JP2012511690A - Self-cooling vessel and cooling device - Google Patents

Abstract

  The present invention relates to a container for storing a beverage, the container comprising a container body and a closure, and defining an internal chamber, the internal chamber defining an internal volume and containing a predetermined volume of the beverage. The container further comprises a cooling device having a housing defining a housing volume. The cooling device includes at least two separate substantially non-toxic reactants that initiate an irreversible entropy increasing reaction that produces a stoichiometric number of substantially non-toxic products. The at least two separate substantially non-toxic reactants initially retained in the chiller are separated from each other, causing an entropy increasing reaction and reducing the calorific value of at least 50 joules of beverage per ml of beverage. . The cooling device further comprises an actuator for initiating a reaction between at least two separate substantially non-toxic reactants.

Description

  Beverage cans and beverage bottles are carbonated beverages such as beer, cider, sparkling wine, carbonated mineral water, or various soft drinks, or non-carbonated beverages such as non-carbonated water, dairy products such as milk and yogurt, wine, or It has been used for decades to store beverages such as various fruit juices. Beverage containers, such as bottles, especially cans, are typically designed to contain the maximum amount of beverage, minimize the amount of material used, and ensure the mechanical stability of the beverage container .

  Most beverages have an optimum serving temperature that is significantly lower than the standard storage temperature. Beverage containers are typically stored at room temperature in supermarkets, restaurants, homes, and storage facilities. The optimum ingestion temperature for most beverages is about 5 ° C., so it needs to be cooled before serving the beverage. Typically, the beverage container is stored in a refrigerator or refrigerated storage room or the like long before serving the beverage so that the beverage can be brought to a temperature of about 5 ° C. before serving. Therefore, a person who wants to be able to drink the beverage immediately must always store the beverage at a low temperature. Many commercial facilities, such as bars, restaurants, supermarkets, and gas stations, always need to run a refrigerator to meet the consumer's cold beverage requirements. This can be regarded as a waste of energy because the beverage can may have to be stored for a long time before being consumed. In this context, the applicant company alone will install about 17,000 refrigerators per year to serve cold beverages, each refrigerator typically consuming about 200 W of power. It should be mentioned.

  As described above, cooling of the beverage container by refrigeration is very slow and wastes energy. Some people will reduce the time required for cooling by placing the beverage container for a short time in a refrigerator or similar storage facility whose temperature is well below freezing. However, this entails a safety risk because if the beverage is not removed from the freezer sufficiently before the beverage freezes, the beverage container may break due to the expansion of the beverage. Alternatively, buckets with ice and water can be used for more efficient cooling of the beverage because the thermal conductivity of water is significantly higher than that of air.

It would be advantageous if the beverage container itself was equipped with a cooling element that could be activated just prior to drinking to cool the beverage to a suitably low temperature. Within the beverage packaging, certain techniques related to cooling beverage cans and self-cooled beverage cans are described in particular in US Pat. No. 4,403,567, US Pat. No. 7,117,684, European Patent No. 0498428, US Pat. No. 2886991, British Patent No. 2384846, International Publication No. 2008/000271, British Patent No. 2261501, US Pat. No. 4,209,413, US Pat. No. 4,273,667, US Pat. No. 4,303,121, US Pat. No. 4,470,917, US Pat. No. 4,689,164, U.S. Patent Application Publication No. 2008/0178865, JP-A No. 2003-207243, JP-A No. 2000-265165, U.S. Pat. No. 3,309,890, International Publication No. 85/02009, U.S. Pat. No. 3,229,478, U.S. Pat. No. 4599872, National Patent No. 4669273, International Publication No. 2000/077463, European Patent No. 87859 (corresponding to US Pat. No. 4,470,917), US Pat. No. 4,277,357, German Patent No. 3024856, US Pat. No. 5,261,241 (European Patent) No. 0498428, British Patent No. 1596076, US Pat. No. 6,558,434, International Publication No. WO02 / 085748, US Pat. No. 4,993,239, US Pat. No. 4,759,191, US Pat. No. 4,752,310, International Publication No. WO 01/10738. No. 1, European Patent No. 1746365, US Pat. No. 7,117,684, European Patent No. 0498428, US Pat. No. 4,784,678, US Pat. No. 2,746,265, US Pat. No. 18,97723, US Pat. No. 2,886,691, British Patent No. 2,384,846. U.S. Pat. No. 4,802,343, U.S. Pat. No. 4,993,237, International Publication No. 2008/000271, British Patent No. 2261501, U.S. Patent Application Publication No. 20080178865, JP 2003-207243, U.S. Pat. No. 3,309,890, U.S. Pat. No. 3229478, International Publication No. 2000/077463, International Publication No. 02/085748.

  In the above-mentioned patent documents, techniques for cooling by chemical reaction or evaporation are described. When such a technique as described above is used, the beverage can be instantly cooled, no prior cooling is required, and consumption of electrical energy can be avoided. In the above technique, the cooling device is larger than the beverage container. In other words, the material and volume are wasted because a large beverage container must be prepared to accommodate a small amount of beverage. Accordingly, there is a need for a cooling device that cools better and / or occupies less space in the beverage container.

  It is an object of the present invention to provide a cooling device that can be used in a beverage container to reduce the temperature of the beverage from about 22 ° C. to 5 ° C. to eliminate or at least substantially reduce the need for motorized external cooling. It is to be.

  A further advantage according to the invention is that after the beverage container and the cooling device have been stored for a long period of time, for example for weeks, months or years, just before the beverage is about to be drunk, The beverage can be cooled to an appropriate intake temperature. Therefore, a further object of the present invention is to provide an actuating device that activates the cooling device just before the beverage is about to be drunk.

The above objects and various other objects will become apparent from the following detailed description of the preferred embodiment of the cooling device according to the present invention and the first aspect of the present invention obtained by a container for storing beverages. . The container comprises a container body and a closure and defines an internal chamber, the internal chamber defines an internal volume and contains a predetermined volume of beverage,
The container further comprises a cooling device having a housing defining a housing volume not exceeding about 33% of the predetermined volume of the beverage and not exceeding about 25% of the internal volume;
The cooling device includes at least two separate substantially non-toxic reactants that, when reacted with each other, are at least 3 (factor 3), preferably at least 4, than the stoichiometric number of the reactants. More preferably initiates an irreversible entropy increasing reaction that produces a substantially non-toxic product of at least 5 greater stoichiometry,
When at least two separate substantially non-toxic reactants are initially separated from each other and held in a cooling device and react with each other in the irreversible entropy increasing reaction, it is 5 minutes or less, preferably 3 minutes or less, more preferably In a time of 2 minutes or less, the calorie of the beverage is reduced by at least 50 joules per ml of beverage, preferably at least 70 joules, for example 70-85 joules, preferably about 80-85 joules,
The cooling device further comprises an actuator for initiating a reaction between at least two separate substantially non-toxic reactants.

  The container is typically a small serving container having a beverage volume of about 20-75 centimeters. However, in some cases, the cooling device may be used with a larger container, such as a large bottle or container capable of containing 1 liter of beverage, or a keg capable of containing 5 liters or more of beverage. In such a case, the cooling device is intended to instantly cool the beverage to a drinking temperature suitable for the first serving of the beverage, and after cooling, the beverage may be stored in a refrigerator for later serving. . The container is preferably formed from aluminum that is easy to manufacture, ie, stamped out, and that can be melted and recycled in an environmentally friendly manner. Alternatively, the shrinkable or non-shrinkable container can be made from a polymeric material such as PET plastic. In a further alternative, the container can be a conventional glass bottle.

  The cooling device is preferably fixed to the beverage container by fixing it to the bottom of the beverage container or the lid of the beverage container. The cooling device should have a housing for separating the beverage and the reactants. If the cooling device is too large, the amount of beverage contained in the beverage container will be reduced and should not require a significant portion of the internal volume of the beverage container. This requires either a larger beverage container or a larger number of beverage containers to accommodate the same amount of beverage, and both options require more raw material to be used in the manufacture of the container and storage. This is undesirably ecologically and economically because it increases the bulk of transportation. It is contemplated that a refrigerator housing volume of approximately 33% of the beverage volume and 25% of the total internal volume of the beverage container is an acceptable trade-off between cooling efficiency and the volume of beverage to be contained. . A cooling device that is too small will not be able to cool the beverage to a sufficiently low temperature.

The two reactants used in the cooling device are kept separate prior to operation of the cooling device, and the two reactants react with each other during operation of the cooling device. The reactants can be held separately, for example, by being housed in two separate chambers, or one or both reactants can be provided with a coating to prevent all reactions until the start of the reaction. The two reactants should be substantially non-toxic, which means that they are not lethal if the appropriate amount used in the cooling device is accidentally ingested. I want you to understand. It is further contemplated that more than two reactants may be present, for example, three or more reactants. The reaction should be an entropy increasing reaction, i.e. the number of reaction products should be greater than the number of reactants. In this context, it is surprising that an entropy increasing reaction that produces a product with a stoichiometric number of at least 3, preferably 4 or more, more preferably 5 greater than the reactant stoichiometry, is less than the lower stoichiometry. It has been found that it provides cooling efficiently. The stoichiometric number is the relationship between the number of products and the number of reactants. The reaction should be irreversible, which should be understood to mean that reversal of the reaction is not possible without significant difficulty, which can lead to the possibility of reheating the beverage. The temperature of the beverage should be at least 15 ° C., preferably 20 ° C. lower, which corresponds to a calorie reduction of about 50 to 85 joules of beverage per liter of beverage in the case of water-based beverages. A smaller temperature drop or calorie reduction will not provide sufficient cooling to the beverage, so the beverage will be improperly sown even when the chemical reaction is complete and the beverage is served. Preferably, the chemical reaction results in a heat loss of 120-240 J / ml of reactants, most preferably 240-330 J / ml of reactants. Such cooling efficiency is generally the cooling efficiency obtained by melting ice in water. The chemical reaction is preferably as rapid as possible, but some time is allowed for heat energy transfer to avoid the formation of ice near the cooling device. Preferably, it is contemplated that the heat loss or temperature reduction is achieved within 5 minutes, preferably within 2 minutes. There is an acceptable time to drink. Comparison In this context, carbonated beverages, typically because the generation of the bubble CO ₂ occur in the beverage temperature is rapidly equally within the beverage to increase the amount of turbulence in the beverage, and non-carbonated beverages Note that a lower temperature of the cooling device is allowed.

  Furthermore, the term “irreversible” should be considered synonymous with the word “irreversible”. The term “irreversible reaction” refers to a reaction in which the reaction product and reactant are not in a chemical equilibrium that can be reversed by simple changes such as reactant and / or reaction product proportions and / or external conditions such as pressure and temperature. Should be understood to mean Examples of irreversible reactions include reactions where the reaction product is a complex, precipitate, or gas. A chemical reaction, for example, a reaction involving dissolution of a salt in a solution such as water and dissociation of the salt into an ion that causes equilibrium, stops spontaneously when the forward and reverse reactions occur at the same rate, for example, In solutions or mixtures of the above, the reaction is limited by the solubility of the reactants. The irreversible reaction defined above continues until all reactants have reacted.

  German Offenlegungsschrift 2 150 305 A1 describes a method for cooling beverage bottles or beverage cans. A cooling cartridge containing a soluble salt is included in the beverage bottle or beverage can. By dissolving the salt in a certain amount of water, a cooling effect can be obtained utilizing negative enthalpy of dissolution. However, with the use of the proposed negative dissolution enthalpy, if the initial temperature is 21 ° C., the minimum temperature achieved is about 12 ° C. In any embodiment example, the desired temperature of about 5 ° C. is not reached. Due to the calculation of heat loss in the beverage (Q = c × m × ΔT), the exemplary embodiment achieves only about 15-38 J / ml of heat reduction in the beverage. Also, all examples of embodiments require a reactant having a total volume that exceeds 33% of the volume of the beverage. In addition, all reactions proposed in the above literature are considered reversible reactions because they can be reversed simply by removing water from the solution. By removing the water, the dissolved salt ions recombine to form the original reactant.

