CA1130738A - Method of stabilizing colloidal and taste qualities of beverages under simultaneous deactivation of enzymes - Google Patents
Method of stabilizing colloidal and taste qualities of beverages under simultaneous deactivation of enzymesInfo
- Publication number
- CA1130738A CA1130738A CA295,570A CA295570A CA1130738A CA 1130738 A CA1130738 A CA 1130738A CA 295570 A CA295570 A CA 295570A CA 1130738 A CA1130738 A CA 1130738A
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- enzymes
- liquid medium
- polymeric substances
- beer
- stabilizing
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Abstract
ABSTRACT OF THE DISCLOSURE
The disclosure describes a method of stabilizing both the colloidal and taste qualities of beverages while simultane-ously deactivating the enzymes which are present therein. The method involves contacting a beverage containing turbidity pre-cursors, enzymes or both at a temperature of from about -2°C to about 80°C with organic polymeric substances which are polycon-densates of diols and dicarboxylic acids, such a polyethylene terephthalate or derivatives thereof. The polymeric substances are thereafter separated from the liquid medium. This method enables to reduce the contents of polyphenol precursors of colloi-dal cloudiness as well as to deactivate the enzymes which are present thus avoiding undesirable beverage flavors.
The disclosure describes a method of stabilizing both the colloidal and taste qualities of beverages while simultane-ously deactivating the enzymes which are present therein. The method involves contacting a beverage containing turbidity pre-cursors, enzymes or both at a temperature of from about -2°C to about 80°C with organic polymeric substances which are polycon-densates of diols and dicarboxylic acids, such a polyethylene terephthalate or derivatives thereof. The polymeric substances are thereafter separated from the liquid medium. This method enables to reduce the contents of polyphenol precursors of colloi-dal cloudiness as well as to deactivate the enzymes which are present thus avoiding undesirable beverage flavors.
Description
This invention relates to beverages such as beer and wine there are more or less present certain groups of colloidal substances which are responsible for the formation of non-biolo-gical sediments or cloudiness in the final product. Moreover oxidation changes in certain groups of these substances tend to impair the organoleptic properties of beverages. Precursors responsible for colloidal cloudiness include especially polypep-tides, polyphenols and polysaccharides. The formation of colloi-dal sediments or cloudiness is promoted and accelerated by the oxidation reactions which are provoked by the presence of oxygen, temperature conditions and certain metal ions.
To increase the colloidal stability of beverages of the afore-mentioned types a plurality of stabilizers are used. The purpose of the stabilizing processes is to remove high molecular weight substances which are unstable in solutions. To reduce the concentration of polypeptidic cloudiness precursors there are used adsorbents based on silica gel and bentonite as well as pre-cipitants or coagulants such as tannin and enzymatic agents ca-pable of cleaving high molecular weight substances into low mole-cular weight components which are stable in solution, or are evensoluble.
The concentration of polyphenol can be reduced by using adsorbents based on polyvinyl pyrrolidone, or a precipitating agent such as formaldehyde. To prevent any oxidation changes in the beverages the bottling plants can be operated under carbon dioxide protection as well as with antioxidant dopes such as as-corbic acid, sulphur dioxide or the like.
Adsorbents such as silica gels and bentonites are in-soluble, as it is the case with those allowable from the viewpoint of human health protection. They are used either as constituents of filtering materials, such as diatomaceous earth, or during the maturation of the product, or are introduced into collecting and 1~30738 pressurized tanks prior to the bottling process. Silica gel based adsorbents are substantially inert in respect of both the chemical and organoleptic properties of the beverages. The use of bentonites is frequently accompanied by some modifications of the taste of the product such as in the case of beer, which de-velops an earthy flavour and is accompanied by a reduction of the foaminess.
