CN1035993C - Method for preparing tetrahydro-iso-humulone from hop extract - Google Patents
Method for preparing tetrahydro-iso-humulone from hop extract Download PDFInfo
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- CN1035993C CN1035993C CN94100149A CN94100149A CN1035993C CN 1035993 C CN1035993 C CN 1035993C CN 94100149 A CN94100149 A CN 94100149A CN 94100149 A CN94100149 A CN 94100149A CN 1035993 C CN1035993 C CN 1035993C
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- humulone
- iso
- tetrahydro
- tetrahydrochysene
- aqueous solution
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Abstract
The present invention provides a method for separating tetrahydro-iso-humulone from hop extract, which comprises: humulone and lupulone are directly separated from the hop extract by a raw extract material, and humulone is isomerized into iso-humulone; then, iso-humulone and lupulone are synchronously hydrogenized to tetrahydro-iso-humulone and tetrahydro-oxygen-free-humulone; finally, tetrahydro-oxygen-free-humulone is oxidized and isomerized into tetrahydro-iso-humulone. The obtained product can be used for preparing beer and similar products, and has improved blowing characteristics, increased bacterial inhibition and doubled bitterness.
Description
The present invention relates to a kind of method for preparing tetrahydro-iso-humulone by hop extract.
For a long time, people use hops to produce distinctive bitter taste of beer and local flavor in the brewage process.
Contain humulone, lupulone in the hops and some are without completely specified hops olein composition, wherein humulone is the precursor in beer acerbity source, lupulone then do not have bitter taste and in wheat juice and beer solubleness extremely low, in the composition of beer and local flavor, have little significance, generally all it is discarded.Humulone can change into isohumulone in the chemical transformation of wine brewing process, and isohumulone gives beer distinctive bitter taste.
But isohumulone is to light, particularly ultraviolet auroral poles instability.In the beer that contains isohumulone is loaded on transparent or green bottle, tanned by the sun in daylight or light following time, just can produce a kind of stink that is unfavorable for beer flavor.
Had found that a kind of stablely to light, and still had the material tetrahydro-iso-humulone of the peculiar bitter taste of beer simultaneously, this material can be used for the preparation of beer.Tetrahydro-iso-humulone also has good foam performance and bacteriostatic action, and it than the bitter 1.8-2 of isohumulone doubly.
The raw material of preparation tetrahydro-iso-humulone can be natural humulone or lupulone.US patent 3,552,925 discloses the method for a kind of lupulone through hydrogenation, atmospheric oxidation and lead salt processing and preparing tetrahydro-iso-humulone.The shortcoming of this method is time-consuming a lot, and might be in product residual lead compound.
US patent 3,923,897 discloses the another kind of method for preparing tetrahydro-iso-humulone, and the anaerobic tetrahydrochysene humulone that this method adopts peroxide oxidation to obtain through hydrogenated lupulone forms tetrahydro-iso-humulone through isomerization reaction again.
US patent 4,644,084 also discloses a kind of method for preparing tetrahydro-iso-humulone, and this method is after lupulone is hydrogenated to tetrahydrochysene anaerobic humulone, simultaneous hydrogenation isomerization in alkaline-earth metal and alkali alcosol and form tetrahydro-iso-humulone.
US patent 5,013,571 discloses and has a kind ofly prepared the method for tetrahydro-iso-humulone from humulone, is through isomerization progressively hydrogenation or synchronous and heterogeneousization hydrogenation humulone and make tetrahydro-iso-humulone more in the method.
Although the method that can adopt above-mentioned document to provide prepares tetrahydro-iso-humulone, but as can be seen, the raw material of aforesaid method is single humulone and lupulone, that is to say if prepare the words of tetrahydro-iso-humulone from the hops raw material, just must at first humulone be separated with lupulone, up to the present also not have directly to adopt the mixture of humulone and lupulone to prepare the report of tetrahydro-iso-humulone.Owing to need the sepn process of two kinds of ketone, make industrial production form inconvenience, increase efficient reduction etc. as cost.The method of separating two kinds of ketone from hop extract respectively is recorded in US patent 4,342,791; 4,590,296; 4,666,731.