  German utility model No. 29911156U1 discloses a beverage can with an external cooling element. The cooling element can be activated by applying pressure to mix the two chemical species within the cooling element. In the above document, there is only one chemical reaction involving dissolution and dissociation of potassium chloride, nitrate and salmiac salt in water, where the temperature of the cooling element is stated to reach 0 ° C. or −16 ° C. Although described, this description does not touch on the starting temperature of the cooling element. This description also does not mention the dimensions used for the cooling element and what volume of beverage and reactants were used.

Many irreversible entropy increasing reactions are well known as such. An example is the Internet URL: http: // web. archive. org / web / 20071129232734 / http: // chemed. chem. purdue. edu / demo / demosheets / 5.1. Found in html. The above reference proposes the following reaction.
Ba (OH) ₂ .8H ₂ O (s) + 2NH ₄ SCN (s) → Ba (SCN) ₂ + 2NH ₃ (g) + 10H ₂ O (l)

  The above reference suggests that the reaction is an endothermic entropy increasing reaction and is lower than the freezing temperature of water. However, there is no description as to whether this reaction can be used in connection with cooling of the beverage, and there is no information about the amount of available reactant required, or whether an actuator is used to initiate the reaction.

  Note that, unlike most solution reactions, the reaction can be initiated without any addition of liquid water. Some other irreversible entropy increasing reactions require only a drop of water for initiation.

  The use of ammonia is not preferred in this context, as ammonia is considered toxic and will give the beverage a very unpleasant taste when it enters the beverage. Preferably, all reactants and reaction products should have a neutral taste in addition to being non-toxic, even when accidentally released into the beverage.

  An actuator is used to initiate a chemical reaction between the reactants. The reactant may comprise a pressure transmission device for transmitting an increase or decrease in pressure from within the beverage container to the cooling device to initiate the reaction. Since the pressure drop is typically achieved when the beverage container is opened, the cooling device can be configured to operate when the beverage container is opened. Alternatively, a chemical reaction can be initiated using a mechanical actuator. The mechanical actuator can be a string or a rod or communicate with the exterior of the beverage container to initiate a chemical reaction. Alternatively, the mechanical actuator can be connected and attached to the closure of the container so that a chemical reaction is initiated when the container is opened. Initiating a reaction places two reactants in different chambers provided by a breakable, meltable, or breakable membrane that brings the two reactants into contact with each other, i.e., destroyed, dissolved, or broken by an actuator. Can be done by. The membrane can be broken using, for example, a penetration element. The reaction product and reactant should be substantially non-toxic.

  One type of actuator that penetrates a membrane that uses a spike to separate two chemical species is described in the above-mentioned German Patent Application No. 2150305A1. US 2008/0016882 shows a further example of an actuator having two species separated by a peelable membrane or small conduit.

  The volume of the product should not substantially exceed the volume of the reactants, if the volume of the reactants substantially exceeds the volume of the reactants, the cooling device can explode during the chemical reaction. A safety margin of 3-5% can be taken or a discharge opening can be provided. Volume reduction should also be avoided. Since the granules can be easily handled and mixed, the reactants are preferably prepared as granules. The granules can be provided with a coating that prevents reaction. The coating can be dissolved during the reaction by, for example, a liquid that enters the reaction chamber and dissolves the coating. This liquid can be referred to as an activator and can be, for example, water, propylene glycol, or alcohol. It is further contemplated that reaction control agents such as selective absorption control agents or delayed temperature setting agents can be used to slow the reaction rate and catalysts can be used to increase the reaction rate. It is further contemplated that the container may include a guide element that guides the beverage flow to the chiller to increase cooling efficiency. The cooling device can also be used for so-called party kegs. The party keg is a beverage keg that can be pressurized and dispensed inside. In this way, relatively large party kegs need not be pre-cooled before use. Alternatively, the cooling device can be provided as a small device that is freely movable within the container. This would be suitable for glass bottles where it may be difficult to provide a fixed cooling device.

According to a further embodiment of the first aspect of the invention, the two separate reactants comprise one or more salt hydrates. Salt hydrates are known to cause entropy increasing reactions by releasing water molecules. In this context, proof-of-concept was done by conducting experiments in the laboratory. In the laboratory experiments described above, dramatic energy changes were brought about by reacting two salts, each having a large number of crystal water molecules added to the structure, to liberate crystal water as free water. In this laboratory experiment, the following chemical reactions were tried: Na ₂ SO ₄ , 10H ₂ O + CaCl ₂ , 6H ₂ O → 2NaCl + CaSO ₄ , 2H ₂ O + 14H ₂ O. The left side of the reaction formula contains a total of two molecules, while the right side of the reaction formula contains a total of 20 molecules. Accordingly, since ΔS matches k × ln20 / 2, the entropy element −TΔS becomes considerably large.

The above chemical reaction produces a single salt in an aqueous solution of gypsum. It is therefore clear that all components of this reaction are non-toxic and non-contaminating. In this experiment, 64 grams of Na ₂ SO ₄ and 34 grams of CaCl ₂ were used, and the reaction decreased the temperature by 20 ° C., and the stability was maintained for 2 hours or more. A prototype beer can with a total volume of 450 ml was produced, including 330 ml of beer and 100 ml bottle containing two reactants. After opening the can, the reactants react and the beer in the beverage can is dramatically cooled.

  According to the present invention, the cooling device is formed based on a chemical reaction between two or more chemical reactants. This chemical reaction is a natural irreversible endothermic reaction driven by an increase in total entropy. This chemical reaction absorbs heat from the environment and results in an increase in the thermodynamic potential of the system. ΔH is a change in enthalpy and has a positive sign of endothermic reaction. The spontaneous occurrence of the chemical reaction can be confirmed from the change in the Gibbs free energy ΔG.

  At a constant temperature, ΔG = ΔH−T × ΔS. A negative ΔG for the reaction indicates that the reaction is spontaneous. In order to meet the requirements of spontaneous endothermic reaction, the total increase in entropy ΔS for the reaction must exceed the increase in enthalpy ΔH.

  According to a further embodiment of the first aspect of the present invention, the at least two separate substantially non-toxic reactants comprise a first reactant, a second reactant, and a third reactant. The second reactant and the third reactant are present as separate granules, and the first reactant is used as a coating covering the granules of the second reactant and the third reactant . By coating the second reactant and the third reactant with the first reactant, the second reactant and the third reactant are prevented from reacting by the third reactant. It can be ensured that the three reactants are kept separated even if they are mixed. In this way, for example, accidental initiation of chemical reactions, such as by impact, can be avoided, and the coating protects the second and third reactants even if a small amount of water enters the reaction chamber. Therefore, the reaction is not started. The non-reactive coating preferably wastes volume and requires a larger cooling device, so the first reactant is preferably used as the coating.

  According to a further embodiment of the first aspect of the invention, the second reactant and the third reactant undergo a first irreversible entropy increasing reaction to produce an intermediate reaction product, and the third reactant Reacts with the intermediate reaction product to cause a second irreversible entropy increasing reaction. If the intermediate reaction product is toxic or gives off discomfort such as malodor, the intermediate product is reacted with a third reactant to provide a safe final product that does not have any disadvantages of the intermediate reactive organism. By producing the product, the adverse effects of the intermediate product can be avoided.

  According to a further embodiment of the first aspect of the present invention, the intermediate product is a gas and the second irreversible entropy increasing reaction produces a complex or precipitate. For example, if the intermediate product is a toxic or odorous gas, this intermediate product would not be suitable for use in this context. The gas can then be sedated by reacting with a third reactant to produce a safe complex or precipitate.

  According to a further embodiment of the first aspect of the present invention, the first reactant is dissolvable by a liquid such as water or an organic solvent, preferably water, the first reactant and the second reactant. And the third reactant are prevented from reacting by the coating. At the start of the reaction, an amount of water sufficient to at least partially dissolve the coating is introduced into the chiller so that all three reactants can dissolve and react with each other.

  According to a further embodiment of the first aspect of the present invention, the cooling device is housed in a container. In order to ensure that most of the cooling energy is used for cooling the beverage and does not disappear to the surroundings, the cooling device is preferably in direct contact with the beverage, more preferably completely surrounded by the beverage. It can be placed in a container.

Reactant The cooling device according to the present invention, when reacted with each other, produces an irreversible entropy that produces a substantially non-toxic product with a stoichiometry of at least 3, preferably 4, more preferably 5 greater than the stoichiometry of the reactants. It includes at least two separate, substantially non-toxic reactants that initiate an increasing response. The reactant is preferably a solid, but solid-liquid, liquid-liquid, and solid-solid-liquid reactants are also suitable in the context of this context, i.e. the implementation of the cooling device used in the beverage container. I also plan to be. The solid reactant can be present as a powder, granule, or shavings.

  The reactants and products are substantially non-toxic.

In the context of the present invention, non-toxicity should not be construed literally, but any reactant or product that is not lethal when ingested in the amounts and forms used by the present invention. It is. Suitable reactants produce products that are (a) readily soluble in free crystal water or (b) poorly soluble in free crystal water. The easily soluble products and the hardly soluble products are listed below.
Easy solubility Difficult to dissolve NaCl BaSO ₄
KCl BaCO ₃
NH ₄ Cl Bi (OH) ₃
NH ₄ Br CaCO ₃
NH ₄ C ₂ H ₃ O ₂ Ca ₃ (PO ₄ ) _{2
NH 4 NO 3 CaSO 4 · 2H} 2 O
(NH ₄ ) ₂ SO ₄ CoCO ₃
NH ₄ HSO ₄ Co (OH) ₂
CaCl ₂ CuBr
CrCl ₂ Cu (OH) ₂
CuBr ₂ Fe (OH) ₂
LiBr · 2H ₂ O Fe (OH) ₃
LiCl · H ₂ O FePO ₄ · 2H ₂ O
NH ₂ OH Fe ₃ (PO ₄ ) ₂
KBr Li ₂ CO _{3
KCO 3 · 1 1 / 2H 2} O MgCO 3
KOH · 2H ₂ O MnCO ₃
KNO ₃ Mn (OH) ₂
KH ₂ PO ₃ Ni (OH) ₂
KHSO4 SrCO ₃
NaBr ₂ 2H ₂ O SrSO ₄
NaClO ₃ Sn (OH) ₂
NaOH.H ₂ O ZnCO ₃
NaNO ₃ Zn (OH) ₂
NaSCN
SnSO ₄
TiCl ₃
TiCl ₄
ZnBr ₂ · 2H ₂ O
ZnCl ₂
NH ₄ SCN

Further suitable reactants are as follows:
NaAl (SO ₄ ) _2, 12H ₂ O
NH ₄ Al (SO ₄ ) _2, 12H ₂ O
LiOH H ₂ 0
Na ₂ SiO ₃
Na ₂ SiO ₃ . xH ₂ O, x = 5-9
Na ₂ O. xSiO ₂ x = 3-5
Na ₄ SiO ₄
Na ₆ Si ₂ O7
Li ₂ SiO ₃
Li ₄ SiO ₄

  Additional reactants and reactant sets are listed in Tables 1 and 2 below.

  The salt product is preferably a readily soluble salt, but a poorly soluble product is preferably a toxic salt product that is substantially non-toxic.

  The volume change during the irreversible entropy increasing reaction is ± 5% or less, preferably ± 4% or less, more preferably ± 3% or less, or the cooling device has any excess produced in the irreversible entropy increasing reaction. It communicates with the atmosphere so that gas can be released into the atmosphere.