Precipitants such as formaldehyde and the like are non-specific stablLizers and their use in the foodstuff industry is inadmissible under the rules of human health protection of many countries. Enzyme based stabilizers comprise a proteolytic en-zyme as the essential component. The active component of such stabilizers most frequently includes papain, which is a technic-al enzyme of vegetal origin, or another suitable protease. To date enzymatic agents have been used in the form of soluble sub-stances. A catalyzed reaction is stopped by adding a deactivator, or by heating to a temperature at which the enzyme component of the stabilizers becomes denaturized. Because they contaminate the final product with enzymatic catalytic remnants, the soluble enzymatic agents are also inadmissible in many countries for use in the foodstuff industries. In spite of this fact, sometimes the use of enzymes cannot be avoided. For example there can be mentioned the cleavage of pectines which pectinase in juice pres-sing processes, or the stabilization of beer with a protease ad-ditive. Originally, enzymes of vegetal, or animal origin, such as, for instance, amylase derlved from malt, or rennase derived from calf gastric juices have been used.~ However, in view of a rising demand and of the expensive production of such enzymatic preparations, enzymes of microbial origin have been preferred to many of those of vegetal or animal origin.
However, with some enzymatic preparations, their exten-ded contact with the respective medium is accornpanied by further ~` 113073B
undesirable cleavage of a plurality of substrates and even by the formation of by-products whereby the character of the final pro-duct is modified. In other cases only a partial degradation of the substrate is sought since further degradation would change the taste of the product. Finally, a high concentration of cer-tain enzymes or even some accompanying enzymes in the foodstuff may be harmful from a hygienic viewpoint. Therefore, it is desirable that, after having fulfilled their task, such enzymes be deactivated as quickly as possible. In connection with the products, which during further processing, will be subjected to temperatures adjacent the boiling point, the heating is simul-taneously used for deactivation of enzymes since at such elevated temperatures their proteins become denaturized. In some cases, however, only a short-termed pasteurization is used in order to retain the vitamin contents such as with fruit juices, or the taste quality of the beverage such as with beer.
Although a plurality of inhibitors are known that can stop the undesirable enzyme activity, any addition of such agents to the foodstuff products is out of question since they are most-ly of toxic character.
It is an object of the present invention to provide amethod of stabilizing both the colloidal and taste qualities of beverages such as wine and beer while simultaneously deactivat-ing the enzymes present therein, the method comprising contact-ing a wine or beer consisting of a liquid medium containing tur-bidity precursors, enzymes, or both at a temperature about from -2C to about 80C with organic polymeric substances of poly-condensate types based on diols and dicarboxylic acids, prefer-ably polyethylene terephthalate or derivatives thereof, and separating such polymeric substances from the liquid medium.
In such a manner, it is possible to reduce the contents of polyphenol precursors of colloidal cloudiness as well as to ~ . f , ~
113~73~
deactivate the enzymes which are present thus avoiding undesir-able beverage flavours.
The afore-mentioned polymeric material can be used as a sole stabilizer added during any of the beverage production steps, or in a combination with other types of stabilizers. It can be applied as filtering material, or as a constituent in com-bination with the other filtering inorganic or organic materials which are insoluble in water, such as diatomaceous earth.
Furthermore it can be added in powder form prior to filtering whereupon after a certain time, it will be separated by filtering, centrifuginy, or sedimentation. The concentration of polyphenols and enzymes in the beverages can be reduced by allowing the latter to flow over a fabric produced from the respective polymeric sub-stances, or over sheets, wherein either a pulverulent or a fibrous polymer is pressed therein. Other possible applications consist in allowing the solution intended to be treated to flow through columns filled with the respective polymeric material, or through other suitable vessels filled with an adsorbent. A]so, polymeric adsorbent may be incorporated into a plant, such as, for example, in the form of a pipeline through which the liquid substance is allowed to flow into boards or reactors. Advantageously no for-eign matter is allowed to penetrate into the beverages which prac-tising such a process.