The objective of the invention is to need can directly wherein humulone and lupulone be converted into tetrahydro-iso-humulone through the sepn process of humulone and lupulone from hop extract.It is stable and have enhanced foaminess and bacteriostatic action to light to use method of the present invention more effectively more easily the effective constituent in the hop extract synchronously to be changed into, and the tetrahydro-iso-humulone of double bitter taste.According to method of the present invention, except using humulone, also simultaneously useless lupulone is changed into the wine brewing composition of economic worth, total economic benefit can improve 3 times, also can alleviate domestic and international demand to hops simultaneously.
According to the present invention, a kind of method of extracting tetrahydro-iso-humulone from hop extract is provided, present method can with organic solvent also not the nationality organic solvent handle, this method comprises the steps: (1) synchronously separates the mixture of humulone and lupulone simultaneously from hops step; (2) the humulone isomery is turned to the step of isohumulone; (3) with isohumulone and lupulone synchronously respectively hydrogenation be the step of tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone; (4) oxidation of tetrahydrochysene anaerobic humulone is isomerizated into the step of tetrahydro-iso-humulone;
Wherein step (1) and (2) can be carried out step (1) earlier, also can carry out step (2) earlier.The used raw material of the inventive method is the hop extract of Liquid carbon dioxide extraction, also the hop extract that can make for other method.
Alkali aqueous solution in the invention is meant the hydroxide aqueous solution of basic metal, alkaline-earth metal, the aqueous solution of preferred potassium hydroxide, sodium hydroxide.
When at first carrying out step (1), the process of the step of the invention described above method (1) is as follows: make hop extract and alkali aqueous solution carry out thorough mixing under 40-60 ℃ and stirred 15～30 minutes, after leaving standstill, promptly obtain two phase materials, it is oil phase hops olein at the middle and upper levels, lower floor is the aqueous solution of the mixture of humulone and lupulone, is separated two, promptly obtains the aqueous solution of two kinds of alcohol/ketone mixtures of lower floor.
Wherein, the ratio of the molar weight summation of the molar weight of alkali and two kinds of ketone is 0.8-2: between 1.The volume ratio of alkali aqueous solution and hop extract is 1-10: between 1.
Step (2) process of humulone and lupulone aqueous solution isomerization humulone is as follows: the above-mentioned aqueous solution is heated to 60-100 ℃, or preferably in the aqueous solution, add the common heating of alkaline earth salt to promote isomerization reaction, lasting heating needed 1～2 hour to turn to isohumulone until the humulone isomery approximately, then solution is cooled to and adds acid again after the room temperature and carry out acidifying, being neutralized to pH value is below 2.The oil-phase solution that forms the upper strata after the acidifying is the mixture of different humulus flower ketone and lupulone, abandons it through separating lower aqueous solution.The all available two kinds of analytical procedures of all isomerization, oxidation, hydrogenation are measured, and the one, use ultraviolet absorption spectroscopy, another is high pressure liquid chromatography (this kind method has been published in many documents).
The alkaline earth salt that uses in the said process comprises: MgCl
2, MgSO
4, Mg (OH)
2, CaCl
2, CaSO
4, CaCO
3Deng.Described acid is hydrochloric acid, sulfuric acid, nitric acid or phosphoric acid.
When at first carrying out step (2), be with the hops raw material direct heating in stirring to 60-100 ℃, or preferably in heat-processed, add alkaline earth salt to promote reaction efficiency.Lasting heating needed stop to heat when the complete isomery of humulone turns to isohumulone approximately in 1～2 hour.Described alkaline earth salt is the same.
After this, reactant is cooled to 40-50 ℃, the hops olein of upper surface is removed, use the isohumulone of acidifying lower floor and the mixture of lupulone again, acidization and used acid obtain the mixture of isohumulone and lupulone with aforementioned.
It is as follows that the isohumulone that above-mentioned (1) and (2) step are obtained and the mixture of lupulone carry out the hydrogenant step: described mixture is dissolved in the alcoholic solvent that is selected from methyl alcohol, ethanol, propyl alcohol etc., in alcohol, add 0.1～5%, preferred 0.5～1% acid (volume of acid and pure volume ratio), acid is concentrated hydrochloric acid, the vitriol oil or acetic acid.Carry out hydrogenation process then under hydrogen-pressure, synchronously isohumulone is converted into tetrahydro-iso-humulone, lupulone is converted into anaerobic tetrahydrochysene humulone.
