DE1517782A1 - Process for the production of a hop extract containing isohumolones - Google Patents

Description

46 019 I.

Stafford Allen & Sons limited, Wharf Road, London IT. 1st, England

Process for the production of a hop extract containing isohumolones

The present invention relates to a "process for the preparation of solvent extracts Hops, namely from extracts containing isohumolones.

In the patent application St 21 973 IVa / 6a (Patent from which the present patent application dropped out is, a process for the production of purified hop extracts is described, after which a raw Hops extract brought into contact with an aqueous lower alcohol, preferably 90% methanol “Furthermore, a process for isomerizing the humolone component is described in the application mentioned of such a purified hop extract described, wherein the purified extract is dissolved in a water-immiscible solvent, the solution shaken with aqueous alkali, the two phases are separated and the aqueous phase is heated.

Although the aqueous., Lower alcohol for use wi ^ 009841/0168 ^B

Primary extraction solvent is less suitable, it dissolves according to the method described above v / on the humolones and other active flavors contained in hop extracts, which were produced by conventional methods. However, it does not solve certain problems for the time being Components of conventional hop extracts that are detrimental to the taste of the beer impact.

It is desirable to convert the humolones to isohumolones and it has long been known to do so caused by boiling with aqueous alkali. However, this method has no general application found, because hops and most of the hop extracts made from them so far have certain constituents which tend to deliver undesirable flavors when mixed with water Be brought into contact with alkali. This problem was addressed according to the parent application mentioned above (the above-mentioned parent patent) solved in that the purified extract in a water immiscible organic solvent was dissolved and shaken with aqueous alkali, whereupon the Humolone in the aqueous phase pass over, while any other substances that cause undesirable Flavors are in the organic phase

BAOC-L

It has now been found that an isohuraolone containing Hop extract that has many of the advantages of being prepared by the parent application process Hops extract, produced according to a modified method of this process can be.

To the initial manufacture of a purified To eliminate the extract is obtained by the modified method according to the present invention of heads with a rait y / ater "no miscible organic solvent extracted, the solution concentrated, with aqueous alkali shaken, whereupon the two phases are separated. This process leads to the formation of a raw alkaline extract. The Huniolon component this extract becomes more alkaline by heating it. Solution isomerized in the usual way, wherein a raw alkaline extract is formed, the sodium isohumolates and some of the undesirable, in! «! ethanol more insoluble. Contains substances that need to be removed.

It was found that the treatment with 90>; iger. Methanol ger.äß the above-mentioned. Stamni notification (of the above-mentioned Stannpater.tes} not indirect

009841/0 T68. ^{BATHROOM 0RäQ1NAL}

bar can be applied to the purification of an alkaline isoinerized raw Ilopfen extract, since the undesired substances through contact with the alkalis in? 0? oiger. Methanol can be solubilized. It just got. found dat. 1st it possible to produce an acceptable Isohumolone containing extract characterized in that the crude alkaline extract dee with a solvent containing 60-85 ^ methanol in water 15-20 ⁰ Jo "sov / ie with a genügpriden Kenge acid to adjust pH -The value of the solution is brought into contact to a value between 2 ur.ö 7, the solution is separated from the undissolved substances and the methanol is driven off.

The present invention accordingly relates to a displacer. z>; r "'creation of a lsoh.uir.clone containing jlcp * 'ene: -: tract, which is characterized by because 'hops' ::: i.t an organic that cannot be mixed with water. L ^ s-infe-Hrmittel to form a solution of a rawer. licpfenextraktes ir. brought in contact, the solution freed from insoluble Steffen, then brought into contact with aqueous alkali, the aqueous phase of the organic phase separated, the aqueous phase heated, the iscmerized extract from the aqueous. Obtained by adding acid to a phase

009841/0168

BAD ORIGJNAL

-3-

brought pH-value between 2 and 7 is set and with a sufficient to dissolve a portion of the neutralized extract amount of 80-85 ^c p of methanol and 15-20 <fi water-containing solvent into contact, separating the solution from undissolved substances and the dissolved part of the extract is obtained.

Alkali is expediently added to the end product in order to obtain a stable extract, the ITodium isohumolate contains.

Preferred water-immiscible solvents for extracting the hops are hydrocarbons and halogenated hydrocarbon solvents, for example light petroleum, carbon tetrachloride and chloroform. A particularly suitable extract solvent is benzene.

The hops can expediently be ground, for example in a high-speed hammer mill. Then can an excess of the extracting solvent may be seeped through at room temperature. The hops can also be slurried with the solvent and then from the insoluble substances for example

9841/0168

separated by filtration or centrifugation will.

The organic solution is then shaken with aqueous alkali and the two phases become separated. The aqueous phase is boiled to remove any remaining extraction solvent to remove and isomerize the Humolone_.

Potassium hydroxide is preferably used as the alkali. However, sodium hydroxide can also be used. The concentration of the alkali used is not critical. However, a concentration between 2 and 20 fo (weight to volume) is preferred. Preferably, just as much alkali is used as is necessary to bring the pH of the solution to a value between 10.7 and 12, preferably 10.7 and 11, after the extraction.

According to a modified embodiment of the isomerization process Sodium or potassium hydroxide is used as an alkali during cooking the alkaline solution, however, carbon dioxide gas passed through it, causing sodium or potassium carbonate is formed in the solution and an inert atmosphere is maintained.

BATH ORIGINAL 009841/0168

It is long, preferably at least 1 hour boiled at atmospheric pressure and then Solu nr concentrated, for example by Abdes'til? lerer the bulk of the water under reduced pressure.