Suitable solid reactants according to the present invention are salt hydrates and acid hydrates. The salt hydrate according to the present invention is an organic salt hydrate or an inorganic salt hydrate, preferably an inorganic salt hydrate. Some of the following salts are thought to be present only in trace amounts to control selective absorption. Suitable organic salt hydrates, magnesium picric octahydrate _{Mg (C 6 H 2 (NO} 2) 3 O) 2 · 8H 2 O, picric acid strontium hexahydrate _{Sr (C 6} H 2 (NO _{2) 3 O) 2 · 6H} 2 O, potassium sodium tartrate tetrahydrate _{KNaC 4 H 4 O 6 · 4H} 2 O, sodium succinate hexahydrate _{Na 2 (CH 2) 2 (} COO) 2 · 6H 2 O, copper acetate monohydrate Cu (CH ₃ COO) ₂ .H ₂ O, and the like are included. Suitable inorganic salt hydrates according to the invention include alkali metal salt hydrates such as lithium, sodium, and potassium, alkaline earth metal salt hydrates such as beryllium, calcium, strontium, and barium, and chromium, magnesium. Salt hydrates of transition metals such as iron, cobalt, nickel, copper, and zinc, aluminum salt hydrates, and lanthanum salt hydrates. Suitable alkali metal salt hydrates are, for example, LiNO ₃ .3H ₂ O, Na ₂ SO ₄ .10H ₂ O (Grauber salt), Na ₂ SO ₄ .7H ₂ O, Na ₂ CO ₃ .10H ₂ O, Na ₂ CO ₃ · 7H ₂ O, Na ₃ PO ₄ · 12H ₂ O, Na ₂ HPO ₄ · 12H ₂ O, Na ₄ P ₂ O ₇ · 10H ₂ O, Na ₂ H ₂ P ₂ O ₇ · 6H ₂ O, NaBO ₃ · 4H ₂ O, Na ₂ B ₄ O ₇ · 10H ₂ O, NaClO ₄ · 5H ₂ O, Na ₂ SO ₃ · 7H ₂ O, Na ₂ S ₂ O ₃ · 5H ₂ O, NaBr · 2H ₂ O Na ₂ S ₂ O ₆ · 6H ₂ O, K ₃ PO ₄ · 3H ₂ O, etc., and preferred suitable alkaline earth metal salt hydrates are, for example, MgCl ₂ · 6H ₂ O, MgBr ₂ · 6H ₂ O, MgSO ₄ · 7 _{2 O, Mg (NO 3)} 2 · 6H 2 O, CaCl 2 · 6H 2 O, CaBr 2 · 6H 2 O, Ca (NO 3) 2 · 4H 2 O, Sr (NO 3) 2 · 4H 2 O, Sr (OH) ₂ · 8H ₂ O, SrBr ₂ · 6H ₂ O, SrCl ₂ · 6H ₂ O, Srl ₂ · 6H ₂ O, BaBr ₂ · 2H ₂ O, BaCl ₂ · 2H ₂ O, Ba (OH) ₂ 8H ₂ O, Ba (BrO ₃ ) ₂ .H ₂ O, Ba (ClO ₃ ) ₂ .H ₂ O, and the like. Suitable transition metal salt hydrates are, for example, CrK (SO ₄ ) ₂ · 12H ₂ O, MnSO ₄ · 7H ₂ O, MnSO ₄ · 5H ₂ O, MnSO ₄ · H ₂ O, FeBr ₂ · 6H ₂ O, FeBr ₃ · 6H ₂ O, FeCl ₂ · 4H ₂ O, FeCl ₃ · 6H ₂ O, Fe (NO ₃ ) ₃ · 9H ₂ O, FeSO ₄ · 7H ₂ O, Fe (NH ₄ ) ₂ (SO 4) ₂ · 6H ₂ O, FeNH ₄ (SO ₄ ) ₂ · 12H ₂ O, CoBr ₂ · 6H ₂ O, CoCl ₂ · 6H ₂ O, NiSO ₄ · 6H ₂ O, NiSO ₄ · 7H ₂ O, Cu (NO ₃ ) ₂ · 6H ₂ O, Cu (NO ₃ ) ₂ · 3H ₂ O, CuSO ₄ · 5H ₂ O, Zn (NO ₃ ) ₂ · 6H ₂ O, ZnSO ₄ · 6H ₂ O, ZnSO ₄ · 7H ₂ O, etc. . Suitable aluminum salt hydrates are, for example, Al ₂ (SO ₄ ) ₃ · 18H ₂ O, AlNH ₄ (SO ₄ ) ₂ · 12H ₂ O, AlBr ₃ · 6H ₂ O, AlBr ₃ · 15H ₂ O, AlK ( SO ₄ ) ₂ · 12H ₂ O, Al (NO ₃ ) ₃ · 9H ₂ O, AlCl ₃ · 6H ₂ O, and the like. A suitable lanthanum salt hydrate is LaCl ₃ · 7H ₂ O. Suitable acid hydrates according to the present invention are organic acid hydrates such as citric acid monohydrate.

  The salt hydrate or acid hydrate preferably reacts with another salt hydrate or acid hydrate, but as long as the crystal water is liberated in a sufficient amount to drive the endothermic reaction involved in the entropy contribution, It can also react with any non-hydrated compound.

Suitable non-hydrated compounds according to the present invention may include acids, alcohols, organic compounds, and non-hydrated salts. The acid can be citric acid, fumaric acid, maleic acid, malonic acid, formic acid, acetic acid, glacial acetic acid and the like. The alcohol can be mannitol, resorcinol, and the like. The organic compound can be urea or the like. Non-hydrate salts according to the present invention include, for example, anhydrous alkali metal salts, anhydrous alkaline earth metal salts, anhydrous transition metal salts, anhydrous aluminum salts, anhydrous tin salts, anhydrous lead salts, anhydrous ammonium salts, and anhydrous organic salts. can do. Suitable anhydrous alkali metal salt hydrates are, for example, NaClO ₃ , NaCrO ₄ , NaNO ₃ , K ₂ S ₂ O ₅ , K ₂ SO ₄ , K ₂ S ₂ O ₆ , K ₂ S ₂ O ₃ , KBrO ₃ , KCl, KClO ₃ , KlO ₃ , K ₂ Cr ₂ O ₇ , KNO ₃ , KClO ₄ , KMnO ₄ , CsCl and the like. Suitable alkaline earth metal anhydride, for _{example, CaCl 2, Ca (NO 3} ) 2, Ba (BrO 3) 2, SrCO 3, and the like _{(NH 4) 2 Ce (NO} 3) 6. Suitable anhydrous transition metal salts are, for example, NiSO ₄ , Cu (NO ₃ ) ₂ . A suitable anhydrous aluminum salt is Al ₂ (SO ₄ ) ₃ or the like. Suitable anhydrous tin salts are SnI ₂ (s), SnI ₄ (g), and the like. Suitable anhydrous lead salts are PbBr ₂ , Pb (NO ₃ ) ₂ and the like. Suitable ammonium salts are NH ₄ SCN, NH ₄ NO ₃ , NH ₄ Cl, (NH 4) 2 Cr 2 O 7 and the like. Suitable anhydrous organic salts are, for example, urea acetate, urea formate, urea nitrate, and urea oxalate.

It is further contemplated that any hydrated salt or anhydrous form of hydrated acid listed above can be used as the non-hydrated compound in the reaction according to the present invention. The liquid reactant according to the present invention can be a liquid salt such as PBr ₃ , SCl ₂ , SnCl ₄ , TiCl ₄ , VCl ₄ , or a liquid organic compound such as CH ₂ CL ₂ .

  The number of reactants contributing to the reaction is at least two. Some embodiments may use more than two reactants.

One possible reaction according to the present invention is as follows.
Na ₂ SO ₄ .10H ₂ O (s) + CaCl ₂ .6H ₂ O (s) → 2Na ⁺ (aq) + 2Cl ⁻ (aq) + CaSO ₄ .2H ₂ O (s) + 14H ₂ O (l)
ΔH = 2 × (−240 kJ / mol) + 2 × (−167 kJ / mol) + (− 2023 kJ / mol) + 14 × (−286 kJ / mol) − ((− 4327 kJ / mol) + (− 2608 kJ / mol)) = 94 kJ / mol
ΔS = 2 × (58 J / K × mol) + 2 × (57 J / K × mol) + (194 J / K × mol) + 14 × (70 J / K × mol) − ((592 J / K × mol) + (365 J / K × mol)) = 2.361 kJ / K × mol
At room temperature (T = 298K)
ΔG = ΔH−T × ΔS = 94 kJ / mol−298 K × 0.447 kJ / K × mol = −39 kJ / mol

  A negative sign indicates that the reaction is spontaneous.

  The stoichiometric amount of product to reactant is 19/2 = 9.5: 1.

Another possible reaction according to the invention is as follows.
Na ₂ SO ₄ .10H ₂ O (s) + Ba (OH) ₂ .8H ₂ O (s) → BaSO ₄ (s) + 2Na ⁺ (aq) + 2OH ⁻ (aq) + 18H ₂ O (l)
ΔH = −1473 kJ / mol + 2 × (−240 kJ / mol) + 2 × (−230 kJ / mol) + 18 × (−286 kJ / mol) − (− 4327 kJ / mol + (− 3342 kJ / mol)) = 108 kJ / mol
ΔG of this reaction at room temperature (T = 298K) can be calculated directly.
ΔG = −1362 kJ / mol + 2 × (−262 kJ / mol) + 2 × (−157 kJ / mol) + 18 × (−237 kJ / mol) − (− 3647 kJ / mol + (− 2793 kJ / mol)) = − 26 kJ / mol

  This reaction is therefore spontaneous. The stoichiometric amount of product to reactant is 23/2 = 11.5: 1.

Further possible reactions according to the invention are as follows:
Ba (OH) ₂ .8H ₂ O (s) + 2NH ₄ SCN (s) → Ba (SCN) ₂ + 2NH ₃ (g) + 10H ₂ O (l)
ΔH = 102 kJ / mol
ΔS = 0.495 kJ / K × mol
ΔG = ΔH−T × ΔS = 102 kJ / mol−298 K × 0.495 kJ / K × mol = −45.5 kJ / mol

  This reaction is spontaneous. The stoichiometry of the product to reactant is 13/3 = 4.33: 1.

Examples of further reactions are as follows:
a) Ba (OH) ₂ · 8H ₂ O (s) + 2NH ₄ NO ₃ (s) → Ba (NO ₃ ) ₂ + 2NH ₃ (g) + 10H ₂ O (l)
b) Ba (OH) ₂ .8H ₂ O (s) + 2NH ₄ Cl (s) → BaCl ₂ + 2NH ₃ (g) + 10H ₂ O (l)

Additives and activators The reaction is preferably initiated by the addition of a polar solvent such as water, glycerin, ethanol, propylene glycol, etc., but the reaction can also be initiated simply by contacting the reactants. .

  In some reactions, the reactants may become unreactive when contacted or mixed. In such a reaction, a suitable catalyst can be used to enable the reaction.

  In some embodiments, the solid reactant can be coated or microencapsulated. A suitable outer coating is heat resistant but dissolves upon contact with an activation fluid capable of dissolving the coating. Suitable coatings include sugars such as starch and cellulose, polyethers such as polyethylene glycol (PEG), but also shellac or plastic. Suitable activation fluids include water, alcohols, organic solvents, acids. As an alternative to coating, the solid reactant can be embedded in a soluble gel or foam.

  By using a coating, the reactants can be premixed to increase the reaction rate. Furthermore, the coating of reactants prevents premature initiation of the cooling effect due to the storage state of the beverage or heat treatment of the beverage. In some embodiments, a portion of the reactant mass is coated with a thick coating to slow the reaction and extend the cooling provided by the reaction. In other embodiments, more than one coating may be applied to the reactants, and different coatings may be applied to different reactants or portions of the reactant mass. As an alternative to coating, the reactants can be suspended in a non-aqueous fluid such as an organic solvent.

  A delayed temperature setting agent having an appropriate melting temperature can be used in the present invention. A suitable melting temperature is that the retarding temperature setting agent is liquid at any desired temperature that results in a higher temperature than freezing point or the desired cooling of the beverage to be cooled, and solidifies and retards the reaction when the temperature falls below this freezing point. Thus, the temperature of the beverage in the beverage container can be prevented from freezing. The delayed temperature setting agent is a suitable melting temperature higher than the freezing temperature of water, such as a temperature of 0 ° C. to + 10 ° C., for example 2 ° C. to 2 ° C., so that its solidified form reduces the reaction rate of the reaction according to the invention. It can be any compound having 6 ° C. Examples of suitable lag temperature setting agents include polyethylene glycol, fatty acids, or polymers.