Preferably use a kind of this field conventional catalyst to carry out catalysis in hydrogenation process, as palladium catalyst on the carbon or platinum based catalyst, its consumption is preferably 1～10% (weight), on the carbon in the palladium catalyst palladium or platinum content be 1～10% (weight).
The temperature of above-mentioned hydrogenation process can be 20～65 ℃, and hydrogenation time is generally 1～2.5 hour, preferred 1.5～2 hours.Hydride hydrogen air pressure is 0～8Kg/cm
2(pressure be 0 promptly refer to directly ventilate body under normal atmosphere).
When treating that hydrogen no longer absorbs, can stop again logical hydrogen.Just hydrogen-pressure is constant promptly is that reaction is finished, and obtains containing the reaction product of tetrahydrochysene anaerobic humulone and tetrahydro-iso-humulone.
The step that above-mentioned reaction product is finally made single tetrahydro-iso-humulone can adopt following any process: A. to filter out catalyzer excessively from above-mentioned product, boil off alcoholic solvent, and excess tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone are dissolved in the organic solvent.Between 0 ℃ to 35 ℃, add oxygenant and act on it, tetrahydrochysene anaerobic humulone is oxidized to after the tetrahydrochysene humulone, with the alkaline aqueous solution effect and be heated to 60～100 ℃, the aqueous solution of the tetrahydro-iso-humulone that reheat gets final product doublely to boiling.
The used organic solvent of present method is methylene dichloride or hexane; Oxygenant is acetic acid and hydrogen peroxide mixed solution, peracetic acid or perbenzoic acid; The ratio of alkali mole number and tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone total mole number is 0.8～1.2 in the alkaline aqueous solution: between 1; The ratio of the mole number of used oxygenant and tetrahydrochysene anaerobic humulone is 0.8～1.2: between 1.B. above-mentioned product is boiled off alcoholic solvent, the back adds hexane or methylene dichloride, tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone that dissolving is remaining, catalyzer that stays after the mat hydrogenation and air or oxygen effect, tetrahydrochysene anaerobic humulone wherein is oxidized to the tetrahydrochysene humulone, filter then, remove catalyzer, add buck and its effect again, be heated to 60～70 ℃, remove and desolvate, continue to be heated to and boil, treat that the tetrahydrochysene humulone is isomerizated into tetrahydro-iso-humulone fully, the aqueous solution of the tetrahydrochysene humulone that gets final product doublely.
It is at 0～8Kg/cm that the used air or oxygen of this method is pressed
2Between; Temperature of reaction is between 0～25 ℃; The ratio of alkali mole number and tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone total mole number is 0.8～1.2: between 1.C. after from above-mentioned product, filtering out catalyzer excessively, it is directly mixed with alkaline aqueous solution and alkaline earth salt, make itself and air or oxygen play oxidation and heated isomerization reaction, wherein existing tetrahydro-iso-humulone is constant, and tetrahydrochysene anaerobic humulone is a step to change into tetrahydro-iso-humulone, after being acidified with acid, evaporates alcoholic solvent, the remaining oil-phase solution and the aqueous solution are removed lower aqueous solution and can be obtained tetrahydro-iso-humulone.
Described alkaline earth salt and sour same step (1) definition.
The embodiment that below provides can further know understanding method of the present invention, but is not limitation of the invention.
