DE2000689A1 - Process for extraction treatment of hops - Google Patents

Description

DIPL.-JNG. DR.JUR. W.BÖHME «500 NUREMBERG, *» DIPL -ING. E. KESSEL Frtuentoreraben 73 (am Plirrer)

.T β XTiY ^ c Telephone: ((WII) 2273M, 20429 «, 2042 * 7

DIPL.-ING. V. BÖHME Telegram address: PATBOM PATENT LAWYERS

Bank account: Deutsche Bank Nuremberg No. 137315 Postal checking account: Nuremberg Office No. 44852

7.1.197-0 ·

Applicant: Watney Mann (London & Home Counties) Limited

Title:

Process for extraction treatment of hops

description

The invention relates to a method of extraction treatment of resinous hop material. So it concerns hops and in particular such material from hops or Hop flowers obtained by mechanical or extractive treatment and rich in resins. In particular, but not exclusively, the invention relates to such hops material obtained by mechanical processing, which is rich in lupulin.

Hops are used in the brewing industry for various purposes and contain various specific groups more important Links. One of these groups are the so-called alpha acids, the others are the so-called beta acids, which are both more or less resinous, and one

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third group consists of essential oils. These components behave differently and are used in different stages of beer production; however, considerable losses occur if the constituents are not separated from the hop flowers and at least the essential oils are not separated from the resin acids. The resin acids are used to give the beer bitterness; but this bitterness only develops at an elevated temperature, which is why the hops are usually added to the wort before or during boiling. In this way, of course, most of the essential oils are lost. On the other hand, the essential oils which give distinctive taste and aroma are usually added after the seasoning is cooked and can advantageously be added after fermentation has taken place so that the alcohol content aids in extraction of the oils. Of course, if hop blossoms or lupulin-rich hop concentrate is used in this stage of the process, then the rosin acids are normally lost.

The resin acids also behave differently from one another. The alpha acids are conventionally converted into the desired lao alpha acids by boiling with seasoning, which add to the bitterness or part of the bitterness

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to lend. On the other hand, the beta acids are not used at all in the brewing process if they are not consciously used are oxidized.

It should also be mentioned that the hops and also the lupulin-rich hop powder and some hop extracts are different contain unwanted acids, especially the tannic acids. These are largely responsible for the cloudiness, which may develop in the resulting beer if steps are not taken to remove it or keep away.

Accordingly, it is highly desirable for effective decomposition. The lupulin component of hops is divided into different components, which contain the alpha acids, the beta acids and the essential oils separately. The invention provides for this purpose a method of the type mentioned in the beginning before, las is characterized in that extraction of the I. 'Takes place. Ateriales with aqueous alkali at a controlled elevated temple ¹ .- door ¹ and at controlled pH for selectively alpha- S ^: iures to extract, and then extraction of the best is done to extract the beta SMurs.

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Generei], the invention orders ¹ in a process for the treatment of resinous hops material, in which the material is separated from the material with an aqueous medium, preferably a sodium or potassium hydrogen phosphate solution or another buffer solution, under control of temperature and pH value Tannic acid and other ureic acids other than alpha and beta acids are extracted as a pre-extract, from the remainder with aqueous alkali, preferably disodium or dipotassium hydrogen phosphate, at a controlled elevated temperature, generally above 40 C, and controlled pH separately Alpha acids are extracted from earth to form a first extract and then the remainder is extracted with other aqueous alkali to dissolve beta acids out as a second extract. The essential oils are separated as a third extract when the remaining, used lupulin or other resinous hop material is thrown away.

The term "resinous hop material" denotes a hop material whose alpha acid content is at least 1? i> ew, ⁱ ; 5 or the total resin content of which was at least 24 wt. ^. This often requires a concentration of the resin content a, e.g. by mechanical treatment, but some resin-rich hops have a sufficiently high resin acid content that allows the hops j to use η reduced form «

It has been found that the various groups are more acidic Connections can be extracted separately

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without the aid of organic solvents, if temperature and pH - // ert are sufficiently taken into account during the extraction steps. A key point of the invention is the ability tannins that fatty acids and other undesirable acidic substances separate before the ^Alphao: -iuren be separated; and it is particularly advantageous that these two separations are with the same buffer solution or ^r Jem same alkali feasible.

The resinous hop material used normally has an alpha acid content of 20 to 30 wt /. If the alpha acid content exceeds $ 30, the process according to the invention can be modified by omitting the pre-extraction step, since the content of undesired types of acid present is then quite low. tienn the other hand, the alpha acid content is less than $ 20, but 12? S, is located, then the hop material solution buffer can advantageously an initial wash with a pH of 4 to 9, for example a sodium or the like Kaliurahydrogenphosphat -Buffer solution, undergo. The resulting pre-extract, which contains the undesired tannic acids, can be disposed of as waste. Generally the washing is carried out cold; However, if the pH value is below about 6, then temperatures above about 40 ° C are taken into account.