  The reactants can be in the form of granules of various sizes to tailor the reaction rate for a particular application. Granules can also be coated as described above.

  In some reactions, it is preferred to add solvents or trace contaminants such as glycerol to prevent the formation of product crystals from the reactants with the coating remaining, thereby inhibiting further reactions. In order to control the reaction rate and / or ensure complete reaction, an adsorbent can be used to selectively absorb the product. In some reactions, the liquid activator used to initiate the reaction also functions as a selective absorption control agent to control the reaction.

  For reactions that produce acidic or basic products, a pH adjusting buffer may be included. This buffer may also be used to facilitate dissolution of the product in gas form.

  It is contemplated that one or more reactants can be formed in situ from the precursor. This would be advantageous in preventing premature activation or pre-activation of the cooling device after it has been placed in the container.

  Additives: 3,7-diamino-5-phenothiazinium acetate, 18 crown 6 ether, 1,3-dimethyl-2-imidazoline dinone may be suitable for some reactions in the context of reaction control I intend further.

Presently preferred reaction The presently preferred reaction is a reaction between strontium hydroxide octahydrate and ammonium nitrate. Magnesium nitrate hexahydrate is added as a third reactant to safely produce the final product. Most preferably, magnesium nitrate hexahydrate is used as a coating to separate strontium hydroxide octahydrate and ammonium nitrate. The reactants react in a primary reaction and an NH3 purification reaction. The primary reaction having a high cooling effect is as follows.
3Sr (OH) ₂ 8H ₂ O (s) + 6NH ₄ NO 3 (s) → 3Sr ²⁺ + 6NO ₃ ⁻ + 6NH ₃ + 30H ₂ O

Since NH ₃ is considered toxic and can have at least an unpleasant odor, it must be sedated by further reactions. The reaction that calms NH ₃ has a cooling efficiency lower than that of the following primary reaction.
3Sr ²⁺ + 6NO ₃ ⁻ + 6NH ₃ + 30H ₂ O + Mg (NO ₃ ) ₂ 6H ₂ O (s) → 3Sr ²⁺ + 8NO ₃ ⁻ + Mg (NH ₃ ) 6 ²⁺ + 36H ₂ O

  The end product is a completely safe white gel with a slight ammonia odor.

  In order to cool 330 ml of beverage at 20 ° C., 88 ml of the above-mentioned reactants are required. Thus, a typical 440 ml beverage can can be used to contain 330 ml of beverage and 88 ml of reactant.

Beverage Cooling A wide range of cooling effects can be obtained, depending on the reaction used, the heat capacity of the reaction mixture and beverage, the initial temperature of the beverage, and the amount of beverage and reactant. The cooling device according to the invention can contain any amount of reactants as long as the volume of the cooling device does not exceed 30% of the volume of the container.

  The cooling effect of the cooling device in the beverage container should be sufficient to allow the beverage volume to cool at least 10 ° C. in a time of within 5 minutes, preferably within 2 minutes.

  In the case of a beverage mainly made of water, the specific heat capacity can be approximated to a specific heat capacity of liquid water: 4.18 kJ / kg · K. The cooling effect q required for cooling the beverage can be obtained by the equation: q = m · ΔT · Cp. Therefore, in order to cool 1 kg of beverage at 20 ° C., the cooling device must absorb 83.6 kJ of heat from the beverage to be cooled. Thus, in the present invention, the reduction in the calorie of the beverage is at least 50 joules per ml of beverage, preferably at least 70 joules per ml of beverage, in a time of within 5 minutes, preferably within 3 minutes, more preferably within 2 minutes, for example Should be 70 to 85 joules per ml of beverage, preferably about 80 to 85 joules per ml of beverage.

  According to a further embodiment, the container body can comprise a beverage keg made of a polymer or metal material with a volume of 3-50 liters, the keg being shrinkable or rigid and the closure connected to the keg is doing. Alternatively, the container body may comprise a bottle of glass or polymer material, the bottle having a volume of 0.2 to 3 liters, and the closure is a screw cap, cap or stopper. In a further alternative, the container body may comprise a beverage can and beverage lid made of a metallic material, preferably aluminum or aluminum alloy, the beverage can having a volume of 0.2-1 liter, It is comprised by the embossed area | region of a drink lid. In a further alternative, the container can preferably comprise a bag as a bag-in-box, bag-in-bag, or bag-in-keg.

  According to a further embodiment, the container comprises a guide element for guiding the flow of the beverage from the container body. The guiding element may serve to guide the beverage flow through the cooling device towards the closure. The cooling device can be placed in the container, or alternatively, the cooling device is placed outside the container. The container body can constitute a double-walled container that constitutes an inner wall and an outer wall, and the cooling device can be disposed between the inner wall and the outer wall.

  According to a further aspect, the container body can comprise a pressure generating device housed in the container or connected to the container by a pressurized hose. The pressure generator preferably comprises a carbon dioxide generator for pressurizing the beverage in the beverage container.

  According to a further embodiment, the container can comprise a tap line and a tap valve for selectively dispensing the beverage from the beverage container. Beverage containers are carbonated beverages such as beer, cider, soft drinks, mineral water, sparkling wine, or non-carbonated beverages such as fruit juice, dairy products such as milk and yogurt, tap water, wine, alcoholic beverages, iced tea Or can be filled with beverages that make up a cocktail.

  According to a further embodiment, the cooling device forms an integral part of the beverage container or part of the top of the beverage container or part of the wall or bottom of the beverage container. The cooling device is secured to the base of the beverage container, the wall of the container, or the top of the container. Alternatively, the cooling device constitutes a small device, which can be freely moved within the container.

  According to a further embodiment, the cooling device is a metal can of the size of a beverage can, as a cooling box containing a number of containers containing beverages, as a cooling stick placed in a beverage bottle or the like, part of a container, For example, it can be configured as a bottle neck or a sleeve placed around a metal can or body portion of the metal bottle, or as a part of a closure or bottle cap.

  The present invention and its many advantages are described in detail below with reference to the accompanying schematic drawings for purposes of illustration showing some non-limiting embodiments.

1 shows a self-cooling beverage container having a cooling device with a gas permeable membrane. 1 shows a self-cooling beverage container having a cooling device with a gas permeable membrane. 1 shows a self-cooling beverage container having a cooling device with a gas permeable membrane. A self-cooling vessel having a cooling device with an auxiliary reaction chamber. A self-cooling vessel having a cooling device with an auxiliary reaction chamber. A self-cooling vessel having a cooling device with a fusible plug. A self-cooling vessel having a cooling device with a fusible plug. A self-cooling vessel having a cooling device with a fusible plug. A self-cooling vessel having a cooling device with a pierceable membrane. A self-cooling vessel having a cooling device with a pierceable membrane. A self-cooling beverage container having a cooling device with a cap. A self-cooling beverage container having a cooling device with a cap. A self-cooling beverage container having a cooling device with a breakable diaphragm. A self-cooling beverage container having a cooling device with a breakable diaphragm. A self-cooling beverage container having a cooling device with a telescope valve. A self-cooling beverage container having a cooling device with a telescope valve. A self-cooling beverage container having a cooling device with a water-soluble diaphragm. A self-cooling beverage container having a cooling device with a water-soluble diaphragm. A self-cooling beverage container having a cooling device with a flexible cylinder. A self-cooling beverage container having a cooling device with a flexible cylinder. A self-cooling beverage container having a cooling device with a flexible cylinder. A self-cooling beverage container having a cooling device with a flexible cylinder. A self-cooling beverage container having a cooling device with a flexible cylinder. A self-cooling beverage container having a cooling device with a pair of caps. A self-cooling beverage container having a cooling device with a pair of caps. A self-cooling beverage container having a cooling device with a cap and a breakable diaphragm. A self-cooling beverage container having a cooling device with a cap and a breakable diaphragm. A self-cooling beverage container having a cooling device with a pierceable membrane and a breakable membrane. A self-cooling beverage container having a cooling device with a pierceable membrane and a breakable membrane. A self-cooling beverage container having a cooling device constituting a small device. A self-cooling beverage container having a cooling device constituting a small device. A self-cooling beverage container having a small device and a cooling device constituting an operation control fluid. A self-cooling beverage container having a small device and a cooling device constituting an operation control fluid. A self-cooling beverage container with a cooling device that constitutes a small device with an additional reaction chamber. A self-cooling beverage container with a cooling device that constitutes a small device with an additional reaction chamber. It is a rectangular cooling box with a cooling device having the shape of a can. It is a rectangular cooling box with a cooling device having the shape of a can. A cooling box having a brown shape in which a cooling device is arranged at the center. It is a brown-shaped cooling box in which a cooling device is arranged at the center. It is a brown-shaped cooling box in which a cooling device is arranged at the center. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container fitted with a cooling device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 5 shows a filling process of a self-cooling beverage container having a cooling device constituting a small device. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. Fig. 4 shows a filling process of a self-cooling beverage container having a cooling device with a lid. A self-cooling party keg system is shown. A self-cooling party keg system is shown. Figure 2 shows a beverage dispensing system having a keg with a cooling device to achieve instant cooling. Figure 2 shows a beverage dispensing system having a keg with a cooling device to achieve instant cooling. 1 shows a beverage dispensing system having a beverage keg with a cooling device provided with a piercing membrane. 1 shows a beverage dispensing system having a beverage keg with a cooling device provided with a piercing membrane. Figure 2 shows a beverage bottle with a button-actuated cooling device. Fig. 2 shows a beverage bottle with a pressure-actuated cooling device. Figure 2 shows a beverage bottle having a capped cooling device activated by a user. Figure 2 shows a beverage bottle having a capped cooling device activated by a user. Fig. 2 shows a cooling device constituting a beverage stick with an internal cooling device. Fig. 2 shows a cooling device constituting a beverage stick with an internal cooling device. Fig. 2 shows a cooling device constituting a beverage stick with an internal cooling device. Fig. 2 shows a cooling device constituting a beverage stick with an internal cooling device. Figure 3 shows a bottle sleeve attached to the neck of a beverage bottle. Figure 3 shows a bottle sleeve attached to the neck of a beverage bottle. Figure 3 shows a bottle sleeve attached to the neck of a beverage bottle. Fig. 3 shows a bottle sleeve attached around the body of a beverage bottle. Fig. 3 shows a bottle sleeve attached around the body of a beverage bottle. Fig. 3 shows a bottle sleeve attached around the body of a beverage bottle. Fig. 3 shows a bottle sleeve attached around the body of a beverage bottle. The selective sorbent shows crystals of the reaction that prevented growth at the corners. A dispensing / refrigeration system for containing a plurality of beverage cans. It is a refrigeration system for accommodating a plurality of beverage cans.

  Each drawing illustrates various exemplary embodiments of a cooling device according to the present invention.