The hop extract (containing 40% humulone and 42% lupulone) of embodiment (1) 1076 gram mixes stirring with the potassium hydroxide of 195.4 grams and 2000 milliliters water in 5 liters container, be heated to 50 ℃, remove the hops olein and the impurity on upper strata after static 30 minutes, remaining lower aqueous solution.(2) will be by the water-soluble direct heating of the lower floor that (1) obtains or to the sal epsom that wherein adds 76 grams, be heated to 60～100 ℃, treat promptly to stop heating after humulone is isomerizated into isohumulone fully, the hydrochloric acid that adds 6N is acidified to pH less than 2, after static ten minutes, oil-phase solution floats on the upper strata, remove lower aqueous solution, can obtain 1113.5 gram oil-phase solutions, know after by analysis to contain 35% isohumulone and 43% lupulone.(3) will be dissolved in the ethanolic soln (250 milliliters) that contains 5 milliliters of hydrochloric acid by 65 gram oil phase isohumulones and the lupulone mixtures that (2) obtain after, add palladium catalyst (Palladium on activated carbon on 5.5 carbon that restrain, 5%Pd, Aldrich Chemical Company, Milwaukee, WI USA), feeds 0.7Kg/cm
2The hydrogen effect, temperature of reaction was carried out 1.5 hours between 50～55 ℃ approximately, hydrogenation is finished, filter out catalyzer, merge after cleaning with 50 milliliters of ethanol 291 gram ethanolic solns, by analysis, contain 7% tetrahydrochysene anaerobic humulone (20.37 gram) and 7.4% tetrahydro-iso-humulone (21.53 gram) in this solution.(4) alcoholic solution that obtains in (3) is evaporated alcoholic solvent, the hexane that remaining fluid adding is 100 milliliters makes its dissolving and is cooled between 0～20 ℃, adds peracetic acid (15.35 grams with mole numbers such as tetrahydrochysene anaerobic humulones; 35% purity) after effect treated that tetrahydrochysene anaerobic humulone was completely oxidized to the tetrahydrochysene humulone in about 1 hour, clean three times with 50 milliliters water, adding the potassium hydroxide of 9.47 grams and 350 milliliters water then acts on it, be heated between 65～67 ℃, remove hexane after 1 hour, remaining alkali aqueous solution reheat boils to the tetrahydrochysene humulone and is isomerizated into tetrahydro-iso-humulone, behind the cold filtration, can obtain the aqueous solution of the tetrahydro-iso-humulone of 386 grams 10%; Wherein half is to be come by the isohumulone preparation.(5) product that obtains after the hydrogenation in (3) is together evaporated alcoholic solvent without filtering with catalyzer, the hexane that the back adding is 200 milliliters mixes feeding 4Kg/cm with excess
2The air effect, after a few hours, remove by filter catalyzer, add the potassium hydroxide and 350 milliliters the water of 9.48 grams and be heated to 65～70 ℃, remove hexane after 1 hour, remaining alkali aqueous solution continues heated and boiled to tetrahydrochysene humulone and is isomerizated into fully till the tetrahydro-iso-humulone, cooling, after the filtration, can obtain the aqueous solution of the tetrahydro-iso-humulone of 385 grams 9.5%.The sal epsom that adds 28 grams in the alcoholic solution of 291 grams that (6) (3) obtained, the potassium hydroxide (or sodium hydroxide) of 19 grams and 360 milliliters water mix feeding 1Kg/cm
2Reheat played isomerization reaction after air (or oxygen) acted on one hour, and temperature of reaction is between 60～75 ℃, and through 4 hours, original tetrahydro-iso-humulone was constant, and tetrahydrochysene anaerobic humulone promptly changes into tetrahydro-iso-humulone.Add hydrochloric acid (or sulfuric acid) and be acidified to the pH value less than 2, evaporate alcoholic solvent, upper oil phase solution can be separated with the aqueous solution and obtain 57.2 medicinal extract that restrain, and contains 67% tetrahydro-iso-humulone, and it is dissolved in the aqueous solution that potassium hydroxide aqueous solution can prepare tetrahydro-iso-humulone.
Claims (17)
1. one kind prepares the method for tetrahydro-iso-humulone from hop extract, and this method comprises the steps: that (1) separate the step of the mixture of humulone and lupulone from hops; (2) the humulone isomery is turned to the step of isohumulone; (3) with isohumulone and lupulone synchronously respectively hydrogenation be the step of tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone; (4) oxidation of tetrahydrochysene anaerobic humulone is isomerizated into step into tetrahydro-iso-humulone.
2. according to the method for claim 1, it is characterized in that from hops, separating the step of the mixture of humulone and lupulone, comprise following process: hop extract and alkali aqueous solution are carried out the thorough mixing stirring under 40～100 ℃, the lower floor's water that obtains is the aqueous solution of humulone and lupulone mixture, alkali aqueous solution wherein is a basic metal, the aqueous solution of alkaline earth metal hydroxides.
