WO2000030478A1

WO2000030478A1 - Composition containing additives for beverages

Info

Publication number: WO2000030478A1
Application number: PCT/BR1998/000093
Authority: WO
Inventors: Roberto Hermínio MORETTI
Original assignee: Rhodia-Ster S.A.
Priority date: 1997-04-18
Filing date: 1998-11-19
Publication date: 2000-06-02
Also published as: AU1654499A; BR9700569A

Abstract

The formulation developed by the Applicant is characterized by presenting in its composition: (A) one or more enzymatic complexes; (B) one or more preservative agents and optionally, (C) other food additives. The main function of the enzymatic complex (A) is the catalysis of reactions consuming the oxygen dissolved in the beverage and in the 'headspace', without affecting the beverage's sensorial characteristics. During the shelf-life, the oxygen penetrating through the plastic packaging walls shall also be consumed by the same process. The preservatives (B) preserve the beverage microbiologically. Jointly, such preservatives have a total and synergistic action, preventing the multiplication of microorganisms. Due to the characteristics of the beverage in which the formulation proposed has been added, any type of packaging can be used.

Description

COMPOSITION CONTAINING ADDITIVES FOR BEVERAGES

The invention refers to composition containing additives and coadjuvants associated to a mild thermal treatment for chemical, physical, microbiological and sensory preservation of beverages in plastic package (permeable containers) or in order to preserve beer (with draft-beer close characteristics) for long time in non permeable containers. Beverages may be alcoholic or not, fermented or not, carbonated or not. As example we can mention: fruit juice, beer, draft beer, wine, soft drinks, isotonic beverages, vinegar, etc. In the case of production of fermented beverages, especially beers, the packages used are: the traditional glass bottle and metallic cans. The commercial use of plastic recipients for such application still presents some problems.

Plastic recipients are not commercially used on a large scale, since they present two main problems: high oxygen-permeability and low thermo-resistance. The first problem causes the beverage accelerated oxidation, reducing its shelf-life, while its low heat resistance prevents the conventional pasteurization of the beverage inside it or the product's packaging when it is still hot. With the objective of solving these problems, a formulation has been developed containing the enzymatic complex, preservatives and other food additives in association with a thermal treatment non aggressive to the beverage's delicate components.

As mentioned in the article "Practical Experiences of Packaging Beer in PET Bottles", by Iain D. M. Oag and Timothy J. B. Webb, plastic packages are used for beer packaging in the English market, since 1982. However, due to the high oxygen- permeability of monolayer PET bottles, giving them only a 20-week shelf-life, studies have been developed on the product's stability in PET bottles recovered with a PVDC layer-barrier.

In comparison with aluminium cans and glass bottles which present a 36-week shelf-life, the beer packed in PET bottle recovered with PVDC, maintains its original characteristics for 20 weeks. However, the high costs of such type of package make this solution commercially less competitive, when compared with the use of traditional package.

As mentioned in the article " PET Bottle Prime Contender in Japan's Beer Packaging War", by Yoshiro Miki, Kirin Brewery Co., Ltd., Tokyo, Japan, due to the increase in beer consumption in Japan, the preference for one-way bottles, easy to carry and to dispose of, has also increased. Although the performance obtained as to the gas barrier properties is worse, the interest in the use of PET in the packaging of beverages is due to the easiness to obtain bottles of several forms and sizes and also, because they are a novelty.

As mentioned in the article "Australian Brewer Test Markets PET Beer Bottles", Packaging Strategies, December 15, 1996, an Australian company launched in the market the filtered beer cold-packed in monolayer PET bottles of 500 ml. Due to the fact that PET is not efficient as regards the gas barrier, the beer has its original characteristics preserved during 30 to 50 days only, and besides that, it must be commercialized under refrigeration conditions.