Figure 1A shows a partial cross-sectional view of a self-cooled vessel 10 ^I according to the invention. Self-cooled vessel 10 ^I includes, for example, a beverage can 12 made of a thin metal sheet such as aluminum or an aluminum alloy. The beverage can 12 has a cylindrical body closed by a beverage can base 14 and a lid 16. The lid 16 includes a tab and an embossed area that forms a closure (the tab and the embossed area are not visible in this view). The beverage can 12 includes a cooling device that is juxtaposed to the beverage can base 14 within the beverage can 12. The cooling device ²⁰¹ includes a thin metal sheet cylinder similar to the beverage can 12 but significantly smaller in size. Alternatively, the cooling device 20 ^I may be a similar polymer material coated with a laminate or thin aluminum foil formed from plastic. The size of the cooling device is about 20% of the total volume of the beverage can 12 in order to achieve a sufficient cooling effect and not to substantially reduce the amount of beverage that can be accommodated in the beverage can 12. ~ 30%, preferably about 25% of the total volume of the beverage can 12. A beverage, preferably a carbonated beverage, such as beer, sparkling wine, or various soft drinks, is filled into the beverage can 12 and typically occupies 70% of the volume of the beverage can 12, with the lid 16 and the top surface of the beverage. A space of about 5% is formed between the two. The cooling device 20 ^I extends between the bottom 22 and the top 24. The bottom 22 is preferably secured to the beverage can base 14 so that the cooling device 20 takes a stable position within the beverage can 12. Alternatively, the cooling device 20 ^I constitutes a unique part of the beverage can 12. For example, the beverage can 12 with the cooling device 20 can be punched from a piece of metal sheet. The upper part 24 of the cooling device 20 and the lid 16 of the beverage can 12 are separate parts, and the upper part of the cooling device is attached after the cooling device 20 ^I is filled, and the lid is attached after the beverage can 12 is filled. It is attached. Cooling device 20 ^I top 24 seals the interior of the cooling device 20 ^I that turning the beverage at all. The top 24 is provided with a gas permeable membrane 26, the gas permeable membrane is entry into the cooling device 20 ^I of gases such as air or carbon dioxide allows, entry of liquids such as beverages is prevented. The interior of the cooling device 20 ^I includes a pressure space 32 disposed close to the gas permeable membrane 26, a main reactant chamber 28 disposed near the bottom 22, a pressure space 32, and a main reactant chamber 28. And a water chamber 44 disposed between the two. The main reactant chamber 28 constitutes most of the cooling device 20 ^I and is filled with the granular reactant 29. The granular reactant 29 includes at least two separate reactants that, when reacted with each other, absorb energy from the surrounding beverage and cool the beverage. The reaction is typically initiated when two reactants come into contact with each other. The exact composition of the reactants is described in detail later in the chemistry section of this description. At least one compound constitutes a granule with a water-soluble coating, which prevents the reactants from contacting each other and prevents any reaction from starting. The water soluble coating can be, for example, starch. In an alternative embodiment, the reaction can be prevented by embedding one or more granules in a soluble gel or foam. In a further alternative, the reactants can be provided as highly compressed thin disks or plates separated from each other by the coatings, gels, or foams described above.

  The pressure space 32 is separated from the water chamber 44 by a flexible diaphragm 30. The flexible diaphragm 30 is funnel-shaped and extends from a round circumferential reinforcing bead 34 that forms the periphery of the flexible diaphragm 30 to a circular wall 40 that forms the center of the flexible diaphragm 30. ing. A circular wall 40 separates the pressure space 32 from the main reactant chamber 28. The round circumferential reinforcement bead 34 is juxtaposed to the washer 36, and the washer 36 seals the round circumferential reinforcement bead against the upper portion 24. A water chamber 44 is separated from the main reactant chamber 28 by a rigid cup-shaped wall 38 that extends inwardly downward from the top 24. The flexible diaphragm includes a circumferential gripping flange 42 that extends downwardly with a circular wall 40. A circumferential gripping flange 42 grips around the end of the cup-shaped wall 38 to isolate the water chamber 44 from the main reactant chamber 28.

Cooling device fills the main reactant chamber 28 in granular reactant 29, filled with water chamber 44 with water, and then prepared by sealing by attaching a top to the cooling device 20 ^I. Subsequently, the beverage can 12 is filled with beverage, pressurized and sealed with a lid 16. The pressure of the beverage cans 12, because the pressure is equal in the beverage can 12 and the cooling device 20 ^I is maintained, ensuring that cooling device 20 ^I is not working.

1B is a beverage can 12 is opened, a partial cross-sectional view of a self-cooled vessel 10 ^I when chemical reaction is initiated in the cooling device 20 ^I. The beverage can 12 is opened by tilting the tab 18 from a normal horizontal position juxtaposed to the lid 16 to a vertical position extending outward with respect to the lid 16. By tilting the tab 18 to a vertical position, the tab 18 protrudes into the embossed area of the lid 16, breaking the embossed area and defining the beverage outlet (not shown) of the beverage can 12. When the beverage can 12 is opened, the high-pressure CO 2 gas in the beverage can 12 escapes to the outside atmosphere. When the inside of the beverage can 12 becomes atmospheric pressure, gas slowly escapes from the pressure space 32 to the beverage can 12 through the gas permeable membrane 26. At the same time, the high pressure in the main reactant chamber 28 applies pressure to the flexible diaphragm 30, causing the flexible diaphragm 30 to move toward the top 24. A round circumferential reinforcing bead 34 and washer 36 fluidly seal the pressure space 32 and the main reactant chamber 28. As the flexible diaphragm 30 assumes the operative position, i.e., moves toward the top 24, the circumferential gripping flange 42 disengages from the rigid cup-shaped wall 38 and the water retained in the water chamber 44 becomes the main reactant chamber 28. Flows in. Water entering the main reactant chamber dissolves the water-soluble coating of granular reactant and initiates a chemical reaction. Reaction is an endothermic reaction, absorbing energy from the beverage, i.e. while the beverage is cold, the thermal energy is moved to the cooling device 20 ^I from the beverage. Further details on the chemical reaction will be described later. The thermal energy absorbed by the cooling device 20 ^I cools the beverage in the beverage can 12. After a few seconds, the beverage's relative temperature drops by about 10 ° C., typically 20 ° C., and the drinker can taste the cold beverage immediately after opening the beverage can 12. Beverage cans 12 stored in a retail store without being refrigerated can typically be at a temperature of about 22 ° C. After opening, the beverage is rapidly cooled to about 6 ° C. due to heat loss or the like. The time required for cooling is typically less than 5 minutes, more typically less than 3 minutes. When the drinker has finished drinking, the beverage can 12 can be discarded and the metal of the beverage can 12 can be recycled in an environmentally friendly manner.

Figure 1C is a beverage can 12 is opened, a partial cross-sectional view of an alternative embodiment of a cooling device 20 self-cooled vessel immediately after the chemical reaction has been initiated by the ^I 10 ^I, similar to FIG. 1B . FIG. 1C further illustrates a first enlarged view showing the upper portion of the reactant chamber 28 and a second enlarged view showing the lower portion of the reactant chamber 28. From the enlarged view, at this point, the water, shown in dotted lines in FIG. 1C, is in contact with the granular reactant 29 at the top of the reactant chamber 28, but the bottom of the reactant chamber 28 remains dry.

  The granule reactant 29 has a core and a coating that completely covers the core. Granule reactant 29 is a type of granule reactant 29 having a first reactant coating, designated 29A, and a second reactant core, designated 29B, and a second reactant designated 29A. Divided into two, one reactant coating and another type of granule reactant 29 having a third reactant core shown as 29C.

  In the second enlarged view showing the lower part of the reactant chamber 28, the chemical reaction cannot be initiated because the cores 29B and 29C are not in contact with each other. In the first enlarged view showing the top of the reactant chamber 28, the granular reactant 29 is exposed to water and the coating 29C begins to decompose, thereby causing all the reactants 29A, 29B, 29C to mix and react with each other. To do.

  Reactants B and C initially react to form a reaction product that is sedated by reacting with reactant A.

FIG. 2A is a partial cross-sectional view of a further embodiment of a self-cooling vessel 10 ^II with all the features of the self-cooling vessel 10 ^I of FIG. However, the self-cooling vessel 10 ^II of the present invention further comprises an auxiliary cup-type wall 46 attached to the lower side outside the main cup-type wall 38. An auxiliary gripping flange 48, which constitutes an extension of the main gripping flange 42, together with the auxiliary cup mold wall 46 and the main cup mold wall 38, defines the auxiliary reactant chamber 50. The auxiliary reactant chamber 50 is filled with auxiliary granule reactant, which constitutes one of the reactants in the reaction. The other reactants are located in the main reactant chamber 28 so that no granular reactant coating is required.

2B shows a self-cooled vessel 10 ^II of Figure 2A when the beverage can is opened chemical reaction has been started. In the started state, the circumferential gripping flange is disengaged from the cup-shaped wall 38 as shown in FIG. 1A so that water in the water chamber 44 can flow into the main reactant chamber 28. At the same time, the auxiliary gripping flange 48 connected to the flexible diaphragm 30 by the circumferential gripping flange 42 is disengaged from the auxiliary cup mold wall 46, allowing the auxiliary reactant to enter the main reactant chamber 28, thereby causing a chemical reaction. Is started. This embodiment has the advantage that an additional chamber is required, but no coating of granular reactant is required since the reactant is stored in a separate chamber.

FIG. 3A shows a self-cooling vessel 10 ^III similar to the self-cooling vessel 10 ^II shown in FIG. The self-cooling vessel 10 ^III has a pressure space 32, but a water-soluble plug 27 is accommodated in the upper part 24 of the cooling device 20 instead of the gas permeable membrane. The water-soluble plug 27 can be any water-soluble material, and such water-soluble material is non-toxic and can form a sufficiently hard pressure-resistant plug that is exposed to an aqueous solution such as a beverage. It dissolves within a few minutes. Non-toxicity is intended to mean a material that is approved for use in consumables, for example by the National Health Organization. Such materials can include sugar, starch, or gelatin. With the water-soluble plug 27, the cooling device 20 can be prepared and pressurized for a long period of time, for example several days or weeks, until it is used in a beverage can. The water-soluble plug 27 prevents the pressure in the cooling device 20, that is, the main reactant chamber 28, the water chamber 44, and the pressure space 32 from escaping from the upper portion 24 to the outside. The flexible membrane is formed from rubber in this embodiment, and is similarly formed from rubber, juxtaposed to the cup-shaped wall 38, and extending between the circular wall 40 and the round circumferential reinforcing bead 34. A diaphragm 31 is provided. In order to equalize the pressure between the flexible diaphragm 30 and the support diaphragm 31, a pressure port 52 is provided in the flexible membrane, whereby the space between the support diaphragm 31 and the flexible membrane 30 is provided. It is possible to make the pressure equal between the space and the pressure space 32.

FIG. 3B shows a self-cooling container 10 ^III comprising a beverage can 12 and a cooling device 20 arranged in the beverage can 12 before a chemical reaction is started. The water-soluble plug 26 ^I prevents the pressure in the pressure space 32 from escaping to the outside of the cooling device 20 when the beverage can 12 is filled with beverage and carbon dioxide gas is injected / pressurized. After a certain time or during pasteurization, the water-soluble plug 26 ^I dissolves, and fluid communication is established between the interior of the beverage can 12 and the pressure space 32 of the cooling device 20. The pressure in the beverage can 12 maintains the cooling device 20 ^III in a pre-reaction state, that is, a state in which no chemical reaction is started.

Figure 3C shows a self-cooled vessel 10 ^III according to FIG. 3B when the chemical reaction is initiated beverage can 12 is opened. When the beverage can 12 is opened, the pressure in the beverage can 12 and the pressure in the pressure space 32 are reduced to the ambient pressure outside the beverage can 12. For this reason, as already described with reference to FIG. 2, a chemical reaction occurs in the cooling device 20.

FIG. 4A shows a further embodiment of a self-cooling vessel 10 ^IV . The self-cooling container 10 ^IV comprises a beverage can 12 ^I similar to the beverage can described with reference to FIGS. Beverage cans 12 ^I includes a beverage can base 14 ^I, and the lid 16 ^I, the cooling device 20 ^I extending in the lid 16 fixed beverage can 12 ^I to ^I. The cooling device 20 ^IV includes a cylindrical aluminum tube extending toward the beverage can base 14. A pressure port 52 is defined in the lid 16 ^I to allow fluid communication between the external atmospheric pressure and the pressure space 32, which pressure space is cooled between the lid 16 ^I and the diaphragm 30 ^I. Defined within the device. The diaphragm 30 ^I is made of a flexible material such as rubber, and forms a fluid tight barrier between the pressure space 32 ^I and the water chamber 44 ^I. Water chamber 44 is separated from the main reactant chamber 28 ^I by breakable diaphragm 54. Rupturable diaphragm 54 is made of a similar flexible material diaphragm 30 ^I. Rupturable diaphragm 54 may be broken, that the needle can be opened irreversibly by penetrating element 56 constituting the, the needle is placed in the main reactant chamber 28 within ^I, the tip of it rupturable diaphragm It is suitable for 54. The main reactants chamber 28 ^I is similar coated granules reactants were are filled to the embodiment described in connection with FIGS. The main reactants chamber 28 ^I the deployed bottom 22 ^I adjacent without contacting the base 14 ^I of beverage cans, is separated from the beverage cans 12 ^I. Bottom 22 ^I may be the same material as the outer wall of the cooling device 20, i.e., preferably made of aluminum. The bottom portion 22 ^I is connected to the outer wall of the cooling device 20 ^IV by a corrugated portion 58, and this corrugated portion causes the bottom portion 22 ^{I to} be flexible and bistable, that is, mechanically stable toward the inner side and the outer side, respectively. Sex can be defined. Beverage cans 12 ^I is filled and pressurized, the pressure inside the beverage can 12 ^I, and bottom 22 ^I, and the diaphragm 54 ^I breakable, and the diaphragm 30 ^I inflates inwardly.

