously with alkaline ethanol, make α, β acid mixing solutions;
(2) from α, β acid mixed solution, isolate β acid with CO2 gas, and souring soln, α acid separated out;
(3) the different α acid crude of tetrahydrochysene is made in catalysis in the alkaline ethanol aqueous solution, hydrogenation isomerization α acid;
(4) with the alkaline ethanol method the different α acid crude of tetrahydrochysene is made the solution that contains the different α acid 5%～10% of tetrahydrochysene.
2, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that used medicinal extract is liquid CO
2Medicinal extract, subcritical or supercritical CO
2Medicinal extract.
3, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that used alkaline ethanol in the step (1) is the ethanolic soln for KOH or NaOH, this solution contains 5%～20% water, the consumption of KOH or NaOH aqueous ethanolic solution is 0.5～1 times of medicinal extract amount, and the mole number of KOH or NaOH consumption is 1.1～1.8 times of α acid mole number in the medicinal extract.
4, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, the specific operation process that it is characterized in that step (1) is: after medicinal extract is dissolved in KOH or NaOH solution, add 8～12 times of water, behind stirring, the standing demix, separate, the gained water-phase product is α, a β acid mixed aqueous solution.
5, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that the specific operation process of step (2) is: under 20～40 ℃, lead to CO in the solution of step (1) gained
2Gas till the pH value reaches at 8.0～9.0 o'clock, continues to stir 1～2 hour, filters to isolate β acid solid then, uses 40%H
2SO
4Or 6N HCl is acidified to pH value 1～2 with filtrate, and the thickness oily liquids is separated out from solution, carries out next step hydrogenation.
6, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that in the step (3), alcohol and the ratio of water be for counting 1.5～3: 1 by volume in the aqueous ethanolic solution, and catalyzer is 10% or 5%Pd-C, and catalyst consumption is 5～15% of the sour weight of α.
7, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that in the step (3), extraordinarily goes into MgSO by 0.1～0.5 of α acid mole number in the reaction system
47H
2O presses 6% of α acid weight and adds salt of wormwood.
8, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, and it is characterized in that the concrete operations condition of step (3) is: hydrogenation pressure is gauge pressure 0～10kg/cm during hydrogenation
2, the pH value of solution value is 7～12, and temperature is 40～100 ℃, and the reaction times is 5～10 hours.
9, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that step (3) after hydrogenation is finished, removes by filter catalyzer, uses 40%H again
2SO
4Or 6N HCl transfers to 1～2 with the pH value of solution value, the different α acid of tetrahydrochysene separated out from solution, and use 1%H
2SO
4Or 0.1NHCl washs precipitate 2～3 times.
10, according to claim 1 is the method for the different α acid of feedstock production tetrahydrochysene with the hop extract, it is characterized in that alkaline ethanol used in the step (4) is the ethanolic soln of KOH or NaOH, wherein moisture 5～10%, the mole number of the different α acid of tetrahydrochysene in the mole number of KOH or NaOH consumption and the different α acid crude of tetrahydrochysene is identical or slightly many, after the different α acid crude of tetrahydrochysene is dissolved in alkaline ethanol, add the water that is equivalent to 8～10 times of liquor capacities again, separate out and isolate water-insoluble, make the different α acid solution of the tetrahydrochysene that contains the different α acid of 5～10% tetrahydrochysenes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98120079A CN1058699C (en) | 1998-10-06 | 1998-10-06 | Preparation of tetrahydroisoalpha acid from hops extract |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98120079A CN1058699C (en) | 1998-10-06 | 1998-10-06 | Preparation of tetrahydroisoalpha acid from hops extract |
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| Publication Number | Publication Date |
|---|---|
| CN1216303A CN1216303A (en) | 1999-05-12 |
| CN1058699C true CN1058699C (en) | 2000-11-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98120079A Expired - Fee Related CN1058699C (en) | 1998-10-06 | 1998-10-06 | Preparation of tetrahydroisoalpha acid from hops extract |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966638B (en) * | 2006-11-11 | 2011-04-20 | 玉门拓璞科技开发有限责任公司 | Isomerized carbon dioxide hops extract production method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134719B (en) * | 2006-08-31 | 2010-08-18 | 北京理博兆禾酒花有限公司 | Method for preparing tetrahydrochysene isohumulone by hop concrete or lupulone oil |
| CN101307275B (en) * | 2008-07-15 | 2011-04-13 | 新疆大学 | Process for producing dihydro-isomerized lupulus extractum |
| AU2010239691B2 (en) * | 2009-04-21 | 2015-09-03 | Haas, John I. | Animal feed compositions and feeding methods |
| CN110951559A (en) * | 2019-12-31 | 2020-04-03 | 齐鲁工业大学 | Method for improving beer foam performance by adding tetrahydro or hexahydro isomeric hop extract |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013571A (en) * | 1990-01-31 | 1991-05-07 | Pfizer Inc. | Methods for making tetrahydroisoalpha and hexahydroisoalpha acids |
-
1998
- 1998-10-06 CN CN98120079A patent/CN1058699C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013571A (en) * | 1990-01-31 | 1991-05-07 | Pfizer Inc. | Methods for making tetrahydroisoalpha and hexahydroisoalpha acids |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966638B (en) * | 2006-11-11 | 2011-04-20 | 玉门拓璞科技开发有限责任公司 | Isomerized carbon dioxide hops extract production method |
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| CN1216303A (en) | 1999-05-12 |
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