The microbiological stabilization may be traditionally achieved from several forms:

(1) tunnel pasteurization (thermal treatment inside the final package); (2) "flash" pasteurization in heat exchangers before packaging the beverage;

(3) sterile filtration (0.45 micra) capable of retaining microorganisms which might be present in the beverage;

(4) continuous refrigeration and

(5) addition of stabilizer. As mentioned in the article " Economies of a New Microbiological Stabilizer", by Dr. John B. Bockelmann, Tenafly, N.J., (1) the Tunnel pasteurization is considered an old-fashioned heating process, having a successful background and being widely used by brewers. The disadvantage of such a process is the fact that the use of heat provides a faster deterioration of the taste. The cost of the equipment is high, and its size requires the use of large areas, besides requiring large quantities of steam and water. This may unchain serious problems in the future, in terms of costs and environmental preservation. In the meantime, is widely used in industry in order to guarantee quality on a complete basis, seen that product and container are treated at the same time.

In comparison with the tunnel pasteurization, in the (2) "Flash" Pasteurization, there is a reduction in cost and in the space constructed. The speed in taste deterioration along the time is significantly reduced, once the product remains in high temperatures for little time. Lower weight packages can be used due to lower pressures obtained by the cold process. The cost of this system is quite high, since the package's filling up and sealing requires the use of aseptic systems. Provided that only the product beer is being pasteurized, the probability of recontamination during the filling up-sealing phase is very high. Due to the fact that packaging is effected at low temperatures, a transpiration of the package may occur, causing a subsequent damage to labels and cards. Technically qualified persons are needed to operate the equipment, to maintain the asepsis and to effect the microbiological quality control of the system, in order to achieve a minimum commercial biological stability.

The equipment used in (3) the Sterile Filtering is compact, the space being used in a rational manner. Once the heating phase of the product is eliminated, there is a better taste quality. It represents a high cost method, because the use of the filling up and sealing aseptic system is essential, in order to avoid an eventual recontamination of the product.

The (4) Continuous Refrigeration, when carried out accordingly, retards the multiplication of microorganisms. It has the advantage of being stored at low temperature, thus maintaining the freshness and quality characteristics of the product. The system is quite expensive, because the costs for the construction of an isolate area, acquisition of refrigeration equipment and cold-stored trucks are quite high. The transpiration of the product during commercialization may cause considerable damage to its presentation, therefore requiring the product's repackaging. It is necessary to inform the consumer as to the product's storage under refrigeration conditions. It is essential that an intensive monitoring be maintained to assure the product's proper refrigeration and protection.

The (5) Direct Addition of Preservative Stabilizer (Heptylparaben) does not require the use of additional equipment within the plant, thus allowing space saving and rational utilization. The product is protected before and after packaging, therefore, the use of aseptic systems is not necessary. Never the less, the use of heptylparaben, bring some alterations to flavour and maintenance of the foam, besides the product's clouding. The use of propylene glycol alginate compensates such deficiencies at an additional cost and the flavour alterations, as small as the additive's concentration (that causes a sensible microbiologic estabilization capacity loss). The US 792166 shows a 6 to 10 ppm product concentration to reach good results for non pasteurized beer.

The use of P.H.M.B. (biguanide poly-hexamethylen hypochlorite) does not cause such problems. The usage of heptylparaben requires attention due to its limited water and beer solubility, while with P.H.M.B such problem does not occur.

Briefly, the use of biological stabilizers together with additive and a especial mild thermal treatment (time and/or low temperatures) in the product have more advantages in relation to the other four alternatives. This system is easily controllable, protecting the product as from its addition during the process until the final consumer.

Comparatively, the costs even related to the additive amount used, even related to the thermal treatment are lower. Due to the high potential of this method, studies have been carried out in order to find a stabilizer which would supply additives and conventional pasteurization deficiencies, maintaining the product's original properties. The beer is a complex system, extremely sensitive to the action of the oxygen.

Together with the influence of external factors, such as temperature (as on a flash or tunnel pasteurization) , light and shaking, over the organoleptic stability of the packed beer, the presence of oxygen causes, among other things, the formation of carbonyl links, conferring "oxidation taste" (aging), the oxidation of the aromatic substances of the lupulus, as well as the beer darkening.

In order to ensure the organoleptic stability, in which the reduction of the oxygen action plays an important role. Normally, in can (impermeable) or glass containers, anti-oxidants agents are added as ascorbic acid or iso-ascorbic acid plus SO₂.

Nevertheless, this protector agent acts only during the beginning days after the beverage bottling. When the existing oxygen in consumed.