Figure 4B shows the self-cooled vessel 10 ^IV having a beverage can 12 ^I, the beverage can has been opened the tab 18 is tilted. By tilting the tab 18, the embossed area of the lid 16 is broken and an opening is formed in the lid 16 so that a beverage can be poured and the pressure is released. When the pressure escape, bottom 22 ^I of the cooling device ^{20 IV} is inflated toward the beverage can base 14 by the internal pressure of the cooling device ^{20 IV.} The bottom 22 ^I is bistable, so that when it expands in the direction of the beverage can base 14, the breakable diaphragm 54 and the diaphragm 30 are formed by the main reactant chamber 28 ^I which becomes subatmosphere pressure. It swells toward the beverage can base 14. Accordingly, the breakable diaphragm 54 bulges toward the piercing element 56, so that the breakable diaphragm 54 ruptures. When the pierceable diaphragm 54 is inserted into the ruptureable diaphragm 54 such that the diaphragm 54 is ruptured, has a predetermined breaking point, or is provided with a tension portion, An opening is formed between chamber 44 ^I and main reactant chamber 28 ^I so that water in water chamber 44 ^I enters main reactant chamber 28 ^I and a chemical reaction begins to cool the beverage. Can be. The chemical reaction absorbs energy from the surrounding boundary and cools relatively at least 10 ° C., preferably 20 ° C. or more.

FIG. 5A shows a self-cooling vessel ^10V similar to the self-cooling vessel ^10IV of FIG. Instead of a rupturable diaphragm, self-cooled vessel 10 ^V separates main reactant chamber 28 ^I water chamber 44 has a main cap 60 made of plastic material. The main cap 60 is held at a predetermined position by a main cap seat 62 constituting a flange protruding inward, and this flange is fixed to the inner wall of the cooling device 20 ^V and applies a low pressure to the main cap 60. The main cap 60 comprises a thin circular plastic element that forms a fluid tight connection between the water chamber 44 ^I and the main reactant chamber 28 ^I.

Figure 5B shows a self-cooled vessel 10 ^V according to FIG. 5A operatively been opened similarly to the beverage can shown in Figure 4B. When a beverage can 12 ^I is opened, bulging bottom 22 ^I of the cooling device 20 ^V is toward the beverage can base 14, thereby the pressure of the main reactant chamber 28 within the ^I is reduced, the main cap 60 is mainly cap seat It deviates from 62 falls into the main reactant chamber 28 ^I, This enables fluid communication between the water chamber 44 ^I and the main reactant chamber 28 ^I. Therefore, the water flows into the main reactant chamber 28 ^I of water chamber 44, thereby the chemical reaction is cooled beverage starting. When granules reactants are dissolved, the main cap 60 may fall toward the bottom 22 ^I of the cooling device 20 ^V.

Figure 6A is similar to the self-cooled vessel 10 ^V as shown in Figure 5, instead of the main cap seat and the main cap, this embodiment includes a support mesh 66, the water chamber 44 ^I and the main It shows a self-cooled vessel 10 ^VI that a frangible diaphragm 54 which separates the reactants chamber 28 ^I. The support mesh constitutes a grid of metal or plastic juxtaposed to the breakable diaphragm 54, which faces the main reactant chamber 28, and the breakable diaphragm 54 is in the water chamber 44. Facing. Rupturable diaphragm 54 constitutes a rupture membrane, the rupture membrane to prevent fluid communication between the water chamber 44 ^I and the main reactant chamber 28 ^I. The support mesh 56 prevents the breakable diaphragm 54 ^I from expanding upward toward the pressure port 52 and ruptures when the pressure in the main reactant chamber exceeds the pressure in the water chamber 44.

Figure 6B shows a self-cooled vessel ^{10 VI} when beverage can 12 ^I has been opened. By beverage can is opened, the pressure drops of the beverage can 12 ^I, bottom 22 ^I bulge toward the beverage can base 14, thereby the pressure of the main reactant chamber 28 within ^I decreases. The pressure drop in the main reactant chamber 28, rupturable diaphragm 54 ^I bulges toward the beverage can base 14 ^I. The breakable diaphragm 54 ^I is a rupture membrane, which ruptures without the use of a piercing element. The breakable diaphragm 54 ^I is ruptured by a pressure difference between the main reactant chamber 28 and the water chamber 54 ^I, and an inelastic membrane that fluidly communicates between the water chamber 44 ^I and the main reactant chamber 28 ^I. can do. Water entering the water chamber 44 ^I in the main reactant chamber 28 ^I may react chemically, leading to the cooling effect on the beverage around as already described in FIG. 4 and FIG. 5.

FIG. 7A is similar to the self-cooling vessel 10 ^VI of FIG. 6, but instead of a breakable diaphragm and insertion element, a telescoping valve 68 is provided with a water chamber 44 ^I and a main reactant chamber 28 ^I. 2 shows a self-cooling vessel 10 ^VII separating the two. The telescopic valve 68 constitutes a plurality of valve elements 69, 70, 71. The valve element constitutes a circular cylindrical flange element. The first valve element 69 having the largest diameter is fixed to the inner wall of the cooling device 20 ^VII . The first valve element 69 slightly protrudes toward the bottom 22 ^I of the cooling device 20 ^VII , and constitutes a bead protruding inward. The second valve element 70 includes an upper protruding outer bead that seals against the first valve element, and an inner protruding bead that seals against the bead protruding outside the first valve element 69. The flange element which has is comprised. The third valve element 71 has an upper bead that protrudes outwardly and seals against a bead that protrudes outside the second valve element 70, and a lower bead that protrudes inside the second valve element 70. A cup-shaped element having a lower horizontal surface to be sealed is formed.

7B shows a self-cooled vessel ^{10 VII} in Figure 7A when the beverage can 12 ^I has been opened. As already described in FIG. 6B, the opening of the beverage can 12 ^I, the bottom 22 of the cooling device 20 ^I bulge outward, thereby the pressure of the main reactant chamber 28 within ^I decreases, the second and third Valve elements 70, 71 move in the direction of the bottom 22 of the cooling device 20 ^VII , so that the bead protruding outside the second valve element 70 is against the bead protruding inside the first valve element 71. The bead that seals and protrudes to the outside of the third valve element 71 is sealed against the bead that protrudes to the inside of the second valve element 70. The second and third valve elements 70, 71 include circumferentially arranged valve openings 72 that allow fluid communication between the water chamber 44 ^I and the main reactant chamber 28 ^I. To do. Thus, water can flow from the water chamber 44 to the main reactant chamber 28.

FIG. 8A is similar to the self-cooled vessel 10 ^IV described in connection with FIG. 4, except that an auxiliary reactant chamber 50 ^I is provided between the water chamber 44 ^I and the main reactant chamber 28 ^I. A self-cooling vessel 10 ^VIII is shown. The water chamber 44 ^I is separated from the auxiliary reactant chamber 50 by a support 74 and a breakable diaphragm 54 ^II . Support 74 is sealed between the cooling device 20 ^I inner wall rupturable diaphragm 54, the rupturable diaphragm covers the downcomer 76 in the center, the downcomer, the main reactants It protrudes toward the chamber 28 ^I. The auxiliary reactant chamber 50 ^I and the main reactant chamber 28 ^I are separated by a water-soluble diaphragm 78.

Figure 8B shows a self-cooled vessel ^{10 VIII} described in Figure 8A when the beverage can 12 ^I has been opened. The opening of the beverage can, the bottom 22 of the cooling device 20 ^I is, with reference to FIGS can bulge outward as described above. Due to the pressure drop in the main reactant chamber 28 ^I , the water-soluble diaphragm 78 swells toward the bottom 22 ^I , the pressure in the auxiliary reactant chamber 50 ^I drops and the breakable diaphragm 54 ^II ruptures, and the water chamber 44 The water in ^I enters the downcomer 76 and flows toward the water-soluble diaphragm 78. When the water-soluble diaphragm is dissolved by the water from the downcomer, the auxiliary reactant constituting the first reactant of the two reactants held in the auxiliary reactant chamber 50 and required for the start of the chemical reaction is held in the main reactant chamber 28 ^I, it is possible to react with the main reactants which constitute the second reactant two reactants required for initiation of chemical reactions. The initiation of the resulting chemical reaction is brought about by the mutual contact of these reactants. This reaction provides a cooling effect.

Figure 9A is similar to the self-cooled vessel 10 ^IV of FIG. 4 shows a self-cooled vessel 10 ^IX with a cooling device 20 ^IX which is formed entirely from polymeric material. The cooling device 20 ^II constitutes a polymer cylinder having three parts, the first part being a rigid cylinder part 80 fixed to the lid 16 of the beverage can 12 ^I. Because the lid is hermetically sealed, there is no fluid communication between the exterior and the upper rigid cylinder portion 80. The upper rigid cylinder portion 80 projects into the beverage can 12 ^I and is connected to a second cylinder portion that constitutes an intermediate flexible cylinder 82, which flexible cylinder constitutes a lower rigid cylinder portion 81. The lower rigid cylinder portion is sealed near the beverage can base 14. The upper hard cylinder portion 80 constitutes a water chamber and the lower hard cylinder portion is filled with granular reactant. When the beverage can ^12I is filled and pressurized, the pressure in the cooling device 20 ^IX is lower than the pressure in the beverage can 12, so that the intermediate flexible cylinder is squeezed to form a throttle valve. To do.

FIG. 9B shows the self-cooling container 10 ^IX of FIG. 9A when the beverage can 12 ^I is opened. Due to the pressure drop in the beverage can 12 ^I , the intermediate flexible cylinder 82 is not squeezed, allowing fluid communication between the upper hard cylinder portion 80 and the lower hard cylinder portion 81. Since the intermediate cylinder 82 thus forms a passageway, the water retained in the upper hard cylinder portion flows into the lower hard cylinder portion and thereby the coated granule reactant retained in the lower hard cylinder portion 81. Is activated.

FIG. 9C is similar to FIGS. 9A and 9B, but with the addition of an optional circumferential gripping member 83 located on the inner wall of the intermediate flexible cylinder 82, the beverage can 12 with the cooling device 20 ^{IX. 1} shows a self-cooled container 10 ^IX with I; The gripping member 83 accommodates a separating element 84 which constitutes a small disk-shaped element of plastic material, this separating element being held in the water held in the upper hard cylinder part 80 and in the lower hard cylinder part 81 More reliable blockage between granule reactants. The gripping member 83 and the separating element 84 are preferably made of substantially rigid plastic. The gripping member 83 comprises a gripping element that can be interlocked with a corresponding bead of the separation element 83.

9D shows an enlarged view of the gripping member 83 and the separation element 84 in FIG. 9C of the state where the beverage can 12 ^I is pressurized not been opened.

FIG. 9E is opened beverage can 12 ^I is, by the pressure drop from the outside of the intermediate flexible cylinder 82, the separation element wall portion of the intermediate flexible cylinder 82 is separated off from the gripping member 83, which 9D shows an enlarged view of FIG. 9D when fluid communication between the upper hard cylinder portion 80 and the lower hard cylinder portion 81 is enabled. By using the gripping member 83 and the separation element 84, a well-defined separation is achieved with the upper rigid cylinder portion 80 when the cooling device 20 ^II is activated and the wall of the intermediate flexible cylinder 82 is separated. This is achieved between the lower rigid cylinder portion 81.

