SI8811843A

SI8811843A - Procedure for the production of isomerized hops tablets.

Info

Publication number: SI8811843A
Application number: SI8811843A
Authority: SI
Inventors: Ronald Burkhard; Richard Wilson
Original assignee: Steiner Hops Ltd
Priority date: 1987-10-02
Filing date: 1988-10-03
Publication date: 1996-12-31

Abstract

Postopek za stabilizacijo in izomerizacijo alfakislin v hmelju z obdelavo zdrobljenega hmelja s kalcijevim ali magnezijevim oksidom ali hidroksidom, da tvorimo kovinske soli in nadalje z izpostavitvijo povišani temperaturi, medtem, ko poteka izomerizacija v izo-alfa-kisline, značilen po tem, da zmes hmelja in kalcijevega ali magnezijevega oksida ali hidroksida oblikujemo v obliko tablet pod nadzorovanimi pogoji, da minimiziramo izomerizacijo.Tablete pakiramo ob odsotnosti kisika in zavarimo v pakete in nadalje podvržemo nadzorovanemu segrevanju na okoli 40-50 stopinj Celzija za obdobje vsaj ene ure.Temperaturo in vsebnost kalcijevega ali magnezijevega oksida ali hidroksida izberemo tako, da poteče skoraj popolna izomerizacija.Process for the stabilization and isomerization of alphacids in hops by treating crushed hops with calcium or magnesium oxide or hydroxide, to form metal salts and further by exposure elevated temperature while the isomerization takes place to iso-alpha-acids, characterized in that the mixture hops and calcium or magnesium oxide or hydroxide is formed into a tablet form under controlled conditions conditions to minimize isomerization.Tablets packed in the absence of oxygen and welded into packages and further subjected to controlled heating at about 40-50 degrees Celsius for a period of at least one hours.Temperature and content of calcium or magnesium of the oxide or hydroxide is selected such that almost complete isomerization expires.

Description

POSTUPAK ZA DOBIVANJE IZOMERIZOVANIH TABLETA HMELJAPROCEDURE FOR OBTAINING ISOMERIZED TABLES OF HOPES

Oblast tehnike u koju spada pronalazakFIELD OF THE INVENTION

Ovaj pronalazak se odnosi na postupak za proizvodnju tableta hmelja u kojima su alfa-kiseline izomerizovane u izo alfa-kiseline.The present invention relates to a method for the production of hop tablets in which alpha acids are isomerized to iso alpha acids.

Poštoji veliki interes za tablete hmelja, zbog uobičajenog načina koriščenja gorkog potencijala u kombinaciji sa aromatičnim potencijalom, u odsustvu neželjenih pratečih sastojaka kao što su organski rastvarači.There is a great deal of interest in hops pills, because of the usual way of using bitter potential in combination with aromatic potential, in the absence of unwanted side ingredients such as organic solvents.

Tehnički problemTechnical problem

Tehnički problem koji je rešen ovim pronalaskom sastojao se u torne da se u postupku proizvodnje izomerizovanih tableta hmelja obezbedi takvo zagrevanje tableta u vakuuraskom pakovanju da unutrašnje tablete u paketu prime odgovarajuču količinu toplote, a da pri torne ne dode do pregrevanja spoljašnjih tableta u paketu.A technical problem solved by the present invention consisted in the towers in the process of manufacturing isomerized hops tablets to provide such a warming of the tablets in a vacuum package so that the inner tablets in the package receive an adequate amount of heat without causing the external tablets in the package to overheat.

Stanje tehnikeThe state of the art

U SAD patentu 4132561 opisan je postupak za stabilizaciju alfa-kiselina u hmelju protiv razaranja preko oksidacije na skladištenju. Stabilizacija se ostvaruje reagovanjem alfa-kiselina u sprašenom hmelju sa oksidom zemnoalkalnog metala ili hidroksidom zemnoalkalnog metala, naročito magnezijum oksidom koji se dodaje kao suvi prah. Grade se magnezijumove soli alfa-kiselina koje štite kiseline od razaranja.U.S. Patent 4132561 discloses a process for the stabilization of alpha acids in hop destroys via oxidation on storage. Stabilization is achieved by reacting the alpha acids in the powdered hops with alkaline earth metal oxide or alkaline earth metal hydroxide, especially magnesium oxide, which is added as a dry powder. Magnesium salts of alpha acids are built to protect acids from destruction.

U ovom patentu je takode opisano da dejstvo toplote na magnezijumove soli prevodi ove u magnezijumove soli alfa-kiselina. Obezbedjen je postupak koji obuhvata gradenje smeše praha hmelja i magnezijum i/ili kalcijum oksida, koja po izboru može da sadrži malu količinu alkohola, na primer metanola, zagrevanje smeše do temperature od oko 40°C do oko 100°C, održavanje smeše na ovoj temperaturi kratko vreme, na primer od oko 5 do oko 60 minuta, dok se odvija izomerizacija, i tada hladenje smeše do sobne temperature. Kako se pri formiranju tableta presovanjem stvara toplota, postupak je predvideo kombinaciju dva stupnja tako da se tablete ostave da dostignu temperaturu od oko 75°C i dalje se drže na toj temperaturi kratko vreme kako bi se dozvolilo da se izvrši izomerizacija.This patent also describes that the effect of heat on magnesium salts translates these into magnesium salts of alpha acids. A process is provided comprising the construction of a mixture of hop powder and magnesium and / or calcium oxide, which may optionally contain a small amount of alcohol, for example methanol, heating the mixture to a temperature of from about 40 ° C to about 100 ° C, maintaining the mixture at this for a short time, for example from about 5 to about 60 minutes, while the isomerization takes place, and then the mixture is cooled to room temperature. As the heat of the tablets is formed by pressing, the process envisaged a combination of two steps so that the tablets were allowed to reach a temperature of about 75 ° C and kept at that temperature for a short time to allow isomerization to take place.