The afore-mentioned properties are not present with the individual components used for preparing polymers, such as mono-mers, or polymerization catalysts. It is only a macro-molecule of the above type that possesses a desirable property of adsor-bing polyphenol substances and deactivating the enzymes. By re-ducing the concentration of the polyphenol substances in the beverage, there is an increase not only of the colloidal stabil-ity from the viewpoint of postponing the sediment or the forma-tion of cloudiness but also the stability of the organoleptic properties. sy reducing the concentration of the polyphenol com-pounds the possibility of oxidation thereof will be decreased.
It is in fact the oxidation products of such substances that un-desirably influence the taste qualities of the final products.
Advantageously, the proteinaceous substances are not resorbed in the process according to the invention but remain in the respect-ive media so that the taste qualities of the final product are not affected.
The amount of polymeric substances depends on the de-sired properties of the beverages to be treated and on the requestfor reducing the concentration of the precursors cloudiness, or the concentration of undesirable enzymes, respectively, be it enzymes of vegetal origin such as, for instance, papain, or of microbial origin such as bacterial amylases, or pectinases.
The range of activity of the adsorbents which are added is not limited by the temperature. The treatment can be used in any phase of the manufacturing process, at any temperature and at any pH value.
The following examples are given as illustrative only without, however, limiting the invention to the specific details thereof.
EX~MPLE 1 Deactivation of alpha-amylase BACILLUS SUBTII.IS
To increase the colloidal stability of beverages of the afore-mentioned types a plurality of stabilizers are used. The purpose of the stabilizing processes is to remove high molecular weight substances which are unstable in solutions. To reduce the concentration of polypeptidic cloudiness precursors there are used adsorbents based on silica gel and bentonite as well as pre-cipitants or coagulants such as tannin and enzymatic agents ca-pable of cleaving high molecular weight substances into low mole-cular weight components which are stable in solution, or are evensoluble.
The concentration of polyphenol can be reduced by using adsorbents based on polyvinyl pyrrolidone, or a precipitating agent such as formaldehyde. To prevent any oxidation changes in the beverages the bottling plants can be operated under carbon dioxide protection as well as with antioxidant dopes such as as-corbic acid, sulphur dioxide or the like.
Adsorbents such as silica gels and bentonites are in-soluble, as it is the case with those allowable from the viewpoint of human health protection. They are used either as constituents of filtering materials, such as diatomaceous earth, or during the maturation of the product, or are introduced into collecting and 1~30738 pressurized tanks prior to the bottling process. Silica gel based adsorbents are substantially inert in respect of both the chemical and organoleptic properties of the beverages. The use of bentonites is frequently accompanied by some modifications of the taste of the product such as in the case of beer, which de-velops an earthy flavour and is accompanied by a reduction of the foaminess.
Precipitants such as formaldehyde and the like are non-specific stablLizers and their use in the foodstuff industry is inadmissible under the rules of human health protection of many countries. Enzyme based stabilizers comprise a proteolytic en-zyme as the essential component. The active component of such stabilizers most frequently includes papain, which is a technic-al enzyme of vegetal origin, or another suitable protease. To date enzymatic agents have been used in the form of soluble sub-stances. A catalyzed reaction is stopped by adding a deactivator, or by heating to a temperature at which the enzyme component of the stabilizers becomes denaturized. Because they contaminate the final product with enzymatic catalytic remnants, the soluble enzymatic agents are also inadmissible in many countries for use in the foodstuff industries. In spite of this fact, sometimes the use of enzymes cannot be avoided. For example there can be mentioned the cleavage of pectines which pectinase in juice pres-sing processes, or the stabilization of beer with a protease ad-ditive. Originally, enzymes of vegetal, or animal origin, such as, for instance, amylase derlved from malt, or rennase derived from calf gastric juices have been used.~ However, in view of a rising demand and of the expensive production of such enzymatic preparations, enzymes of microbial origin have been preferred to many of those of vegetal or animal origin.