FIG. 10A shows a cooling device ^10X similar to the cooling device ^10V of FIG. The cooling device 20 ^X has an auxiliary reaction chamber 50 ^I , which is disposed between the water chamber 44 ^I and the main reactant chamber 28 ^I. Auxiliary reaction chamber 50 ^I is separated from the main reactant chamber 28 ^I by the main cap 60 ^I and a main cap seat 62 ^I. The auxiliary reaction chamber is separated from the water chamber 44 ^I by an auxiliary cap 86 and an auxiliary cap seat 88. The main cap seat 62 and main cap 60 and the auxiliary cap seat 88 and auxiliary cap 86 function in the same manner as the main cap seat and main cap described in connection with FIG.

10B is a beverage can 12 is opened, the bottom 22 ^I of the cooling device 20 ^X is, shows a self-cooled vessel 10 ^X in Figure 10a when inflated outward by the pressure drop in the beverage can 12 ^I . The bulge to the outside, the auxiliary fall downwardly towards the bottom 22 ^I cap 62 and the main cap 60 ^I is the pressure, water and auxiliary reactant and the main reactants and is mixed chemical reaction starts.

Figure 11A is self is similar to the self-cooled vessel 10 ^X described in connection with FIG. 10, in place of the auxiliary cap seat supporting cap, the frangible diaphragm 54 ^I and the supporting mesh 66 is provided A cooled container ^10XI is shown. The support mesh 66 and the breakable diaphragm 54 ^I function in the same manner as the self-cooling container 10 ^VI of FIG.

Figure 11B shows a self-cooled vessel ^{10 XI} of Figure 11A when the cooling device ^{20 XI} been opened beverage can 12 ^I is is activated.

Figure 12A and 12B are breakable diaphragm 54 and penetrating element 56 of FIG. 4 in combination with breakable diaphragm 54 ^I and support mesh 66 of FIG. 6, self-cooling similar to a self-cooled vessel 10 ^{X Shown} is the formula container 10 ^XII .

FIG. 13A shows a self-cooling container 10 ^XIII having a beverage can 12 ^II having a ^submerged cooling device 20 ^XII constituting a small cooling device. The cooling device 20 ^XII preferably defines a cylinder of polymer material, which can move freely in the beverage in the beverage can 12 ^II . The cooling device 20 ^II includes a pressure space 32 ^II , a water chamber 44 ^II, and a main reactant chamber 28 ^II . The pressure space 32 ^II is provided with a pressure port 52 ^I that allows a small amount of beverage to enter the cooling device 20 ^II . The pressure space 32 ^I and the water chamber 44 ^II are separated by a flexible diaphragm 40 ^II . The water chamber 44 ^II and the main reactant chamber 28 ^I are separated by a plug seat 90 and a main plug 89 disposed at the center of the plug seat 90. The plug seat 90 interrupts between the main plug 89 and the inner wall of the cooling device 20 ^II . The main plug 89 is connected to the diaphragm 30 ^II . Excess pressure in the beverage can 12 ^I relaxes the diaphragm 30 ^II and keeps it out of operation. The main plug 89 separates the water in the water chamber 44 ^{II from} the granular reactant in the main reactant chamber 28 ^II .

FIG. 13B shows the self-cooling container 10 ^XIII shown in FIG. 13A when the beverage can 12 ^II is opened. When the beverage can 12 ^II is opened, the pressure in the beverage can 12 ^II and the pressure space 32 ^II decreases, and the diaphragm 30 ^II expands toward the pressure port 52 ^II due to the pressure in the water chamber 44 ^II . When the diaphragm 30 ^II expands toward the pressure port 52 ^I , the main plug 89 connected to the diaphragm 30 ^II is detached from the plug seat 90 and fluid communication between the water chamber 44 ^II and the main reactant chamber 28 ^II is achieved. And water enters the main reactant chamber 44 to cause a chemical reaction, thereby cooling the beverage.

FIG. 14A is similar to the self-cooled vessel 10 ^XIII shown in FIG. 13, but the cooling device 20 ^XIV additionally comprises an auxiliary reactant chamber 50 ^II containing a reaction control fluid that reduces the reaction time. FIG. 2 shows a self-cooled container 10 ^XIV . The auxiliary reactant chamber 50 ^II is located between the water chamber 44 ^II and the main reactant chamber 28 ^II . Water chamber 44 ^II and auxiliary reactant chamber 50 ^II are supported by main plug seat 90 and main plug 89, and auxiliary reactant chamber 50 ^II and main reactant chamber 28 ^II are provided by auxiliary plug seat 94 and auxiliary plug 92. It is supported. The auxiliary plug 92 is connected to the main plug 89.

FIG. 14B shows the self-cooling container 10 ^XIV of FIG. 14A when the beverage can 12 ^II is opened. The pressure drop when opening the beverage can ^{12 II,} the diaphragm 30 bulges toward the pressure port 22 ^I. Since both main plug 89 and auxiliary plug 92 are connected to diaphragm 30 ^II , both water chamber 44 ^II and auxiliary reactant chamber 50 ^II establish fluid communication with main reactant chamber 28 ^II . This causes the water in the water chamber 44 ^II and the reaction control fluid in the auxiliary reactant chamber 50 ^{II to} flow into the main reactant chamber 28 ^II filled with the coated granular reactant. When both reactants are mixed together in water, a chemical reaction takes place and cooling begins. The reaction control fluid extends the cooling effect and can be used, for example, to prevent ice formation within the beverage can 12.

Figure 15A and Figure 15B is similar to the self-cooled vessel 10 ^XIV shown in FIG. 14, as an alternative to the flow control fluid, the second reactant is held in an auxiliary reactant chamber 50 ^II , Which shows a self-cooled vessel 10 ^XV that eliminates the need for reactant coatings. When actuated by opening the beverage can 12 ^II , the first granular reactant in the main reactant chamber 28 mixes with the second granular reactant in the aqueous solution and a chemical reaction begins.

FIG. 16A shows a self-cooling vessel 10 ^XVI constituting a cooling box with a heat insulating carrier 96 made of a hard heat insulating material such as foamed styrene. Insulation carrier 96 is a space suitable for accommodating six standard beverage cans 12 ^III , ie, a typical size beverage can having a shape corresponding to the beverage can described above, indicated by reference numeral 12. But has no cooling device. Inner cavity 97 defines a flat bottom surface and an inner continuous side wall that defines a curved portion 98 that defines a plurality of interconnected arcs that coincide with the outer surface of the six beverage cans. This bend defines the position of the individual placement of the beverage can 12 ^III when placed in a known 3 × 2 “6-pack” configuration so that a stable and reliable placement is achieved. Accordingly, the inner cavity 97 is configured to accommodate a total of six beverage cans 12 ^III arranged in two rows with three beverage cans 12 ^III in each row. A spacer 99 is provided to fill the inner space of the six beverage cans 12 ^III to increase stability. The spacer 99 is preferably formed from a non-insulating material such as plastic, metal or cardboard or a weak insulating material. In self-cooled vessel ^{10 XVI,} 1 piece beverage can ^{12 III} is replaced by the cooling device ^{20 XVI} having a contour that matches the beverage can ^{12 III.} The cooling device 20 ^XVI has an operation button 100, and when this operation button is pressed, a chemical reaction in the cooling device 20 ^XVI starts. The interior of the cooling device 20 ^XVI should be consistent with any of the above cooling devices shown in FIGS. 1-15 except that it is actuated by external mechanical actuation, ie, pressing the button 100. Can do. Because the button can be attached directly to, for example, a breakable diaphragm that separates the two reactants, pressing the button breaks the diaphragm and allows the two reactants to contact each other. Alternatively, the button 100 can act on the pressure space, and this change in pressure causes the flexible diaphragm to move and initiate a chemical reaction.

FIG. 16B shows a plan view of a self-cooling container 10 ^XVI with a heat insulating carrier 96 containing five beverage cans 12 and a cooling device 20 ^XVI . The self-cooled container 10 ^XVI can be stored at room temperature. Immediately before the beverage in the beverage can is drunk, the operation button 100 of the cooling device 20 ^XVI is pressed to start cooling. As an additional insulation, an optional cover can be provided that hangs over the insulation carrier 96.

FIG. 17A shows a self-cooling vessel 10 ^XVII that constitutes an alternative structure to the self-cooling vessel 10 ^XVI . A cooling device 20 ^XVII corresponding to the cooling device 20 ^XVI in FIG. 16 is accommodated in a spacer 99 ^I disposed in the center, and six beverage containers are accommodated in an insulating carrier 96 ^I surrounding the spacer 99. ing. The insulating carrier 96 ^I has a round profile, and the inner cavity 97 ^I has a curved portion 98 ^I for accommodating six beverage cans 12 ^III in a circumferential structure around a centrally located spacer 99. .

FIGS. 17B and 17C show a perspective view and a plan view, respectively, of the self-cooling vessel 10 ^XVI .

  FIGS. 18A-18F illustrate the filling and pressurization process of the beverage can 12 of the type shown in FIGS. 1-3, including the cooling device 20 of the type shown in FIGS. 1-3. Yes.

FIG. 18A shows a process of ventilating the beverage can 12 before filling. The beverage can 12 includes a cooling device 20 and a lid flange 104. Beverage cans are typically ventilated three times by inserting a ventilation hose 102 and injecting carbon dioxide (CO ₂ ) into the beverage can 12. The air in the beverage can 12 is replaced with carbon dioxide. If any air remains in the beverage can 12, the beverage can deteriorate. Following ventilation, the beverage can 12 is filled with beverage as shown in FIG. 20B.

  FIG. 18B shows a beverage filling process in which the filling hose 103 is inserted into the beverage can 12 and the beverage is injected into the beverage can 12. The beverage is pre-injected with carbon dioxide and has a low temperature that is only a few degrees higher than the freezing point so that the maximum amount of carbon dioxide is dissolved in the beverage.

  FIG. 18C shows the filled beverage can 12 when the filling hose 103 is removed. The beverage is maintained in a carbon dioxide atmosphere having a temperature slightly above the freezing point where carbon dioxide can be saturated without the need for a high pressure environment.

  FIG. 18D shows the beverage can 12 with the lid 16 sealed to the lid flange 104. The lid 16 is folded over the lid flange 104 to form an airtight seal.

  FIG. 18E shows the beverage can 12 in the pasteurization plant 106. The pasteurization plant is equipped with a water bath at about 70 ° C. Pasteurization processes are known to retard the growth of any microorganisms in food products. During pasteurization, the pressure in the beverage rises to about 6 bar due to the heating of the beverage and the resulting release of carbon dioxide from the beverage. The cooling device should be sufficiently rigid to withstand such high pressures. In addition, the reactants used in the chiller are maintained unaffected by temperature and pressure increases, i.e., the reactants are not allowed to burn, react, melt, boil, or initiate subsequent reactions. No other changes to the enabled or disabled state should occur. Also, in the case of non-pasteurized beverages such as mineral water, the reactants should remain unaffected up to a temperature of at least 30 ° C. to 35 ° C., which can be reached during indoor or outdoor storage. Please also note that.

  FIG. 18F shows the beverage can 12 at room temperature. The pressure in the beverage can 12 is about 3-5 bar, which is sufficient to prevent the cooling device 20 from operating. When the beverage can is opened and the internal pressure escapes to the surrounding atmosphere, the beverage can 12 is at 1 bar atmospheric pressure and the cooling device 20 operates as already described with reference to FIGS. .

  FIGS. 19A-19E show the filling and pressurizing steps of the beverage can 12 of the type shown in FIGS. 13-15 with a cooling device of the type shown in FIGS. Yes. The manufacturing process is similar to the filling process described above with reference to FIG. 18 except that the arrangement of the cooling device 20 of FIG. 21C is performed after filling before the lid 16 is attached.

  FIGS. 20A-20F show the filling and pressurizing steps of a beverage can 12 of the type shown in FIGS. 4-12 with a cooling device of the type shown in FIGS. 4-12. Yes. Since the cooling device 20 is attached to the lid 16, the cooling device and the lid are attached to the beverage can 12 as an integral part in FIG. 20D.