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application of the solubility of the alpha-acids ie t, / Vi rd der pll- // ert kept below about 7 so is an iriphr in length Drawn washing with more effective tannic acid removal possible. The first extract is preferably obtained using an aqueous, edible acid salt, such as Dinntrium- or dipotassium hydrogen phosphide rrii t a pll-, 7ert in area from 7 to 9 »but with a temperature above 50" C, preferably in the range from 60 ° G to 90 ° G. In this case, the Solution generally less vigorous. 3o gives a 1.4 wt / S solution of dipotassium hydrogen phosphate has a pH value of 8.5 at about 80 ° G.

If stronger alkali is used, then its concentration is too high and to precisely control its amount in order to obtain the desired selectivity of the extraction.

When the undesirable acidic materials and alpha acids have precipitated, then the remaining residue is treated with a suitable aqueous alkali to extract the remaining beta acids as a second extract. For this purpose, preferably aqueous sodium or potassium carbonate at a temperature above 40 - 5O ⁰ C, preferably used between 60 ° G and 90 ° C. A solution of about 0.5 wt, # is preferred; but this strength is by no means critical, because the strength can for example be between 0.2 and 2 wt. #. Depending on

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fetches before ¹ -U ; ■ '? i-rwen i ·' th alkali, the temperature is between 2 ^r ; ⁿ G and K) O ⁰ C inclusive, where a stronger alkali corresponds to a lower temperature.

When the rings are extracted, the essential oils are usually separated by means of solvent extraction; Internally it is also not possible to use the remainder left after the previous extractions either directly in the brewing process either by adding it to the hot short at the time or near the cooking process or by adding it to the kidney i'f-i each "state. Ks is a characteristic of the invention that the essential oils are left in the remainder that remains after the extraction of the hearing aid, and is used in this form, v / he can; if of course previously known solvent extraction techniques are used, the essential oils are first removed and the reads remaining after extraction of the acids are worthless. As a solvent, ethanol is particularly useful, which is at room temperature, ie without: - Jrhitzun- _'lf verv / is completed. Selective extraction can be achieved by adjusting the ethanol concentration. Other edible beer treaty Liehe solvents used to know,

"Ie f .: η my iixtraktionsschritte or all are with the ^lnber:;!. Hrun; brin; -en a fixed}, örpers and a liquid known techniques durchfuhrbar. In particular, if any of the extrusion steps is carried out in such a way that the lupulin concentrate occurs with the liquid extractant

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is brought into contact at the conclusion of the extraction step to produce what will be referred to as the "last pass" can give, then such last distillates are preferably kept separate from the appropriate fraction and added to the lupulin concentrate or solvent used to prepare the next batch or filling of the corresponding Extract is used. This technique is used both in continuous extraction processes and in filling extraction is applicable, serves to improve the selectivity of the extraction, it is used with a special »advantage in the Case of the first extract containing the alpha acids applied,

Better utilization of the resin fractionally is made through improvement the purity of the fractions achieved, in particular by minimizing the content of beta acids in the Alpha acid fraction, A greater purity is achieved by adding lupulin or other powdery hop material that is packed in a bed, one layer, which during de * Extraction of the various extracts undisturbed eats, This is, for example, feasible in the following two ways ^

i) By replacing the alkali with a fill of lupulin-rich » Powder or other resinous hop broth filtered will.

ii) By putting the powder in a Jiorb * »centrifuge in such a way

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pack that the layer depth is greater than 5.08 cm, and the hot alkali is sprayed on the inside of the storage. The speed of rotation of the centrifuge and the amount of alkali to be used must be coordinated so that the layer is neither seriously submerged in water nor dries out. In both cases it is generally necessary to add filter aids in order to ensure sufficient permeability of the layer. Preferred materials are either Zellu- like loose or sand. However, any similar materials, such as, for example, Kieseiguhr, gray powder or diatom powder, can also be used. It is also advantageous to maintain an inert atmosphere when extracting the alpha acid fraction, for example by means of carbon dioxide, but preferably by means of nitrogen in contact with the fractionating and fractionated solutions, and to vent the alkaline solution before use, preferably by cooking. Many continuous extractors are suitable provided that they can operate with an undisturbed storage and that the equipment can be enclosed such that an inert atmosphere is in contact with the extracting alkalis and the packed bed.