Mada je oblast od 40°C do 100°G navedena u patentu, jasno je da je krajnja granica ove oblasti bitna za izomerizaciju. U stvari, u poslednjoj publikaciji (M3AA Technical Quarterly, Vol 16, br. 2, 1979), Grantje pokazao da alfa-kiseline mogu biti držane mesečima na temperaturama od 40°C ili čak visim bez gubitka gorkog potencijala i mogu biti efikasno prevedene u izo alfa-kiseline kada se dodaju u ključalu pivsku siru.Although the range of 40 ° C to 100 ° G is stated in the patent, it is clear that the extreme limit of this area is essential for isomerization. In fact, in a recent publication (M3AA Technical Quarterly, Vol 16, No 2, 1979), Grantje showed that alpha acids can be held for months at temperatures of 40 ° C or even higher without losing their bitter potential and can be effectively translated into alpha-acid iso when added to boiling cheese.

- . -3.--: Kratki periodi na visokoj temperaturi izazvace izomerizaciju ali stepen dobivene izomerizacije zagrevanjem u kalupu za tabletiranje ili tretman tableta pomocu visoke temperature za relativno kratko vreme, nije standardan i podložan je raznim varijacijama. Dalje, grejanje na relativno visokim temperaturama u priusustvu vazduha krajnje je nepoželjno. Cak i kada su alfa-kiselinezašticene tako što se prevode u svoje magnezijumove soli i izomerizuju se, druge komponente hmelja, naročito isparijiva ulja mogu se izgubiti ili pokvariti. Takode postoji tendencija da se tablete nepotrebno isuše i ovaj problem ne bi trebalo rešavati zagrevanjem pod inertnim gasom.-. -3 .--: Short periods at high temperature will cause isomerization, but the degree of isomerization obtained by heating in a tablet mold or treating the tablet with high temperature for a relatively short time is not standard and is subject to various variations. Furthermore, heating at relatively high temperatures in the presence of air is highly undesirable. Even when alpha acids are protected by being converted to their magnesium salts and isomerized, other components of hops, especially volatile oils, can be lost or spoiled. There is also a tendency for the tablets to dry out unnecessarily and this problem should not be solved by inert gas heating.

Alternativno zagrevanje tableta posle njihovog vakuumskog pakovanja vrlo je teška operacija. Problem je osigurati da adekvatna količina dosegne unutrašnje tablete u centru paketa, bez pregrevanja spoljašnjih tableta.Alternatively heating the tablets after vacuum packing is a very difficult operation. The problem is to make sure that the adequate amount reaches the inner tablets at the center of the package without overheating the outer tablets.

Ovo se može postici mikrotalasnim zagrevanjem, ali visoko temperatursko mikrotalasno zagrevanje vakuumiranih paketa povlači sobom i problem kontrole delimično i zato što je reakcija egzotermna ali uglavnom zato Što stepen zagrevanja zagrevanja dobiven u jedinici vremena zavisi od sadržaja vode u hmelju, koji može da varira od uzorka do uzorka. Dalje, bilo bi vrlo teško sprečiti sporedne reakcije kada se tablete ne bi mogle ohladiti brzo i ravnomerno.This can be achieved by microwave heating, but the high temperature microwave heating of the vacuum packets entails a control problem partly because the reaction is exothermic but mainly because the degree of warming obtained in a unit of time depends on the water content of the hops, which may vary from sample to the sample. Further, it would be very difficult to prevent side effects when the tablets could not be cooled quickly and evenly.

Medutim, problemi mogu nastati u pivari ako hmeljni proizvod datog sadržaja alfa-kiseline nema konstantan stepen izomerizacije. Tako, proizvod koji sadrži uglavnom neizomerizovane alfa-kiseline duže če ključati od proizvoda koji sadrži istu celokupnu koncentraciju alfa-kiselina, ali u kojem je znatan deo izomerizovan. Uniformnost standarda je od najveceg značaja za korisnika u pivari.However, problems can arise in a brewery if the hop product of a given alpha-acid content does not have a constant degree of isomerization. Thus, a product containing substantially unisomerized alpha acids will boil longer than a product containing the same overall concentration of alpha acids, but in which a substantial portion is isomerized. The uniformity of the standard is of paramount importance to the user at the brewery.

Stoga, poštoji potreba za postupkom za proizvodnju tableta hmelja koje su hemijski stabilne i koje su izomerizovane sasvim ili bar u standardizovanoo i ponovijivom obimu.Therefore, there is a need for a process for producing hops that are chemically stable and isomerized entirely or at least on a standardized and reproducible scale.

Opis rešenja tehničkog problemaDescription of solution to a technical problem

Neočekivano, mi smo sada pokazali da je moguce dobiti visok i ponovljiv stepen izomerizacije podvrgavanjem vakuumiranih paketa mnogo nižim temperaturama tokom dužeg vremenskog perioda. Postupak je bezbedan i vrlo efikasan, kojim se dobiva vrlo uniformna izomerizacija kroz pakete, i lako se može industrijski ostvariti.Unexpectedly, we have now shown that it is possible to obtain a high and repeatable degree of isomerization by subjecting the vacuum packets to much lower temperatures over a long period of time. The process is safe and very efficient, which gives a very uniform isomerization through packages, and is easily industrially achievable.

Prema pronalasku mi smo obezbedili postupak za stabilizaciju i izomerizaciju alfa-kiselina u hmelju tretiranjem isitnjenog hmelja sa kalcijum ili magnezijum oksidom ili hidroksidom u cilju gradjenja soli metala i njenim podvrgavanjem povišenoj temperaturi radi odvijanja izomerizacije u izo alfa-kiseline, okarakterisan time, što se smeša hmelja i kalcijum ili magnezijum oksida ili hidroksida oblikuje u tablete pod kontrolisanim uslovima radi minimizacije izomerizacije, tablete se pakuju i zatapaju u odsustvu kiseonika i zatopljeni paketi se podvrgavaju kontrolisanom zagrevanju na oko 40°C do 55°C tokom perioda od bar jednog dana, vreme, temperatura i sadržaj kalci jum ili magnezijum oksida ili hidroksida se tako biraju da obezbede potpunu izomerizaciju.According to the invention, we have provided a process for the stabilization and isomerization of alpha acids in hops by treating the squeezed hops with calcium or magnesium oxide or hydroxide for the purpose of forming a metal salt and subjecting it to an elevated temperature to carry out isomerization to iso alpha acids, characterized by being blended hops and calcium or magnesium oxide or hydroxide form into tablets under controlled conditions to minimize isomerization, the tablets are packaged and sealed in the absence of oxygen and the warmed packages are subjected to controlled heating at about 40 ° C to 55 ° C for a period of at least one day, time , the temperature and content of calcium yum or magnesium oxide or hydroxide are thus chosen to ensure complete isomerization.