For a continuous action in permeable containers, an enzymatic complex can be added with the objective of consuming even the remaining oxygen in the bottle's "head space", the dissolved oxygen, besides the oxygen which, occasionally, might permeate through the walls or through the closing system. Such enzymatic complex is constituted by, at least, five enzymes, of which the glucose-oxidase and catalase actuation is emphasised. The glucose-oxidase catalyses the reaction of the oxygen with the glucose, forming the gluconic acid and the oxygenated water that is later consumed by catalase, forming water and half the original oxygen. These two are chain reactions which occur until the total elimination of the oxygen. During the shelf-life, the oxygen penetrating through the plastic package walls shall also be consumed by the same process.

Glucose + O₂ + H₂O ^{Rlucose oxidase} -» Gluconic acid + H₂O₂ [1]

H ²*⁵ -M/2 O₂ + H₂O [2] In general, a quantity of 1 to 100 ppm of enzyme is employed, sufficient to consume the oxygen which has permeated through a polyethylene tereftalate bottle, based on the principle that, through a 500 ml polyethylene tereftalate package there is a penetration of 0.03 cm³/package/day. Glucose oxidase may be produced by the Aspergillus niger. Its substratum may be constituted by glucose, followed or not by other sugars such as: lactose, raffinose, fructose, saccharose, galactose, maltose and water. Its pH of actuation is lower than 5.0. It is added into beer before thermal treatment. An important problem, however, is the possibility of a preferential reaction between the hydrogen peroxide produced at the reaction [1] and the beer components. This problem had to be solved to ensure the use of this types of enzyme. The U.S. patent 5,010,007 mentions that the enzymatic complex used in the process may comprise an oxidase and the substrct thereof, catalase and superoxide dismutase. The use of these three enzymes generates a synergistic effect in relation to the antioxidant properties thereof. In fact, the use of such enzymes separately provides inconclusive results. The use of preservatives for microbiological preservation of beverages is well- known of the state-of-the-art. Due to the need of applying a high dosage of sorbic or benzoic acid, a widely used preservative, preservatives synergistically used and dosed in quite lower quantities are being used, since they are more efficient.

As mentioned in the article " New Technique for the Cold Sterilization of Beer, by J. A. Kozulis; P. D. Bayne and J. Cuzner, Milwaukee, Wis.", the n-heptyl p- hydroxibenzoate, a member of the paraben family, was the first cold stabilizer to be used by the brewer industry in the United States. This composition has an optimum antimicrobian activity at low concentrations. However, it exercises an influence on the beer's superficial tension, causing a reduction in the foam's stability. The n-heptyl p- hydroxibenzoate when used on levels over its solubility limit in beer, may cause a clouding effect in the final product, .

As mentioned in the article "n-Octyl Gallate, a New Beer Microbiological Inhibitor, by M. Loncin (Brussels, Belgium); J. A. Kozulis; P. D. Bayne (Milwaukee, Wisconsin)", the use of n-heptyl p-hydroxibenzoate, jointly with n-octyl gallate is reported. It is a comparative study of the properties of these two preservatives, and n- octyl gallate has proved to be the most soluble, not causing, consequently, problems of application during the process. We must add to this, its minimum influence in the foam's properties, in the beer's hydrolysis and in the alteration of odour and taste. With the objective of solving the problems mentioned above, a new formulation was developed to be utiled in the preservation of beverages.

The idea developed by the Applicant is characterized by presenting in its composition: (A) one or more enzymatic complexes; (B) one or more preservative agents and optionally, (C) other food additives associated to a mild thermal treatment (D) specially thought to minimize the beverage degradation, but due to the big synergistic effect with (A), (B), (C), is capable to have good microbiologic stability, maintaining organoleptics characteristics and other inherent beverage characteristics.

The invention consists on formulation that has a high synergistic potential mild thermal treatment. The association of this factors has high technical importance once that without aggressive treatments (that may degrade the food's characteristics) and a low food additives rate (what is good for organoleptic characteristics), it's possible to add microbiologic stability to sensible products, as beer in example, in sensible containers at temperatures normally used in pasteurization treatments. Besides that the container may have a permeable level to oxygen, avoiding oxidative degradation to product.