The pre-extract containing the fatty acids and other unerwUnachte Säureatoffe is normalevweiκ :: tiggeworfen * "The first extract is regardless ve ;, -., -.-- ^ m last

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Run-through that is added to a subsequent alpha-acid filling, e.g. boiled; For example, at atmospheric pressure for about 2 hours at a pil-v / ert 9, or longer at a lower pH, or at a higher pressure for a shorter period of time in order to isomerize the alpha acid. At pH 10, the alpha-acid fraction can be left at the extraction temperature overnight. The resulting solution of iso-alpha acids is preferably added directly to the wort or the fermenting beer. In this connection it is important that a satisfactory isomerization and utilization of the alpha-acid is only achieved if these are cooked separately from the beta-acids and parts of plants. The second extract is placed normally with molecular oxygen, preferably oxygen gas, at an elevated temperature, for example 70 to 90 ⁰ C in non-contact to bitter oxidation, primarily to obtain Hulupone. These can be added to the wort during cooking to give it a bitter taste, if they also support the subsequent fermentation of the wort; however, they can also be added to the fermented beer to increase the bitter substances. It has been found to be advantageous to add catalysts which allow the oxidation reaction to begin. This is achievable by adding the oxidation products to the subsequent amount of beta acid fraction that is to be oxidized.

In general it is advantageous to use the aqueous extracts

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iiiwike.l-.t

to be used as they arise at the end of the procedure. In some cases, however, it is beneficial to use the solutions focus. This can be done in two ways,

i) By evaporation or cold drying of the fractions.

ii) By crystallizing or otherwise precipitating the alpha and beta acids from their respective solutions and reusing the redissolved substances in more concentrated solutions, *

This process also serves to further purify the alpha and beta acids and creates a convenient form in which the resins can be stored either for subsequent processing or for direct use in brewing. In order to obtain a good yield of alpha acids "is suitably an edible acid salt solution such as aqueous KaIiMm- or sodium citrate, used for the first extraction stage and edible during crystallization g öäure, such as citric acid, is added slowly until a pH - ^,! / ert 5 is reached, Hach the filtering of the alpha-acids which is at least partially present in the form of their potassium or Jia-rtriumsalze makes the addition of potassium or sodium hydroxides, the remaining solution suitable for Wiedeiv extraction of lupulinreicherem jPulver, an advantageous The technique for slowly lowering the pH during crystallization consists in passing carbon dioxide through the solution

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to bubble, with carbon dioxide being considered an edible acid. This is the preferred method to lower the pH of the beta acid fraction. In both cases, it is advantageous in terms of yield to keep ^{the temperature close to 0 0 O during the crystallization.}

The remainder after the extraction steps can be as is, used or treated to isolate or concentrate the essential oils. Then, If the oils are extracted using ethanol or other organic solvents, the ethanol can be extracted by low pressure evaporation be removed in an inert atmosphere. The resulting concentrate can either be added directly to beer can be added to give hop flavor or to be further differentiated, e.g. by fractional distillation, before it is wholly or partly added to the beer.

Desirable fractionation of the essential oil is obtained by extracting the remaining lupulin with aqueous ethanol. The concentration of ethanol is generally between $ 60 and $ 100, preferably between $ 80 and $ 90. In the brewing of beer, the residual lupulin containing the essential oils, or any these oils is containing and an incompatible of here- solvent-free extract zti the wort given at or near the end of the cooking period as a substitute for the aromatic hops which often warming added to the final stage of wort boiling.

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The following examples illustrate embodiments of the invention.

example 1

15 grams of lupulin-rich powder obtained from hops of the Bramling Cross variety and with an alpha acid content of $ 20.2 (according to spectrophotometry) is mixed with 150 grams of coarse-grained, acid-washed sand and placed in a "water-jacketed column 10 cm in length and 2 cm diameter packed. 200 ml of cold, 2.4 ^ strength aqueous Dikaliumhydrogenphospat is flushed through the bed, followed by 20 ml of distilled water. the pre-extract obtained by this solution is discarded. water having a temperature of 65 ⁰ C is circulated through the jacket of the column and 2.4 $> aqueous potassium hydrogen phosphate at 70 ° C. is passed through the packed layer, a total washout of 700 ml is obtained which contains 0.40 % alpha acids (according to spectrophotometry), which is a yield of 94 i> . This solution is the first, the AlpHa acid extract. A little distilled water (approx. 20 ml) is again passed through the column, followed by 0.5 tiger aqueous K aliumcarbonat of 70 ⁰ C. A Auewaschung of total 200 ml is obtained, which contains 0.57 $> Beta-acid (according üpectrophotometrie) and represents the second or beta-acid extract is.

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To the alpha acid extract there is enough aqueous solution Potassium hydroxide added to raise the pH to 9. These The mass is boiled under a nitrogen atmosphere, allowing the removal of unwanted volatile substances for the purpose of boiling is. After two hours, the remaining alpha acids are in a concentration of less than 0.02% (according to Spectrophotometry and thin-layer chromatography). If this total amount obtained is added to 60 liters of beer, its bitterness increases by 28 European degrees of bitterness (EBU).