However, with some enzymatic preparations, their exten-ded contact with the respective medium is accornpanied by further ~` 113073B
undesirable cleavage of a plurality of substrates and even by the formation of by-products whereby the character of the final pro-duct is modified. In other cases only a partial degradation of the substrate is sought since further degradation would change the taste of the product. Finally, a high concentration of cer-tain enzymes or even some accompanying enzymes in the foodstuff may be harmful from a hygienic viewpoint. Therefore, it is desirable that, after having fulfilled their task, such enzymes be deactivated as quickly as possible. In connection with the products, which during further processing, will be subjected to temperatures adjacent the boiling point, the heating is simul-taneously used for deactivation of enzymes since at such elevated temperatures their proteins become denaturized. In some cases, however, only a short-termed pasteurization is used in order to retain the vitamin contents such as with fruit juices, or the taste quality of the beverage such as with beer.
Although a plurality of inhibitors are known that can stop the undesirable enzyme activity, any addition of such agents to the foodstuff products is out of question since they are most-ly of toxic character.
It is an object of the present invention to provide amethod of stabilizing both the colloidal and taste qualities of beverages such as wine and beer while simultaneously deactivat-ing the enzymes present therein, the method comprising contact-ing a wine or beer consisting of a liquid medium containing tur-bidity precursors, enzymes, or both at a temperature about from -2C to about 80C with organic polymeric substances of poly-condensate types based on diols and dicarboxylic acids, prefer-ably polyethylene terephthalate or derivatives thereof, and separating such polymeric substances from the liquid medium.
In such a manner, it is possible to reduce the contents of polyphenol precursors of colloidal cloudiness as well as to ~ . f , ~
113~73~
deactivate the enzymes which are present thus avoiding undesir-able beverage flavours.
The afore-mentioned polymeric material can be used as a sole stabilizer added during any of the beverage production steps, or in a combination with other types of stabilizers. It can be applied as filtering material, or as a constituent in com-bination with the other filtering inorganic or organic materials which are insoluble in water, such as diatomaceous earth.
Furthermore it can be added in powder form prior to filtering whereupon after a certain time, it will be separated by filtering, centrifuginy, or sedimentation. The concentration of polyphenols and enzymes in the beverages can be reduced by allowing the latter to flow over a fabric produced from the respective polymeric sub-stances, or over sheets, wherein either a pulverulent or a fibrous polymer is pressed therein. Other possible applications consist in allowing the solution intended to be treated to flow through columns filled with the respective polymeric material, or through other suitable vessels filled with an adsorbent. A]so, polymeric adsorbent may be incorporated into a plant, such as, for example, in the form of a pipeline through which the liquid substance is allowed to flow into boards or reactors. Advantageously no for-eign matter is allowed to penetrate into the beverages which prac-tising such a process.
The afore-mentioned properties are not present with the individual components used for preparing polymers, such as mono-mers, or polymerization catalysts. It is only a macro-molecule of the above type that possesses a desirable property of adsor-bing polyphenol substances and deactivating the enzymes. By re-ducing the concentration of the polyphenol substances in the beverage, there is an increase not only of the colloidal stabil-ity from the viewpoint of postponing the sediment or the forma-tion of cloudiness but also the stability of the organoleptic properties. sy reducing the concentration of the polyphenol com-pounds the possibility of oxidation thereof will be decreased.
It is in fact the oxidation products of such substances that un-desirably influence the taste qualities of the final products.
Advantageously, the proteinaceous substances are not resorbed in the process according to the invention but remain in the respect-ive media so that the taste qualities of the final product are not affected.
The amount of polymeric substances depends on the de-sired properties of the beverages to be treated and on the requestfor reducing the concentration of the precursors cloudiness, or the concentration of undesirable enzymes, respectively, be it enzymes of vegetal origin such as, for instance, papain, or of microbial origin such as bacterial amylases, or pectinases.
The range of activity of the adsorbents which are added is not limited by the temperature. The treatment can be used in any phase of the manufacturing process, at any temperature and at any pH value.
The following examples are given as illustrative only without, however, limiting the invention to the specific details thereof.