U izomerizacionim postupcima iz prethodne tehnike, gubi se znatan deo prirodnih ulja i ima oštecenja arome proizvoda dobivenih sa takvim hmeljnim proizvodima (tretiran hmelj).In the isomerization processes of the prior art, a considerable part of the natural oils is lost and there is damage to the aroma of the products obtained with such hop products (treated hops).

U alternativnom aspektu, ovaj pronalazak obezbedjuje hmeljni proizvod u kome su uglasvnom sve alfa-kiseline izomerizovane u izo-alfa-kiseline i koji je zadržao glavninu prirodnih ulja.In an alternative aspect, the present invention provides a hop product in which substantially all alpha acids are isomerized to iso-alpha acids and which retains the bulk of natural oils.

Pronalazak takodje obezbedjuje pivo zagorčeno pomoču hmelja tretiranog pre*aa ovom pronalsku.The invention also provides a brewed beer with the aid of hops treated with the invention.

Pri pripremanju tableta bazne uslove date u napred-pomenutom SAD patentu treba podesiti. Prvenstveno,sprašeni magnezijum oksid treba dobro sjediniti sa sprašenin ili na drugi način isitnjenim hmeljom na sobnoj tenoeraturi pri količini od 4$ mase hmelja. Odnos magnezijum oksida prema hmelju zavisi delimično od sadržaja alfa“kiseline hmelja i količina magnezijum oksida se tako bira da bude u malom stehiometrijskom višku od količine potrebne za gradjenje soli alfa-kiseline. Veče količine se dodaju radi ubrzavanja izomerizacije, i važno je obezbediti da nedodje do pregrevanja. Alternativno magnezijun oksid iWhen preparing the tablets, the base conditions set out in the aforementioned United States patent should be adjusted. Primarily, the powdered magnesium oxide should be well combined with the powdered or otherwise squeezed hops at room temperature at an amount of $ 4 by weight of hops. The ratio of magnesium oxide to hops depends in part on the content of the alpha 'acid of the hops and the amount of magnesium oxide is thus chosen to be in a small stoichiometric excess of the amount required to build the alpha-acid salt. Larger amounts are added to accelerate isomerization, and it is important to ensure that it does not overheat. Alternatively magnesium oxide and

6.6.

hmelj se mogu izmešati prevrtanjem posle čega se smeša . samelje u prah. Uopšteno sadržaj magnezijum oksida od 0,5 ho tipično 1,2 do 5,2%, naročito oko 1,5 do 2,5% mase, može da se koristi. Ako je potrebno, mogu se dodati male količine vode pre tabletiranja radi postizanja odgovarajuee konzistenci je. iledjutim, nije normalno pogodno činiti to.hops can be mixed by rolling over and then blending. grind to powder. In general, a magnesium oxide content of 0.5 ho, typically 1.2 to 5.2%, especially about 1.5 to 2.5% by weight, can be used. If necessary, small amounts of water may be added prior to tabletting to achieve a consistent consistency. However, it is not normally appropriate to do so.

Poželjno je koriščenje magnezijum oksida ili hidroksida· Kalcijum oksid uopšteno je manje efikasan i teži da izazove oslobadjanje toplote u stupnju kompresije. Magnezijumove soli takve kao karbonat su manje efikasne i ne sprečavaju gradjenje gasa koji uslovljava probleme pakovanja. Oksid sa druge strane, reaguje efikasno, izaziva manje oslobadjanje toplote i sprečava gradjenje gasa koje se inače gradi kada se hmelj zagreva,Use of magnesium oxide or hydroxide is desirable · Calcium oxide is generally less effective and tends to cause heat release in the compression stage. Magnesium salts such as carbonate are less effective and do not prevent the build up of gas, which causes packaging problems. Oxide, on the other hand, reacts effectively, causes less heat release, and prevents the build-up of gas that is otherwise built when the hops are warmed,

U cilju minimiziranja zagrevanja tokom tabletiranja, propusni kapacitet kalupa treba kontrolisati radi sprečavanjapreterane kompresije i dužinu otvora treba držati na minimumu tako da toplota kompresije nože rasturiti. Lokalno zagrevanje u kalupu treba izbeči, zato što se trenutno mogu dobiti visoke temperature koje su vrlo Štetne. Preporčljivo je takodje i poliranje površina kalupa čime se smanjuje trenje. Radi izbegavanja znatnije izomerizacije tokom tabletiranja, obično je potrebno osigurati pomoču gornjeg načina da temperatura tablete koja napušta kalup ne prelazi 60°C. Poželjno je hladiti tablete pre njihovog pakovanja mada ovo r.ije kritično. U vezi sa tim, intezivno hladjenje vazduhom može da izazove oksidaciju, sto može isto i produženo izlaganje vazduhu na višoj temperaturi. Tako poželjno je spakovati tablete oez odlaganja.In order to minimize heat during tableting, the leakage capacity of the mold should be controlled to prevent excessive compression and the length of the orifice should be kept to a minimum so that the compression heat of the blade is dispersed. Local heating in the mold should be avoided, as high temperatures can be present which are very harmful. Polishing of mold surfaces is also recommended, which reduces friction. In order to avoid significant isomerization during tableting, it is usually necessary to provide the above method so that the temperature of the tablet leaving the mold does not exceed 60 ° C. It is advisable to cool the tablets before they are packaged, although this is critical. In this regard, intense air cooling can cause oxidation, which can also cause prolonged exposure to higher temperatures. It is so desirable to pack the pills oez disposal.