The impure isomerized extract is brought into contact with 6O-H5 £ i.-jen: aqueous methanol and acid, preferably hydrochloric acid. Purification can be carried out by bringing the impure extract into just as much absolute! - 'ethanol as is necessary to read the extract, after which hydrochloric acid is added to adjust the pH to 7-2. Finally, "water" is also added in order to bring the water body to 1rr-2C ^r 'ειι.

The product is then centrifuged, and the insoluble residue with 80% aqueous methanol washed. The detergents become the main kidney Solution given and the! 'Ethanol by distillation oil removed. It is preferred to have enough alkali to the. Add product to adjust the pH value to 10-12, " preferably set to 10.5.

The method according to the present invention is

0098-1 / 0168

especial.os for the extraction of dried on hop kilns Hops applicable. It can also be used to extract freshly grown hops.

The invention is illustrated by the following examples explained regarding! kiln hops:

I; egg oriel 1:

-5.36 kr: a crude hop extract obtained by extraction prior hops with benzene using a Lcsunirsr.ittel / LIOP ^ enverhV.ltnisses of 5: 1 was prepared at a temperature of 20-25 ⁰ C, with a such. Amount of a 10 percent by weight solution before potassium hydroxide is stirred as is necessary to give the aqueous layer a pH of 11.0 after separation. The required amount of the alkali solution fluctuates with the :, Hbpfen concentrate used in each case. In the present. For example, it was about 57 liters (12.5 gallons). After allowing several hours to settle, the aqueous solution was poured off and washed with benzene. (23 1 corresponding to 5 gallons). The original Senzene solution was extracted again with water (4.55 equivalent to one gallon). The water was again poured off and with the

009841/0168 ORIGINAL BATHROOM

washed second benzene extract. The watery ones. Solutions were combined and boiled under normal pressure for one hour in order to remove dissolved solvent and to bring about isomerization. The solution was then concentrated under reduced pressure to obtain 45.36 kg of a viscous extract. 27.216 kg of this isomerized viscous extract (moisture content 16 fo) was dissolved in 91 l (20 gallons) of pure methanol. 11.4 liters (2.5 gallons) of 4 normal aqueous hydrochloric acid and 6.8 liters (1.5 balloons) of water were added with stirring so that the total methanol content in the solvent mixture is 80 percent by volume. The mixture was centrifuged and the clear supernatant (pH-l \ ^r ert 3,1) separated. The residue was sequentially washed with 3 servings of 11.4 liters (2.5 gallons) SO volume percent methanol each time, separating each time by centrifugation. The combined methanolic extracts were distilled to remove the methanol, then cooled and treated with 22.751 (5 gallons) of 2 normal aqueous potassium hydroxide solution. After evaporation of the solution, 22.68 kg of a dry solid which could easily be pulverized is obtained.

BATH ORIGINAL 009841/0168

Example 2; ,

The procedure described in Example 1 "was followed repeating the amendment that the unpurified isomerized extract was dried and ground, whereby 22.68 kg of a powder was obtained. This powder was in 91 l (20 gallons) pure ! ■! Ethanol dissolved. Then one after the other 13 »6 Added (3 gallons) 4 normal aqueous hydrochloric acid and 9.1 liters (2 gallons) distilled water. The pH of this mixture was 2.0 and the volume ultimately used was 2 normal aqueous potassium hydroxide solution was 27.3 liters (6 gallons). The yield of the purified isomerized product was 23.13 kg.

Patent claims: 0 09841/0168

Claims (1)

Claims; · Process for the preparation of an Isohumolor.e containing hops extract, characterized in that hops with a water not miscible, organic solvent to form a solution of a crude. Hops extracts brought into contact, the solution freed from insoluble components, then . in contact with aqueous alkali, the aqueous phase separated from the organic phase, the aqueous phase heated, the: somerized extract from the väCrl _; -cr. Obtained by adding acid on a phase. pH adjusted to 2-7 and. ndt of the neutralized extract sufficient amount of an existing one euc solving a part of 80- ^ 5 <· methanol and 15-20 i> water. Bringing the solvent into contact, separating the solution from insoluble substances and recovering the dissolved part of the extract. 2. The method according to claim 1, characterized in that that as a water-immiscible solvent a hydrocarbon or a 009841/0168 halogenated hydrocarbon, preferably benzene, is used 3 * The method according to claims 1-2, characterized in that the solvent with the water-immiscible solvent home room temperature are brought into contact _m. 4. Process according to Claims 1-3, characterized in that hydrochloric acid is used as the acid. 5. Process according to claims 1-4, characterized in that the isomerized extract is made alkaline at the end of the process, preferably to a pH value of at least 10.5. 6. The method according to claims 1-5 » characterized in that ala aqueous alkali a sodium or potassium hydroxide solution is used. 7. The method according to claims 1-6, characterized in that the concentration of the alkali solution is 2-20 percent by weight . 8. The method according to claims 1-7, characterized by 009841/0168 that the pH value of the aqueous phase after the Iη contact with that with water does not miscible solvents between 10.7 and 12, preferably between 10.7 and 11. 9. Process according to claims 1-8, characterized in that that the crude isomerized extract In the final stage, the amount of methanol required to dissolve the extract is added, then the pH value was adjusted to 2-7 by adding hydrochloric acid and finally as much water was added becomes that the water content is 15-20 volume percent. 009841/0168 BATH ORIGINAL