3. by the method for claim 2, it is characterized in that the ratio of the mole number summation of the mole number of alkali and two kinds of ketone is 0.8～2: between 1, the volume ratio of alkali aqueous solution and hop extract is 1～10: between 1.
4. by the method for claim 2, it is characterized in that alkali is potassium hydroxide or sodium hydroxide.
5. by the method for claim 1, the step that the humulone isomery turns to isohumulone comprises: the aqueous solution of two kinds of ketone is heated to 60～100 ℃, finishes the isomerization postcooling to room temperature, be acidified to pH value less than 2 with acid again.
6. by the method for claim 5, it is characterized in that also in the aqueous solution, adding alkaline earth salt.
7. by the method for claim 6, it is characterized in that alkaline earth salt is selected from MgCl
2MgSO
4, Mg (OH)
2, CaCl
2, CaSO
4, CaCO
3Acid is hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid.
8. by the method for claim 1, it is characterized in that to carry out step (2) earlier, carry out step (1) again.
9. by the method for claim 8, it is characterized in that the process of step (1) and (2) is as follows:, stop heating afterwards with hops raw material direct heating to 60～100 ℃ or adding alkaline earth salt; It is cooled to 40～50 ℃, remove the oil phase of upper strata hops olein after, use acidifying, said alkaline earth salt is MgCl
2, MgSO
4, Mg (OH)
2, CaCl
2, CaSO
4, CaCO
3Acidifying acid is sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid.
10. according to the method for claim 1, it is as follows that the mixture that it is characterized in that isohumulone that step (1) and (2) are obtained and lupulone carries out the hydrogenant process: this mixture is dissolved in the alcoholic solvent that is selected from methyl alcohol, ethanol or propyl alcohol, in alcohol, add 0.1～5% acid (volume), under hydrogen-pressure, under a kind of catalyst action, carry out hydrogenation, temperature of reaction is 20～65 ℃, reaction times is 1～2.5 hour, and hydride hydrogen air pressure is 0～8Kg/cm
2, obtain the alcoholic solution of tetrahydro-iso-humulone and anaerobic tetrahydrochysene humulone.
11. the method by claim 10 is characterized in that described catalyzer is palladium catalyst or a platinum based catalyst on the carbon.Its consumption is 1～10% (weight).
12. by the method for claim 10, the hydrogenation in 0.5～1% (volume) acidity alcohol solution synchronously simultaneously of isohumulone and lupulone.
13. method by claim 1, it is characterized in that product that step (3) is obtained after filtration, after removing catalyzer, boil off alcoholic solvent and excess tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone are dissolved in the organic solvent, adding oxygenant between 0～35 ℃ acts on it, tetrahydrochysene anaerobic humulone is oxidized to after the tetrahydrochysene humulone, with the alkaline aqueous solution effect and be heated to 60～70 ℃, removes the aqueous solution of the tetrahydro-iso-humulone that the reheat that desolvates gets final product doublely to boiling.
14. the method by claim 13 is characterized in that described organic solvent is methylene dichloride or hexane; Oxygenant is acetic acid and hydrogen peroxide mixed solution, peracetic acid or perbenzoic acid, and the ratio of the mole number of alkali and total ketone mole number is 0.8～1.2: between 1, the ratio of the mole number of used oxygenant mole number and tetrahydrochysene anaerobic humulone is 0.8～1.2: between 1.
15. method by claim 1, it is characterized in that, the reaction product of filtered in the step (3) being fallen catalyzer boils off alcoholic solvent, the back adds hexane or methylene dichloride, tetrahydro-iso-humulone and tetrahydrochysene anaerobic humulone that dissolving is remaining, with catalyzer that stays after the hydrogenation and air or oxygen effect tetrahydrochysene anaerobic humulone wherein is oxidized to the tetrahydrochysene humulone, filter then, remove catalyzer, add buck and its effect, be heated to 60～70 ℃, remove and desolvate, continue to be heated to and boil, treat that the tetrahydrochysene humulone is isomerizated into tetrahydro-iso-humulone fully, the aqueous solution of the tetrahydrochysene humulone that gets final product doublely.