Tableta treba tada pakovati u odsustvu kiseonika, npr. pod vakuumom ili pod inertnim gasom takvim kao što je azot. Ovo se može ostvariti pomoču nekog od poznatih postupaka. Za komercijalne svrhe, tablete hmelja se poželjno pakauju u količinama od 5» 10» 20 ili 25 kg u plastični film ili folije koje se toplotno zatapaju.The tablet should then be packaged in the absence of oxygen, e.g. under vacuum or under an inert gas such as nitrogen. This can be accomplished with the help of one of the known methods. For commercial purposes, hops tablets are preferably packaged in quantities of 5 "10" 20 or 25 kg in plastic film or heat-sealing foils.

Pakovanje pod inertnim gasom je poželjno u donsu na vakuumsko pakovanje jer tablete ostaju razdvojene i ne povezuju se u Čvrste mase. Jednom spakovane tablete, mogu se toplotno kondicionirati prema pronalssku njihovim održavanjem na temperaturi od oko 4-0 do 55°C, poželjno oko 4-3 do 54°C, najpoželjnije oko 4-5 do 50°C. Temperatura ne treba da prelazi 55°C jer na visim temperaturama postoji jasna opasnost da egzotermna reakcija postane nekotrolisana.Packaging under inert gas is preferable in a vacuum-packed container because the tablets remain separated and do not bind into solids. Once packed, the tablets can be heat-conditioned according to pronals by maintaining them at a temperature of about 4-0 to 55 ° C, preferably about 4-3 to 54 ° C, most preferably about 4-5 to 50 ° C. The temperature should not exceed 55 ° C because at higher temperatures there is a clear risk of the exothermic reaction becoming uncontrolled.

Toplotni tretman treba vršiti bar jedan dan, uopšteno od 2 do 30 dana, poželjnije 5 do 15 dana i naročito 7 do 10 dana. Očigledno, dužine tretmana zavisi od odabrane temperature i takodje u izvesnoj meri od količine kalcijum ili magnezijum oksida ili hidroksida i prisutnih alfakiselina. Kondicioniranje se uobičajeno može izvestiHeat treatment should be performed for at least one day, generally from 2 to 30 days, more preferably 5 to 15 days and especially 7 to 10 days. Obviously, the length of treatment depends on the temperature selected and also to some extent on the amount of calcium or magnesium oxide or hydroxide and the alphacids present. Conditioning can usually be performed

8<8 <

magacioniranjem platformi opterecenih sa kesama na sobnoj tenperaturi od recimo 50°C i tada njihovim premeštanjem iz magacina u odgovarajuče vreme. Radi preciznosti, pogodno je uzimati magacionirani materjal u intervalima i na kraju toplotnog tretmana kada se postigne zahtevani stepen izomerizacoje npr. 90 do 100%, poželjno 95-98%. <->bim izomerizacije može se lako ispitati intervalskim testiranjem individualnih uzoraka platformi (obično oko 5θβ) koje su distribuirani kao minijaturni vakumski paketi na i ispod platformi. Efiksanost cirkulacije vazduha oko kesa i ispod platformi je bitna radi obezbedjivanja potpunog grejanja. Preporučljivo je izolovati pod, zidove i tavanice zagrejane sobe ili skladište koriščeno za izomerizaciju tableta. Poželjno, ali nije bitno izomerizacija se završava premeštanjem tableta u hladnu prostoriju koja ima dobru oirkulaciju vazduha.by magnifying the platforms loaded with bags at room temperature of, say, 50 ° C and then moving them from the warehouse at the appropriate time. For the sake of precision, it is convenient to take the magnesium material at intervals and at the end of the heat treatment when the required degree of isomerization is achieved, e.g. 90 to 100%, preferably 95-98%. <-> bim isomerization can be readily investigated by interval testing of individual platform samples (typically about 5θβ) distributed as miniature vacuum packets on and below the platforms. The efficiency of the air circulation around the bags and under the platforms is essential to ensure complete heating. It is advisable to insulate the floor, walls and ceilings of a heated room or storage used for tablet isomerisation. Preferably, but not important, the isomerization ends with moving the tablet to a cool room that has good air circulation.

Jedan od mogucih načina magacioniranja obuhvata prenošenje paketa platformi izmedju sporo kretajucih nosača kroz odgovarajuču atmosferu. Jedna od značajnih prednosti izbrane oblasti temperature je što je operetori moraju podnositi samo tokom kratkih intervala, tako ds je moguče ostvariti ručnu manipulaciju paketima ako je potrebno.One possible way of magnanimation involves transferring platform packages between slow moving carriers through an appropriate atmosphere. One of the significant advantages of the selected temperature range is that the operators have to bear it only during short intervals, so it is possible to manually manipulate the packages if necessary.

Mi smo našli da ovaj relativno prost postupak obezbedjuje vrlo uniforman i pouzdan proizvod koji je uglavnom sasvim izomerizovan i koji daje visoka rezultate reproduktivnosti i efikasnog zagorčavanja pri kuvanju. Dakle toplotniWe have found that this relatively simple process provides a very uniform and reliable product, which is generally completely isomerized and which produces high reproducibility results and efficient cooking damping. So thermal

9.9.

tretman obuhvata samo relarivno niške temperature i ne izvodi se u prisustvu vazduha, pri čemu se očuvaju esencijalna ulja i druge komponente hmelja. Izomerizacija je dovoljno spora čime se olakšava u masi kontrola paketa. Kvalitet proizvoda je bolji i proizvod je uniforman i sasvim stabilan sa obzirom na sadržaj izo-alfa-kiseline.the treatment only covers relatively low temperatures and is not performed in the presence of air, while preserving essential oils and other hop components. Isomerization is slow enough to facilitate bulk control of packages. The quality of the product is better and the product is uniform and quite stable with respect to the iso-alpha-acid content.

Sledeči primeri ilustruju pronalazak.The following examples illustrate the invention.