The main function of the enzymatic complex (A) is the catalysis of reactions consuming the oxygen that permeates the container during the storage period. The oxygen dissolved in the product that comes from the bottling/manufacturing process is eliminated by other mean, without affecting the beverage's sensorial characteristics. The enzymatic complex may comprise mainly two enzymes: glucose-oxidase and catalase. The glucose-oxidase catalyzes the reaction of the oxygen with glucose, forming the gluconic acid and the oxygenated water that is later consumed by catalase, forming water and half of the original oxygen. These two are chain reactions which occur until the total elimination of the oxygen. During the shelf-life, the oxygen penetrating through the plastic package walls shall also be consumed by the same process.

The preservatives (B) preserve the beverage microbiologically. The following may be used as preservatives: alkyl p-hydroxibenzoic acid or esters derived thereof, as for example: methyl p-hydroxibenzoic acid ester, ethyl p-hydroxibenzoic acid ester, propyl p-hydroxibenzoic acid ester, butyl p-hydroxibenzoic acid ester, heptyl p- hydroxibenzoic acid ester and octyl p-hydroxibenzoic acid ester. All of them are more active against yeasts and bacteria, than the benzoic acid, and lower dosages can be used. Jointly, such preservatives have a total and synergistic action, preventing the multiplication of microorganisms.

Other food additives (C) may also, optionally, be added, like the antioxidants eritorbic acid and salts thereof and/or ascorbic acid and salts thereof, and also stabilizers known of the skilled-in-the-art man, as for example, propylene glycol alginate. The thermal treatment (D), due to the synergy with the formulation components, allows that products as beer , in example, may be microbiologically stabilized under less then 10 UPs (pasteurization units). Each pasteurization unit corresponds to a 1 minute, 60°C treatment.

Due to the characteristics of the beverage in which the idea proposed has been added, any type of container can be used: tin, glass, card or low temperature resistant plastic materials; we can mention, for example, permeable containers as PET, PEN, PVC, PP, PE, PC, PET/PEN blends, one or more polymer multilayers, coating containers, etc. The advantage proportioned by the present invention, is the maintenance of the draft beer organoleptic characteristics and the beer stability, in the final product.

Examples:

Example 1: Adopting, as example, a soft drink with 12% sugar, pH approximately equal to 3, with 2 to 3 volumes of carbonic gas and a initial yeast counting of <2000/100 ml, lactic bacteria < 10/100ml, total counting of mesophyllus < 2000/100ml and oxygen-labile flavours in a content higher than 0.2 ppm dissolved in the beverage, in package allowing the passage of 0.6 ppm of oxygen in 24 hours. Using a group of additives comprising: methyl, propyl and heptyl paraben preservatives in the following concentrations: 100/100/5 ppm in relation to soft drink and with an oxygen consumption catalyzer, an enzymatic complex containing glucose-oxidase and catalase in the concentration of 100 ppm, and 1200 GOX units (IGOX unit is the amount of enzyme which, at 25°C and pH 5.1 catalyses the formation of lμmole H₂O₂) after a thermal treatment equivalent to 1 UP (pasteurization unit) the product preserves its original characteristics, being maintained micro-biologically, physic-chemically and sensory stable during a period of up to 6 months of shelf-life. Example 2: Adopting, as example, a natural filtered grape juice with 18 BRIX, filtered, with initial count of: yeasts < 1500/100ml, lactic bacteria < 20/100 ml, total counting of mesophillus < 2000/100 ml, labile to oxidation and to the growth of deteriorative microorganisms, it can be preserved using a mixed process of thermal treatment (50°C/60 minutes) and methyl propyl/heptyl parabens in concentrations of

150/50/6 ppm plus the addition of 20 ppm (with 1200 GOX units fo example) of an enzymatic complex containing glucose-oxidase and catalase, utilizing a plastic package having a permeability of 0.05 ppm (IGOX) of oxygen/24 h. The juice preserves its original flavour, taste and colour characteristics, without biological, physic-chemical and sensorial modifications up until 12 months.