EX~MPLE 1 Deactivation of alpha-amylase BACILLUS SUBTII.IS
2.5 ml of an aqueous enzyme solution containing 5 en-zyme units in one millilitre were increased to a volume of 5 ml with an aqueous buffer solution of pH 5.5 after which water was added up to a volume of 20 ml. 0.1 g of pulverized polyethylene terephthalate having a molecular weight of 38,100 was added to the solution followed by agitation during 5 minutes after which the liquid was filtered. No amylase activity was found in the clear filtrate. In the present case, pulverized polyethylene terephthalate in combination with polybutylene terephthalate ~130738 could have been used.
Deactivation of PaPain To 100 ml of an aqueous enzyme solution containing 0.2 g of papain concentrate having 2.250 enzyme units per gram there was added 1.5 g of modified polyethylene terephthalate containing 5 mols. of isophtalic acid as modifying component whereupon the solution was allowed to stand for 30 minutes. Within this time interval, the enzyme activity became practically zero.
Deqradation of ~ectinase activitY
Reference test:-To 7 ml of one percent pectin solution, there was added one millilitre of a pectinase solution prepared by dissolving 4 mg of an enzymatic preparation in 2 ml water, and clarifying by centrifuging. Immediately after mixing in a IIoppler falling-ball vis-cosimeter, the ball passage period was examined at a constant temperature of 30C at three minutes time intervals. The results were as follows:-20Time Interval ~all Passage Period (min.) (min.) 2.36
Deactivation of PaPain To 100 ml of an aqueous enzyme solution containing 0.2 g of papain concentrate having 2.250 enzyme units per gram there was added 1.5 g of modified polyethylene terephthalate containing 5 mols. of isophtalic acid as modifying component whereupon the solution was allowed to stand for 30 minutes. Within this time interval, the enzyme activity became practically zero.
Deqradation of ~ectinase activitY
Reference test:-To 7 ml of one percent pectin solution, there was added one millilitre of a pectinase solution prepared by dissolving 4 mg of an enzymatic preparation in 2 ml water, and clarifying by centrifuging. Immediately after mixing in a IIoppler falling-ball vis-cosimeter, the ball passage period was examined at a constant temperature of 30C at three minutes time intervals. The results were as follows:-20Time Interval ~all Passage Period (min.) (min.) 2.36
3 2.08 6 1.48 9 1.36 12 1.27 Test:-To 5 ml of a pectinase solution (2 mg/ml) there was added 0.5 g of pulverized polyethylene terephthalate in which 4%
of the terephthalate units were replaced by adipate units where-upon the solution was agitated during 10 minutes at room temper-ature. After xemoving the sediment by centrifugation, one milli-litre of the clear solution was added to 7 ml of a one per centpectin solution and the viscosity was again measured at three minutes intervals at 30C. The results were as follows:-Time Interval sall Passage Period ~min.) (min.) 0 2.39 3 2.38 6 2.33 9 2.28 1012 2.23 When comparing the above with the reference test a sub-stantial decrease in the pectinase activity can be observed.
Reduction of polyphenol concentration in beer 10 litres of beer were mixed during 30 minutes with lOg of a pulverized copolymer having a molecular weight of 15,QOO and prepared from ethylene glycol, terephthalate and 3.9% of sulfo-isophtalic acid. After filtration a 13.5% polyphenol concentra-tion decrease was found out.
One litre of wine was mixed during 30 minutes with 2 g of a pulverized polymer having a molecular weight of 18,000 and prepared from ethylene glycol terephthalate and 3.0% sulfoisoph-talic acid. The reduction of the polyphenol concentration was 11.~2%.