Primer 1Example 1

Bale smeše hmelja se dobro izmešaju sa magnezijum oksidom (Martin Mariett, Tip 30) u količini od 1,5% masenih i smeša se samelje u prah i žarim rabletira preko kalupa (sa prečnikom otvora od oko 7-5 mm) održavanjem temperature što je moguče nižom bez specijalnog hladjenja. Takodje se pripremaju kontrolne tablete koje ne sadrže magnezijum oksid. Tablete se vakuumski spakuju u kurije od 20kg. •Eksperimentalni uzorci od po 60g se tada posebno vakuumski spakuju u plastične i aluminijumske folije i magacioniraju na 23°θ ili 50°C tokom 3θ dana. Uzorci se analiziraju na početku, posle 10 dana i posle 30 dana na alfakiseline i izo-alfa-kiseline. Rezultati su prdstavljeni grafički na slici 1.Bale mixtures of hops are well mixed with magnesium oxide (Martin Mariett, Type 30) in an amount of 1.5% by weight, and the mixture is ground into a powder and grilled using a mold (with an opening diameter of about 7-5 mm) maintaining the temperature which is possibly lower without special cooling. Control tablets containing no magnesium oxide are also prepared. The tablets are vacuum packed in 20 kg cartons. • Experimental samples of 60g each are then vacuum packed separately in plastic and aluminum foil and magnified at 23 ° θ or 50 ° C for 3θ days. Samples are analyzed at baseline, after 10 days and after 30 days for alpha-acids and iso-alpha-acids. The results are presented graphically in Figure 1.

Primer 2Example 2

Pokazivanje utica,j a temperature na brzinu izomerizacijeIndication of the influence of temperature on the rate of isomerization

EksperimentThe experiment

Sveže osušen Wye Target hmelj je sprašen u mlinu sa čekičem radi dobivanja prilično grubog praha. Prah se dobro izmeša i podeli u dve gomile od po 5 kg svaka. Prva gomila (kontrolna) se obredi u teblere (prečnika 6 mm) pomocu preše za tabletiranje. uruga gomila se stavlja u rotirajuči mikser i doda se 157,5s magnezijum oksida (Anscor 'K', Steetley Co., Ltd., Hartlepool). Smeša se meša 8 minuta pre tabletiranje kao napred. Stabilisane tablete proizvedene na ovaj način su bile malo tvrdje od kontrolnih tableta ali su inače bile sličnog kvaliteta. Analizirane su pomoču HPLCFreshly dried Wye Target hops were ground into a hammer mill to produce a fairly coarse powder. The powder is mixed well and divided into two piles of 5 kg each. The first pile (control) is raked into weights (6 mm in diameter) using a tablet press. The second pile was placed in a rotary mixer and 157.5s magnesium oxide (Anscor 'K', Steetley Co., Ltd., Hartlepool) was added. The mixture was stirred 8 minutes before tabletting as above. The stabilized tablets produced in this way were slightly stiffer than the control tablets but were of similar quality. They were analyzed by HPLC

Izo-alfa-kis (%)alfa-kis. (b) beta-kis.00Iso-alpha-vinegar (%) alpha-vinegar. (b) beta-vinegar.00

Kontrolne C, 2 11,5 4,4Control C, 2 11.5 4.4

Stabilisane 0,2 11,0 4,5Stabilized 0.2 11.0 4.5

Oba seta tableta je vakumski spakovano u količini od 60 g u vrečice alumijumska golija/poliestar koje poseduju visoku otpornost prema prenosu kiseonika. Paketi su tada zamrznuti. Uzorak paketa je tada zagrevan kao što je zahtevano ur'nje, n jam u vodeno kur.··; čilo ture tokom do 14- dana pre analiziranja regulacije temperature s·; kuriščene ss konstantne tempera· tableta. Različite svaki eksperiment, varirajuči izmedju 4-0 i 50°G.Both sets of tablets are vacuum packed in an amount of 60 g in aluminum gallium / polyester bags that have high resistance to oxygen transfer. The packages were then frozen. The sample package was then heated as required, n yam into a water hen. ··; chill tours for up to 14 days before analyzing temperature control s ·; firing ss constant tempera · tablet. Different each experiment, varying between 4-0 and 50 ° G.

olika 2 prikazuje dobiven stepen izomerizacije kao funkciju temperature i vremena.Figure 2 shows the degree of isomerization obtained as a function of temperature and time.

Vidi se da brzina izomerizacije znatno zavisi od temperature u oblasti od 40-50°C. Na primer, posle 7 dana naIt is seen that the rate of isomerization depends significantly on the temperature in the range of 40-50 ° C. For example, after 7 days on

4-0°C, stabilisane tablete su samo izomerizovane, dok na 50°C izomerizacija je skoro potpuna (97 %).4-0 ° C, stabilized tablets are only isomerized, while at 50 ° C the isomerization is almost complete (97%).

Najbolji kvalitet proizvoda se debiva konverzijom na nižim temperaturama ali kao što je prikazano pomoču slike 2, vreme potrebno može biti neprhvatljivo dugo. U proizvodnji izomerizovanih tableti, platforma spakovanih tableta (tipično pakovano po 20 ili 25 kg paketi sa 20 do 50 kutija po platformi) mogu se toplotno tretirati tokom perioda etično 1-5 sedmice. ikupna konverzija od bar 90%, poželjno iznad 958 ce se postiči. konverzija iznad treba očekivati ca je nepoželjna zbog opasnosti od gubitka izo-alfa-kiseline izvanog sporom toplotnom degradacijom.The best product quality is debilitated by conversion at lower temperatures, but as shown in Figure 2, the time taken may be unacceptably long. In the manufacture of isomerized tablets, a platform of packaged tablets (typically packaged at 20 or 25 kg packs of 20 to 50 cartons per platform) can be heat treated over a 1-5 week ethical period. an overall conversion of at least 90%, preferably above 958, will be achieved. the conversion above should be expected ca is undesirable because of the risk of loss of iso-alpha acid out of slow thermal degradation.

U primeru napred, pogodni konverzioni uslovi mogu biti bilo 7 dana na 50°C (97^ konverzije) ili 1^ώ dana naIn the example above, suitable conversion conditions can be either 7 days at 50 ° C (97 ^ conversions) or 1 ^ώ days at

45°C (96 $ konverzije). -olji '.'.vniitet proizvoda treba se postici na nižoj temperaturi, iokušaji konverzije na visim temperaturama dovode do znatno losijeg kvaliteta proizvoda. Dalje, teško je kontrolisati kratko vreme zagrevanja tim pre što je potrebno odgovarajuče vreme da toplota prodre do centra platforme, što može dovesti do neujednačene izoterizacije.45 ° C ($ 96 conversion). Product quality should be achieved at a lower temperature, and conversion attempts at higher temperatures result in significantly lower product quality. Furthermore, it is difficult to control the short warm-up time, before the appropriate time is required for the heat to penetrate to the center of the platform, which may lead to uneven isothermation.