16., it is characterized in that the oxygen pressure is 0～8Kg/cm in the air or oxygen by the method for claim 15
20～25 ℃ of temperature of reaction, the ratio of alkali and total ketone mole number is 0.8～1.2: between 1.
17. by the method for claim 1, the product elimination catalyzer that it is characterized in that step (3) and alkaline aqueous solution or add alkaline earth salt and directly mix and make itself and air or oxygen at 0～8Kg/cm
2Under play the oxidation post-heating and play isomerization reaction, promptly a step changes into tetrahydro-iso-humulone to the constant and tetrahydrochysene anaerobic humulone of wherein existing tetrahydro-iso-humulone, evaporate alcoholic solvent after being acidified with acid, the remaining oil-phase solution and the aqueous solution are removed lower aqueous solution and can be obtained tetrahydro-iso-humulone medicinal extract.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94100149A CN1035993C (en) | 1994-01-15 | 1994-01-15 | Method for preparing tetrahydro-iso-humulone from hop extract |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94100149A CN1035993C (en) | 1994-01-15 | 1994-01-15 | Method for preparing tetrahydro-iso-humulone from hop extract |
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|---|---|
| CN1096509A CN1096509A (en) | 1994-12-21 |
| CN1035993C true CN1035993C (en) | 1997-10-01 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94100149A Expired - Fee Related CN1035993C (en) | 1994-01-15 | 1994-01-15 | Method for preparing tetrahydro-iso-humulone from hop extract |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1079675C (en) * | 1997-07-23 | 2002-02-27 | 上海华光酿酒药业有限公司 | External use drug made of hops and vegetable oil |
| 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 |
| 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 |
| AU2010239691B2 (en) * | 2009-04-21 | 2015-09-03 | Haas, John I. | Animal feed compositions and feeding methods |
| WO2011037630A1 (en) * | 2009-09-22 | 2011-03-31 | Kalamazoo Holdings, Inc. | Process for the preparation of isohumulone compositions |
| WO2011059486A1 (en) * | 2009-11-13 | 2011-05-19 | Kalamazoo Holdings, Inc. | Process for the preparation of tetrahydroisohumulone compositions |
| CN102260146B (en) * | 2010-05-26 | 2014-06-25 | 北京锐拓生物工程设备有限公司 | Method for preparing hydrogenated hop acid |
| CN108103514A (en) * | 2017-12-26 | 2018-06-01 | 万丰航空工业有限公司 | A kind of plant base industrial cleaning agent based on barley and hop and preparation method thereof |
| CN108841554A (en) * | 2018-08-04 | 2018-11-20 | 华阴市哲远酒业有限公司 | A kind of preparation process of persimmon wine |
| 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 |
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|---|---|---|---|---|
| US4342791A (en) * | 1979-05-24 | 1982-08-03 | Brewing Patents Limited | Method of purifying iso-α-acids |
| US4590296A (en) * | 1984-01-25 | 1986-05-20 | Miller Brewing Company | Process for separation of beta-acids from extract containing alpha-acids and beta-acids |
| US4644084A (en) * | 1984-01-25 | 1987-02-17 | Miller Brewing Company | Preparation of tetrahydroisohumulones |
| US5013571A (en) * | 1990-01-31 | 1991-05-07 | Pfizer Inc. | Methods for making tetrahydroisoalpha and hexahydroisoalpha acids |
-
1994
- 1994-01-15 CN CN94100149A patent/CN1035993C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4342791A (en) * | 1979-05-24 | 1982-08-03 | Brewing Patents Limited | Method of purifying iso-α-acids |
| US4590296A (en) * | 1984-01-25 | 1986-05-20 | Miller Brewing Company | Process for separation of beta-acids from extract containing alpha-acids and beta-acids |
| US4644084A (en) * | 1984-01-25 | 1987-02-17 | Miller Brewing Company | Preparation of tetrahydroisohumulones |
| US5013571A (en) * | 1990-01-31 | 1991-05-07 | Pfizer Inc. | Methods for making tetrahydroisoalpha and hexahydroisoalpha acids |
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|---|---|
| CN1096509A (en) | 1994-12-21 |
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