One hectolitre of beer was filtered over a kieselgur filter while a copolymer having a molecular weight of 14,000 and prepared from ethylene glycol terephthalate and 3.9% sulfoisoph-30 talic acid, was added thereto. After filtration, it was ascer-tained that the polyphenol concentration in beer has decreased from the original value of 235.3 to 211.56 mg/litre, i.e. by ~130~3~3 about 10 per cent. The thus treated beer proved to have a two months colloidal stability prolongation when compared to the reference sample. The taste qualities of beer were stabilized during a ~ month storing period.
of the terephthalate units were replaced by adipate units where-upon the solution was agitated during 10 minutes at room temper-ature. After xemoving the sediment by centrifugation, one milli-litre of the clear solution was added to 7 ml of a one per centpectin solution and the viscosity was again measured at three minutes intervals at 30C. The results were as follows:-Time Interval sall Passage Period ~min.) (min.) 0 2.39 3 2.38 6 2.33 9 2.28 1012 2.23 When comparing the above with the reference test a sub-stantial decrease in the pectinase activity can be observed.
Reduction of polyphenol concentration in beer 10 litres of beer were mixed during 30 minutes with lOg of a pulverized copolymer having a molecular weight of 15,QOO and prepared from ethylene glycol, terephthalate and 3.9% of sulfo-isophtalic acid. After filtration a 13.5% polyphenol concentra-tion decrease was found out.
One litre of wine was mixed during 30 minutes with 2 g of a pulverized polymer having a molecular weight of 18,000 and prepared from ethylene glycol terephthalate and 3.0% sulfoisoph-talic acid. The reduction of the polyphenol concentration was 11.~2%.
One hectolitre of beer was filtered over a kieselgur filter while a copolymer having a molecular weight of 14,000 and prepared from ethylene glycol terephthalate and 3.9% sulfoisoph-30 talic acid, was added thereto. After filtration, it was ascer-tained that the polyphenol concentration in beer has decreased from the original value of 235.3 to 211.56 mg/litre, i.e. by ~130~3~3 about 10 per cent. The thus treated beer proved to have a two months colloidal stability prolongation when compared to the reference sample. The taste qualities of beer were stabilized during a ~ month storing period.
Claims (7)
1. A method of stabilizing the colloidal and taste quali-ties of wine and beer while simultaneously deactivating the en-zymes present therein, comprising contacting a wine or beer consisting of a liquid medium containing turbidity precursors, enzymes or both, at a temperature from about -2°C to about 80°C, with polyethylene terephthalate or derivatives thereof and se-parating said polymeric substances from the liquid medium.
2. A method as claimed in claim 1, wherein the polymeric substances are applied to the liquid medium in combination with other stabilizing agents, either simultaneously, or subsequently.
3. A method as claimed in claim 1, wherein the polymeric substances are in powder form and are dispersed in the liquid medium under agitation whereupon after an effective agitation period they are separated therefrom as by sedimentation, filtra-tion, or centrifugation.
4. A method as claimed in claim 1 or claim 2, wherein the liquid medium is contacted with the polymeric substance alone, or mixed with other stabilizing agents, or after the action of the latter, in a continuous throughflow plant.
5. A method as claimed in claim 1, wherein the liquid me-dium is allowed to flow through a layer of a pulverized or fi-brous polymer or mixtures thereof with either inorganic or organic filtering materials.
6. A method as claimed in claim 5, wherein the filtering material consists of diatomaceous earth.
7. A method as claimed in claim 1, wherein the liquid medium is allowed to flow through boards, sheets, cloths, pipe-line or reactors having said polymeric substances incorporated therein.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA295,570A CA1130738A (en) | 1978-01-24 | 1978-01-24 | Method of stabilizing colloidal and taste qualities of beverages under simultaneous deactivation of enzymes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA295,570A CA1130738A (en) | 1978-01-24 | 1978-01-24 | Method of stabilizing colloidal and taste qualities of beverages under simultaneous deactivation of enzymes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1130738A true CA1130738A (en) | 1982-08-31 |
Family
ID=4110615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA295,570A Expired CA1130738A (en) | 1978-01-24 | 1978-01-24 | Method of stabilizing colloidal and taste qualities of beverages under simultaneous deactivation of enzymes |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1130738A (en) |
-
1978
- 1978-01-24 CA CA295,570A patent/CA1130738A/en not_active Expired
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