»»

Zapaža se da porast temperature od samo 5° od 4$ do 46°C prepolovijuje vreme potrebno za postizanje izomerizacije od 90%.It is observed that a temperature increase of only 5 ° from 4 $ to 46 ° C halves the time required to achieve an isomerization of 90%.

Primer 3Example 3

Pokazivanje konzistencije izomerizovanih tableta kada se proivode u masi i izonerizuju u platformisanim paketimaDemonstration of consistency of isomerized tablets when mass-produced and isonerized in platform packages

Stabilisane Cluster tablete su dobivene koriščenjem dodatka od 1,9% MgO (Martin Marietta, tip 30). Ove tablete u gomilama od po 2C kg/ su/spakovane u vrečice aluminijumska folija/poliestar unesene u kartonske kutije. Vrečice su prvo evakuisane radi uklanjanja vazduha i tada su dovedene na tmosferski pritisak produvavanjem azota i zatopljene. Kutije su tada zatvorene, zetvorene trakom i odložene ns platforrau. Platforma je prekrivena sa čtvrtastom pločom i nabranom hartijom za pakovanje. Bilo je 4 kutije po sloju, i 5 slojeva kutija.Stabilized Cluster tablets were obtained using a 1.9% MgO supplement (Martin Marietta, type 30). These tablets are packed in bags of 2C kg / s / s in aluminum foil / polyester bags in cartons. The bags were first evacuated to remove air and were then brought to atmospheric pressure by blowing nitrogen and warmed. The boxes were then closed, sealed with tape and disposed ns platforrau. The platform is covered with a square board and pleated paper. There were 4 boxes per layer, and 5 layers of boxes.

^rlatforma se premesti u zagrejanu prostoriju održavanu na 46° pomoču cirkulacije vazduha izszvane pomoču snažnog tavaničnog fena. Posle 11 dana, platforma se premešta u hladni magacin na oko 2°C i ostavlja u njemu 5 dana. Tada se iz pojedinin kutija uzimaju uzorci sa različitih lokacija na platformi, uzorci se uzimaju upravo ispod površine bloka tableta pri kraju kutije, iz položaja uz ivicu (spoljnje) platforme, iz bližine centra (unutrašnje). ^{r the} latform is moved to a heated room maintained at 46 ° by means of air circulation evoked by the aid of a powerful ceiling fan. After 11 days, the platform is moved to the cold store at about 2 ° C and left there for 5 days. Samples are then taken from individual boxes from different locations on the platform, samples are taken just below the surface of the tablet block near the end of the box, from the position along the edge (outer) of the platform, from near the center (inner).

Tabela ITable I

lokacija sloja location layer alfa-kis,# alpha vinegar, # beta-kis.# beta vinegar # izo-alfa-kis# iso-alpha-vinegar # #konver· zije # converter · yawn Vrh /spoljaš. Top / Outer. 0,50 0.50 4,25 4.25 6,70 6.70 95, £ 95, £ Vrh/unutraš. Top / Inside. 0,27 0.27 4,58 4,58 6,97 6.97 96,5 96.5 Sredina/spoljaš. Center / Outer. 0,27 0.27 4,51 4,51 6,77 6.77 96,1 96.1 Sredina/ unutraš Center / Inside . 0,28 . 0.28 4,57 4,57 6,97 6.97 96,2 96.2 Tno/spoljaš. Tno / Outer. 0,27 0.27 4,67 4.67 6,91 6.91 96,5 96.5 Dno/unutraš. Bottom / Inside. 0,27 0.27 4,64 4,64 6,99 6.99 96,5 96.5 Originalne tablete Original pills 6,71 6.71 4,88 4.88 0,44 0.44 6,2 6.2

U gomjoj Tabeli % koverzije se računa na sledeči način:In the larger Table,% conversion is calculated as follows:

Izo-alfa-kiseline (kraj) % konverzije = —- 1100Iso-alpha-acids (end)% conversion = —- 1100

Izo-alfa-kiseline + alfa-kis.(početak)Iso-alpha-acids + alpha-acid (start)

14;14;

Vrlo je iznenadjujuee kao sto se vidi da uzcrci tableta su skoro identični bez obzira na položaj na platformi.It is very surprising to see that the tablet ups are almost identical regardless of the position on the platform.

Primer 4Example 4

Utica.i produženog zagrevanja stabilisanih tableta na kvalitet proizvodaThe impact and prolonged warming of stabilized tablets on product quality

Šest vrsta hmelja je prevedeno u stabilisane tablete kao u primeru 1 i 250 g uzorka je vakumski spakovano u vrečice aluminijurska folija/poliester. Cvi paketi su onda držani u termostatički održavanoj prostoriji zagrejano na 46°C. ^raketi su povrenenu uzimani i testirani.Six types of hops were converted into stabilized tablets as in Example 1 and 250 g of the sample were vacuum packed in aluminum foil / polyester bags. The cvi packages were then kept in a thermostatically maintained room heated to 46 ° C. ^{The r} akets were injured and taken and tested.

Tabela 2 pokazuje količine alfa-kiseline u stabilisanim tabletama i #dodazka MgO (Karuin Marietta, Tip $0).Table 2 shows the amounts of alpha-acid in stabilized tablets and #dosage of MgO (Karuin Marietta, Type $ 0).

Takodje je prikazan % konverzije do devet dana. (Za ovo vrme sve vrste su bile preko 9Ο',ί prevedene ).It also shows% conversion up to nine days. (For this time all species were over 9Ο ', ί translated).