Example 3: Adopting, as example, filtered draft beer with the following characteristics: pH approximately 4, original dissolved oxygen < 0.25 ppm, 4% alcohol in volume, carbonation of 2.8 volumes of CO₂, initial microbial count: yeasts < 1000/100 ml, mesophylls < 1500/100 ml, using the ascorbic acid as antioxidant in 40 ppm concentration and propylene glycol alginate as stabilizer in 40 ppm concentration. This product can be preserved with the utilization of a mixture of preservatives: methyl/propyl/heptyl parabens in concentrations of 250/200/3.5 ppm and an enzymatic complex of glucose-oxidase/catalase in a concentration of 50 ppm (with 1200 GOX for example), combined with a thermal treatment for 60 minutes at 49°C, ideal condition for the activity of the enzymatic complex, the product maintains its original characteristics preserved for up to 6 months in packages which are impermeable to gas exchanges, or up to 4 months in plastic packages having an oxygen permeability of 0.09 ppm for 24 hours. Example 4 : Considering a beverage of the isotonic type, containing carbonates, phosphates, citrates, sodium, potassium, calcium, magnesium, and having 5% of sugars

(glucose and or fructose and/or saccharose).

Packed in a container at 60°C with addition of methyl/propyl/heptyl parabens in concentrations of 150/75/4 ppm and 30 ppm (1200 GOX units for example) of an enzymatic complex of glucose-oxidase/catalase, this product maintains its initial sensory, chemical, physic-chemical and microbiological characteristics for a period of up to 12 months.

Claims

1. Composition containing additives and coadjuvants for preservation of beverages wherein its formulation contains: (A) one or more enzymatic complexes; (B) one or more preservative agents and optionally, (C) other food additives associated to a mild thermal treatment specifically developed (D) to a maximum of 25 UP of intensity, and less then 10 UP preferentially , and less then 4 UP most preferentially.

2. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, wherein the enzymatic complexes comprise mainly two enzymes: glucose-oxidase and catalase, but also a dismutase / catalase and superoxidase / catalase.

3. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1 and 2, wherein the substratum used in the enzymatic complex comprises mainly glucose and water.

4. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, 2 and 3, wherein it contains 1 to 100 ppm of enzymatic complex.

5. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, 2, 3 and 4, wherein it contains, preferably, 1 to 40 ppm of enzymatic complex.

6. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, wherein the preservatives used are from the paraben family.

7. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1 and 6, wherein it contains as preservatives at least one of the methyl, ethyl, propyl, butyl and octyl parabens in the following concentrations:

(a) from 0 to 600 ppm of methyl paraben and/or

(b) from 0 to 500 ppm of ethyl paraben and/or

(c) from 0 to 400 ppm of propyl paraben and/or (d) from 0 to 200 ppm of butyl paraben and/or

(e) from 0 to 12 ppm of heptyl paraben and/or

(f) from 0 to 8 ppm of octyl paraben and/or

8. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, 6 and 7, wherein it contains as preservatives methyl, propyl and heptyl parabens preferably in the following concentrations:

(a) from 0 to 600 ppm of methyl paraben

(b) from 5 to 300 ppm of propyl paraben (c) from 0.5 to 12 ppm of heptyl paraben

9. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, 6, 7 and 8, wherein it contains as preservatives methyl, propyl and heptyl parabens, more preferentially, in the following concentrations: (a) from 10 to 250 ppm of methyl paraben

(b) from 5 to 150 ppm of propyl paraben

(c) from 0.2 to 5 ppm of heptyl paraben

10. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, wherein it contains other antioxidant and stabilizing additives.

11. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, wherein the preserved beverage is alcoholic or not, fermented or not, carbonated or not, sensitive to the action of oxygen and subject to microbiological deterioration.

12. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1 and 11, wherein the beverage is a beer or draft beer.

13. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, wherein the preserved beverage can be packed in any type of packaging.

14. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1 and 13, wherein the preserved beverage, preferentially, is packed in plastic packaging of the type PET, PEN, PVC, PP, PE, PC, PET/PEN blends or one or more polymer multilayers.

15. Composition containing additives and coadjuvants for preservation of beverages in accordance with claim 1, 13 and 14, wherein the preserved beverage, more preferentially, is packed in a PET type plastic packaging.