The temperature of the second, the beta acid ^{extract, which is collected from the acid, is raised to 80 °} C. and the extract is continuously moved back and forth under an oxygen atmosphere for 8 hours. Low overpressure ensures uniform dissolution of the oxygen. After the eight hours only small amounts of the beta acid remained unoxidized. Adding this volume to the beer mentioned, which has already been dealt with with the first fraction, increases its bitterness by another two EBU.

The remaining lupulin is removed from the column and transferred to the 60 1 prepared bitter beer is given and after 12 hours the hopping of the beer completely.

An equal degree of bitterness (30 EBU) in 60 liters of beer using conventional wort boiling technology would produce 29.7 g of lupulin b * i 2O, 2f

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Alpha acids require that a pus 1.5 g were used for dry hopping necessary aein, as amounts to a total of 31.2 g. The misuse of lupulin is therefore at least doubled by the method according to the invention.

If more Γ - Π ium hydroxide is added to the alpha acid fraction should have been in order to increase the pH to 10, then it could be held at about 65 ° C for 24 hours instead of being boiled if less than 0.03% Alpha acid would remain unisomerized. Of course you can Economic considerations are the use of iso-alpha acid solutions prescribe in which the degree of isomerization has not yet been carried out quite so far.

The remaining lupulin, instead of being added as it is removed from the column, could be extralated with 10 μl of ethanol v / earth, after which the ethanol is evaporated from the extract, so that a viscous liquid containing 0.15 g of oil is obtained.

An addition of this oil, at a ratio of 0.5 parts per million, ^ For beer, it is sufficient to discover the essential oils in the aroma of the beer.

Example 2

15 g lupulin-rich powder from hops of the Styrian variety and with 28,6, ^ alpha acids are mixed with 150g coarse-grained, acid-washed sand and 150g of coarse gravel clock and (then packed in a column as in Example 1. The bed is extracted with 100ml, cold 2.8 # aqueous disodium hydrogen phosphate and then distilled with 20ml cold

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V / assers. The resulting pre-extract is added to the waste. Water of 62 C is circulated through the jacket of the column and 2.8 $ ige3 aqueous disodium hydrogen phosphate is passed through the bed at a temperature of 62 ⁰ C. A total of 700 mL of leaching is achieved containing 0.55 $ Alpha acids wajeinem yield of $ 90. A small amount of distilled water is then passed through the column until 0.5 $ aqueous sodium carbonate with a temperature of 62 ^° C. follows. A total wash of 350 ml is obtained containing $ 1.05 beta acids. The remainder can be treated according to Example 1.

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Claims (12)

Claims 1. A method for the extraction treatment of resin-containing hops material, characterized in that extraction of the material with aqueous alkali takes place at a controlled elevated temperature and at a controlled pH value in order to selectively extract the alpha acids, and then extraction of the residue takes place to form the beta acids to extract 2. The method according to claim 1, characterized in that an initial washing of the material with an aqueous agent at ™ controlled temperature and controlled pH takes place in order to extract separately tannic acids and acidic substances different from alpha and beta acids. 3. The method according to claim H _1, characterized in that the initial washing is carried out with a buffer solution of pH 4 to 9. 4. The method according to claim 3ι, characterized in that the ([buffer solution has a pH value of 7 to 9 and the temperature is kept low enough to prevent a substantial solution of the alpha-acid content of the broken hops. 5. The method according to claim 3, characterized in that the pH of the buffer solution is approximately 4-6. 6. The method according to claim 3 »4 or 5 _f, characterized in that the initial washing is carried out with a sodium or potassium hydrogen phosphate buffer solution, 009849/1215 " ² " 2000889 7. The method according to one of the preceding claims, characterized in that the alpha acids are extracted at a temperature above 40 C and at a pH of 7 to 9. 8. The method according to claim 7, characterized in that edible aqueous sodium or potassium acid salt at a temperature above 50 C is used. 9. The method anch one of the preceding claims, characterized gekennzeichne t, that the beta-acids having a v / ässrigen sodium or potassium carbonate solution are preferably extracted at a temperature of about 5O ⁰ C. 10. The method according to any one of the preceding claims, characterized in that the essential oils which remain after the extraction of the alpha and beta acids are separated from the rest by extraction using an edible solvent. 11. The method according to claim 1, 2 or 3, characterized in that the alpha acids are extracted with aqueous, edible sodium or calcium acid salt and the alpha acid crystallizes out, the crystallization being supported by the uptake of edible acid. 12. The method NaOH claim 1, 2 or 3, characterized gekennze i seframe that aqueous sodium or potassium carbonate used wi.d, 009849/1215 to extract the beta acids, taking the beta acids nut crystallize and the crystallization is supported by the addition of edible acid. 5ο The method according to claim 12, characterized in that the edible acid is carbonic acid and the extract is saturated with carbonic acid. ORIGINAL INSPECTED 009849/121 5