Tabela 5 pokazuje promene u ukupnom sadržaju ulja tablete posle perioda od 14 dana. Ke vidi se značajnija promena i sadržaj ulja je neprom^njen. GC analiza ulje ne pokazuje neku značajanu promenu za razne vrste. Ovo je suprotnosti sa efektom na 100°C, gde se znatne količine ulja gube.Table 5 shows the changes in the total oil content of the tablet after a 14-day period. Significant changes are seen and the oil content is unchanged. GC analysis does not show any significant change for the various species. This is in contrast to the effect at 100 ° C, where considerable amounts of oil are lost.

Iz tabele 2 takoče se može takodje videti da stepen izomerizacije varira sa vrstom hmelja. Tako za neke vrsteFrom Table 2 it can also be seen that the degree of isomerization varies with the type of hops. So for some species

-- 15.-(Perle,Galena) posle 5 dana se dobiva 9C5» izomerizacije. Sve rste dostižu stepen konverzije bar 93$ devetog dana.- 15 .- (Beads, Galena) 9C5 »isomerization is obtained after 5 days. All rst reach a conversion rate of at least $ 93 on the ninth day.

Tabela 2 *Table 2 *

Brzina konverzije na 46°C za razne vrste.Conversion rate at 46 ° C for various types.

Vrsta Kind of % MgO % MgO Original. alfakis,% Original. alfakis,% MgOtalfa-kis % konverzije MgOtalfa-kis% conversion K K 2 2 5 dana 5 days 9 9 Wilamet Wilamet 1,2 1,2 5,2 5.2 5,5 5.5 77 77 89 89 95 95 Cascad. Cascad. 1,5 1.5 5,5 5.5 2,5 2.5 65 65 86 86 95 95 Cluster Cluster 1,5 1.5 6,4 6.4 2,1 2.1 54 54 87 87 96 96 Perl Perl 1,5 1.5 8,2 8.2 1,6 1.6 78 78 94 94 97 97 Galena Galena 1,5 1.5 9,8 9.8 13 13 81 81 95 95 97 97 Nuget Nuget 1,5 1.5 H,2 H, 2 1,2 1,2 62 62 85 85 95 95

k molarni odnosto the molar relation

--16,--16,

Tabela 5Table 5

Uljani sadržaj tablete % koncentracija glavnih komponentiOil content of the tablet% of the concentrations of the major components

Vrsta Kind of dan day ulja ml/lOOg oils ml / lOOg (a) (a) (b) (b) (c) (c) (d) (d) Wilamet Wilamet 0 0 0,4 0.4 15,7 15.7 14,5 14.5 5,5 5.5 4-2,9 4-2,9 9 9 0,3 0.3 n,i n, i 15,4 15.4 5,0 5.0 48,2 48,2 20 20 0,3 0.3 13,8 13,8 15,2 15.2 4,7 4.7 46,4 46,4 44 44 0,3 0.3 11,2 11.2 15,5 15.5 4-,5 4-, 5 48,4 48,4 Oascad Oascad 0 0 0,5 0.5 43,8 43,8 7,7 7.7 5,1 5.1 16,9 16.9 9 9 0,5 0.5 35,2 35,2 9,3 9.3 6,3 6,3 23,2 23,2 20 20 0,5 0.5 33,9 33,9 9,6 9.6 6,0 6.0 24,2 24.2 44 44 0,5 0.5 28,4 28,4 10,9 10.9 6,5 6.5 28,6 28.6 Cluster Cluster 0 0 0,3 0.3 43,4 43,4 9,8 9.8 0,4 0.4 16,6 16.6 9 9 0,3 0.3 24,0 24,0 13,0 13,0 0,2 0.2 29,4 29.4 20 20 0,2 0.2 44,0 44,0 9,9 9.9 θ,2 θ, 2 22,5 22.5 44 44 0,3 0.3 27,4 27,4 12,9 12.9 31,6 31.6 Perl Perl 0 0 13 13 36,5 36,5 12,9 12.9 0,9 0.9 34-,9 34-, 9 9 9 1,2 1,2 40,0 40,0 11,0 11,0 0,9 0.9 33,8 33,8 20 20 1,0 1.0 44,0 44,0 11,0 11,0 0,7 0.7 31,6 31.6 44 44 1,0 1.0 38,2 38,2 13,3 13.3 0,7 0.7 37,2 37,2 Galena Galena 0 0 0,9 0.9 4-7,7 4-7,7 9,9 9.9 0,3 0.3 13,3 13.3 9 9 1,0 1.0 4-7,5 4-7,5 10,3 10.3 0,4 0.4 17,0 17,0 20 20 1,0 1.0 4-3,3 4-3,3 10,9 10.9 0,3 0.3 19,2 19,2 44 44 0,6 0.6 56,3 56,3 10,2 10.2 17,7 17.7 Kuget Kuget 0 0 0,8 0.8 47,4 47,4 10,8 10.8 0,1 0.1 19,7 19.7 9 9 0,9 0.9 41,2 41,2 12,6 12.6 o,i o, i 26,5 26.5 20 20 l,o l, o 39,1 39.1 13,4 13,4 o,i o, i 28,8 28,8 44 44 0,7 0.7 47,9 47.9 12,6 12.6 26,5 26.5

a = nircen c = Karicfilin c = Parnescen iiumulena = nircene c = Caricfilin c = Parnescene iiumulene

Primer 5Example 5

Analiza proizvodnje pivaAnalysis of beer production

Pilotska skala 6001 analize proizvodnje piva je izvršena radi uporedjivanja efikasnosti izomerizacije tableta prema standardnim tabletama napravljenim od istog sprašenog hmelja (Wye Target). Dve indetiene pivske sire (A i B; O.G. 1038) su pripremljene i dovedene do tačke ključanja. Dodaju se tablete hmelja i sira ključa jedan čas, pre nego što se prenese u fermentacionu posudu preko izmenjivača toplote tokom perioda od 0,5 časa. ‘'osle fermentacije i zrenja dobiveno pivo se istoči i ispituje.Pilot scale 6001 of the beer production analysis was performed to compare the isomerization efficiency of the tablets against standard tablets made from the same powdered hops (Wye Target). Two indieten beer cheeses (A and B; O.G. 1038) were brewed and brought to the boiling point. Hops and cheese pills are added for one hour before being transferred to the fermentation vessel via a heat exchanger for a period of 0.5 hours. '' The fermentation and ripening donkey of the brewed beer is weighed and tested.

tabela 4 pokazuje analizu tableta a Tabela 5 količine dodate širi. HPLC analiza piva je prikazana u Tabeli 6.Table 4 shows the analysis of the tablets and Table 5 the quantities added wider. HPLC analysis of beer is shown in Table 6.

Izomerizacija tableta je izvedena najefikasnije. Lkus i aroma piva su bili bez karakteristika hmelja.Tablet isomerization is performed most efficiently. The taste and taste of the beer were devoid of hops.

Tada je pripremljen par pivskog variva (C i D) radi ispitivanja izvodijivosti kasnog dodavanja hmelja (5 minuta pre kraja ključanja) sa izomerizovanim tabletama. Iste tablete su koriščene kao u prethodnom ispitivanju.A brew pair (C and D) was then prepared to test the feasibility of late addition of hops (5 minutes before boiling) with isomerized tablets. The same tablets were used as in the previous study.

Upredjenju sa prethodnim ispitivanjem, zakasneli dodatak standardnih tableta hmelja smanjuje koriščenje gorkog potencijala,dok suprotno važi za izomerizovane tablete.Compared to the previous test, the delayed addition of standard hops tablets reduces the use of bitter potential, while the opposite is true for isomerized tablets.

lo.lo.

Uopšteno, ismorisčer.je zs izomerizovane oablete je bilo iznad 57.-. Cba piva oila su dobrih o-obina, svako je posedovalo blagu ali uočijivu arimu hmelja.In general, the isomerization of the isomerized oblet was above 57.-. Cba beer oils are good o-shins, each possessing a mild but noticeable hop arim.

Tabela 4Table 4

HPLC analize tabletaHPLC tablet analysis

Ξζο-alfa-kis alfa-kis» beta-kis.Ξζο-alpha-vinegar alpha-vinegar »beta-vinegar.

Standardne tablete 0,2Standard tablets 0.2

Izomerizovane tablete 10,7Isomerized tablets 10.7

10,710.7

0,30.3

4,24.2

4,04.0

Tabela 5Table 5

Proizv. Tip tablete pivaManufact. Beer pill type

Dodatek hmelja (g) rani kasni ukunniAddition of hops (g) early late ounces

A A Standardne tablete Standard tablets 362 362 0 0 362 362 B B izomerizovane tebi. isomerized to you. 221 221 0 0 221 221 C C Standardne tabl. Standard Tabl. 242 242 121 121 362 362 D D izomerizovane tabl. isomerized tablets. 101 101 121 121 222 222

19.19.

Tabela 6Table 6

Gorčina piva i iskorisčenjeBitterness of beer and utilization

Proizv. Tip tablete Izo-alfa“kis. alfa“kis -skorišcenjeManufact. Type of pill Iso-alpha “vinegar. alpha vinegar utilization

piva beer (mg/1) (mg / l) ( mg/1) (mg / l) % % A A Stand. tablete Stand. pills 26,6 26.6 1,3 1.3 44 44 B B Izomer. tabl. Isomer. tabl. 27,4 27,4 ne detkuje se it does not detect 67 67 C C ^tand. tabl. ^ tand. tabl. 26,3 26.3 2,7 2.7 41 41 D D Izomer. tabl. Isomer. tabl. 27,6 27.6 tragovi clues 68 68

Claims

Patent claims

A process for stabilizing and isomerizing alpha acids in hops by treating crushed hops with calcium or magnesium oxide or hydroxide to form metal salts and further subjecting them to elevated temperature while isomerization to iso-alpha acids, to form a mixture of hops and calcium or magnesium oxide or hydroxide into tablets under controlled conditions to minimize isomerization, pack the tablets in the absence of oxygen and subject the packets to controlled heating at about 40 to 55 ° C for a period of at least one day, selecting temperature and content calcium or magnesium oxide or hydroxide so that complete isomerization takes place.

Process according to claim 1, characterized in that magnesium oxide or hydroxide is used.

Process according to claim 1, characterized in that magnesium oxide or hydroxide is introduced in an amount of from 0.5 to 4% by weight.

Process according to claim 1, characterized in that magnesium oxide or hydroxide is introduced in an amount of from 1.2 to 3.2 wt. %.

Method according to one of Claims 1-4, characterized in that the heating is carried out at a temperature of from about 43 to 54 ° C.

Method according to one of claims 1-5, characterized in that the heating is carried out at a temperature of from about 45 to 50 ° C.

Method according to one of Claims 1-6, characterized in that the heating is carried out for 2 to 30 days.

Method according to one of claims 1-7, characterized in that the heating is carried out for 5 to 15 days.

Method according to one of Claims 1-8, characterized in that the heating is carried out for 7 to 10 days.

24 Λ

Method according to one of Claims 1-9, characterized in that the tablets are packaged in vacuum packages.

Method according to one of Claims 1-9, characterized in that the tablets are packaged in airtight packages under an inert gas atmosphere at an absolute pressure of from 0 to about 1 atmosphere.

A process according to claim 11, characterized in that the inert gas is nitrogen.

A method according to claim 11 or 12, characterized in that the absolute pressure is about 1 atmosphere.

Method according to one of Claims 1-13, characterized in that the welded packages are placed in cardboard boxes before heating.

Method according to one of Claims 1-14, characterized in that the rolled-up tablet packs are pre-heated.

Process according to one of Claims 1-15, characterized in that the tablet packs are cooled to room temperature or below.

Process according to claim 16, characterized in that the tablets are cooled and stored at a temperature below 20 ° C.

Steiner Hops Limited r- ^

X

Excerpt

Process for the stabilization and isomerization of alpha-acids in hops by treating crushed hops with calcium ah magnesium oxide or hydroxide to form metal salts and further subjecting them to elevated temperature while isomerization to iso-alpha-acids, characterized in that the mixture hops and calcium ah magnesium oxide ah hydroxide are shaped into tablets under controlled conditions to minimize isomerization. The tablets are packaged in the absence of oxygen and packaged and further subjected to controlled heating to about 40 to 50 ° C for at least one day. The temperature and content of calcium or magnesium oxide ah hydroxide are selected so that almost complete isomerization proceeds.