FIG. 21A shows a party keg system 110 having a built-in pressurization system and a self-cooling vessel. This party keg typically constitutes a simple one-time beverage dispensing system and contains about 3-10 liters of beverage, typically 5 liters of beverage. Party kegs are often used in small social events such as private parties. Party kegs often include a pressure / carbonic injection system, and one such party keg system is described in pending unpublished European Patent Application No. 083888041.9. Party Keg is described in European Patent Application No. 083880441.9, but does not provide any internal cooling and therefore requires external cooling until just before the beverage is served. The party keg 110 includes a housing 112, which is preferably made of a thin insulating material such as expanded styrene. The housing includes an upper space 114 and a lower space 116, which are separated by a closure 118. A beverage keg 120 containing an appropriate amount of beverage is housed in the lower space 116 and secured to the closure 118. The beverage keg 120 includes an upwardly facing opening 122 that is fixed to the closure 118 by a fixing flange 123. A tap line 124 extends into the beverage keg 120 through the opening 122. The tap line constitutes a riser pipe, extends through the closure 118 and through the upper space 114 to the outside of the housing 112. Outside the housing 112, a tap valve 126 is used to control the flow of beverage through the tap valve 126. When tap valve 126 is in the open position, the beverage flows through tap line 124 and out of party keg system 110 through beverage tap 127 so that the beverage can be collected in a glass or the like. A gasket 128 seals the tap line 124 to the closure 118. A pressure generator 130 is disposed in the upper space 114. The pressure generator can be a pressurized carbon dioxide cartridge or a chemical pressure generator. The pressure generator 130 is connected to the beverage keg 120 by a pressure hose 132. The pressure hose 132 is connected to the inside of the beverage keg 120 through the opening 122 and is sealed to the closure 118 by the gasket 128. A pressurizing knob extending between the pressure generator 130 and the exterior of the housing 112 is used to initiate pressurization of the beverage keg 120. The beverage keg 120 is filled with a beverage and further contains a cooling device 20 ^XXI . The cooling device includes a main reactant chamber 28 and an auxiliary reactant chamber 50, which are separated by a water soluble diaphragm 78. A fluid inlet 136 is disposed adjacent to the water soluble diaphragm. The fluid inlet 136 allows pressurized fluid to enter the cooling device 20 ^XXI . The fluid inlet 136 includes a check valve 138 that completely prevents reactants from flowing out of the fluid inlet 136 due to pressure fluctuations in the beverage keg 120 and contacting the beverage.

FIG. 21B shows the party keg system 110 of FIG. 23A when actuated by operation of the pressure knob 134. When the pressure knob 134 is operated, pressurized carbon dioxide enters the beverage keg 120 and pressurizes the beverage contained therein. Accordingly, the beverage enters the fluid inlet 136 of the cooling device 20 ^XXI and dissolves the water-soluble diaphragm 78. As a result, the main reactant disposed in the main reactant chamber 28 mixes with the auxiliary reactant disposed in the auxiliary reactant chamber 50, so that the cooling reaction starts. The functional principle of the cooling device 20 is similar to the functional principle of the cooling device 20 ^VIII of FIG. 8, but in the opposite direction, ie the cooling device 20 ^VIII of FIG. The cooling device 20 ^XXI is activated by an increase in pressure. In this way, the party keg system 110 does not need to be cooled in advance and can be stored at room temperature. Immediately before drinking, the operator presses the pressure knob, which automatically initiates a cooling reaction, and after a few minutes, the tap valve 126 can be operated to dispense a cold beverage. It is further contemplated that the party keg system housing may be omitted or replaced with a simpler housing if insulation is not required.

FIG. 22A shows a private or commercial beverage dispensing system 140. Such beverage dispensing systems are known in the art and have already been described in WO 2007/019853. Beverage dispensing system 140 includes a rotatable enclosure 142 that is attached to a substrate 144. The interior of the enclosure 142 defines a pressure chamber 146. The pressure chamber 146 is separated from the substrate 144 by a pressure lid 148. The pressure lid 148 is sealed against the substrate 144 by a sealing 150. A side surface of the pressure lid 148 facing inwardly toward the pressure chamber 146 constitutes a coupling flange 152. The coupling flange 152 is used to secure the beverage keg 120 ^I, which is contained in the pressure chamber 146 and occupies most of it. Beverage keg 120 ^I is a shrink keg that is shrunk by pressure when the beverage is dispensed. A cooling / pressure generator 156 is connected to the pressure chamber 146 to cool and pressurize the beverage disposed in the beverage keg 146. Tap line 124 ^I connects pressure chamber 146 to tap valve 126. The end of the tap line 124 facing the pressure chamber 146 includes a cannula 151 that pierces a coupling flange 152 that allows fluid communication between the interior of the beverage keg 120 ^I and the tap valve 126. Tap handle 154 is used to operate tap valve 126 between a blocking position and a beverage dispensing position. The beverage dispensing position, the handle 154 is moved from its normal vertical orientation to a horizontal orientation, beverage through the beverage tap 127 ^I via a tap valve 126, it flows from the beverage dispensing system 140. The inside of the beverage keg 120 ^I accommodates the beverage and the cooling device 20 ^XXII . The cooling device 20 ^XXII held by the fixed rod 158 includes a main reactant chamber 28 and an auxiliary reactant chamber 50. The main reactant chamber 28 and the auxiliary reactant chamber 50 are separated by a breakable diaphragm 54. The upper part of the cooling device 20 ^XXI comprises a flexible diaphragm 30 to which a penetration element 56 is connected. The piercing element 56 extends towards the breakable diaphragm 54.

FIG. 22B shows the beverage dispensing system 140 of FIG. 24A when the pressure chamber 146 is pressurized. The pressure in the pressure chamber 146 acts to deform the beverage keg 120, thereby causing the flexible diaphragm 30 to swell inward toward the breakable diaphragm 54. Accordingly, the breakable diaphragm 54 is ruptured by the protruding insertion element 56 and a chemical reaction is initiated that results in cooling. Thus, rapid cooling of the beverage in the beverage keg 120 ^I is achieved, within minutes of operation, it is possible to dispense cold drinks from the beverage keg 126 ^I by operating the tap handle 154. In this way, it is not necessary to cool the beverage keg, and there is no need for a long waiting time until the beverage is cooled by the conventional method. The cooling device 20 ^XXII rapidly cools the beverage when the beverage keg is installed.

Figure 23A functions similarly to the cooling apparatus of FIG. 21, except for the cooling apparatus ^{20 XXIII,} shows a beverage dispensing system 140 ^I similar to the beverage dispensing system 140 shown in FIG. 24. The cooling device 20 includes a main reactant chamber 28 and an auxiliary reactant chamber 50, which are separated by a water soluble diaphragm 78. The water-soluble diaphragm 78 is connected to the coupling flange 152 by an operating passage 160. The coupling flange 152 includes a double sealing membrane 162 that blocks the working channel 160 from the interior of the beverage keg 120 ^I and the exterior of the coupling flange 152. FIG. 23A shows the installation procedure of the beverage keg 120 ^I when the enclosure 142 has been pivoted back to gain access to the pressure chamber 146.

FIG. 25B shows the beverage dispensing system 140 when the pressure lid 148 is attached to the enclosure 142 and the enclosure 142 is returned to its normal position to seal the pressure chamber 146. When the pressure lid 148 is attached, double sealing membrane 162 is pierced, it can be fluid to enter the working passageway 60 and tap line 124 ^I. When the pressure chamber 146 is pressurized, the beverage enters the working channel 160 and dissolves the water-soluble film 78 at the end of the working channel 160. Thus, operation is complete and a chemical reaction is initiated and the beverage is cooled as described in connection with FIG.

FIG. 24 shows a bottle 164 having a bottle cap 166 with an integrated cooling device 20 ^XXVI . The bottle cap 166 has a cap flange 170 attached to a thread 168 near the mouth of the bottle 164. The cooling device 20 ^XXVI is fixed to the bottle cap 166 and extends into the bottle 164. The cooling device 20 ^XXVI has an activation button 96 ^I for starting cooling before the bottle cap 166 is removed from the bottle 164.

  FIG. 25 shows a bottle 164 having a cooling device similar to the cooling device shown in FIG. 26A, except that a flexible diaphragm 30 is provided at the bottom of the cooling device 20. As the bottle cap 166 is twisted and the pressurized gas escapes from the bottle 164, the flexible diaphragm 30 expands outward, thereby initiating a chemical reaction similar to the self-cooled container shown in connection with FIG. 4A.

FIG. 26A shows a bottle 164 having a bottle cap 166 and an outer cap 172. The outer cap 172 is connected to a toothed rod, which is arranged in the cooling device 20 ^XXVI . The intermediate diaphragm 174 separates the two reactants in the cooling device 20.

  FIG. 26B shows the bottle 164 of FIG. 27 when the outer cap 172 is twisted. By twisting the outer cap, the toothed rod 176 breaks the intermediate diaphragm 174, thereby mixing the two reactants and initiating a chemical reaction that produces a cooling effect. After a few minutes, outer cap 172 and bottle cap 166 can be removed to provide a chilled beverage.

  FIG. 27A shows a drink stick 180 constituting a cooling stick having an integrated cooling device 20. The drink stick 180 includes a knob 182 that can be used as a handle, and an elongated flexible tank 184 that houses a cooling device. The cooling device 20 includes a breakable tank 186 containing a first reactant. The second reactant is contained in an elongated flexible tank 184 outside the breakable tank 186.

  FIG. 27B shows the operation of the drink stick 180 of FIG. 28A. The drink stick 180 operates when bent in the direction of the arrow. Bending the drink stick 180 breaks the breakable tank 186 and the first reactant mixes with the second reactant, thereby starting a chemical reaction that produces a cooling effect.

  FIG. 27C shows the drink stick 180 of FIG. 28B when the breakable tank breaks and the chemical reaction begins.

  FIG. 27D shows the drink stick 180 of FIG. 28C when the drink stick 180 is inserted into the bottle 164. Bottle 164 may be a conventional beverage bottle containing beer or soft drink at room temperature. Due to the cooling effect of the drink stick 180, the beverage in the bottle 164 is cooled to a temperature significantly below room temperature. It is further contemplated that the drink stick 180 can be used with other beverage containers to instantly cool any beverage. For example, the drink stick 180 can be provided in a bar for use with cold long drinks such as gin tonics to keep the beverage cold for an extended period of time.

  In an alternative embodiment, the drink stick 180 can have a conical shape and can be used with an ice mold to insert the activated drink stick into an ice mold filled with water to instantly freeze the ice cubes. Can be formed. Alternatively, the drink stick can have a square shape for direct use as ice cubes in beverages and the like.

  FIG. 28A shows a first embodiment of a bottle sleeve 188 that is suitable for attachment to the exterior of a bottle 164 used, for example, as a wine cooler. The bottle sleeve 188 includes a main reactant chamber 28 and a water chamber 44, which are separated by a breakable diaphragm 54. The bottle sleeve 188 is fixed to the bottle by a fixing ring 189, which coincides with the first groove 190 of the bottle sleeve 188. The retaining ring 189 is securely attached to the bottle 164. The first groove 190 is located adjacent to the main reactant chamber 28. The second groove 191 is adjacent to the water chamber 44 and is located on the first groove 190.

  FIG. 28B shows the bottle sleeve 188 when it is actuated by being pushed down in the direction of the arrow. By pushing down the bottle sleeve 188 downward, the fixing ring 189 is disengaged from the first groove 190 and accommodated in the second groove 191. Accordingly, the breakable diaphragm 54 is broken by the retaining ring 189 and the water in the water chamber 44 mixes with the reactants in the main reactant chamber 28 and the cooling reaction begins.

  FIG. 28C shows a perspective view of the bottle 164 with the bottle sleeve 190 attached.

  FIG. 29A shows a bottle sleeve constituting a wine cooler 192 having a flat structure. The wine cooler 192 includes an outer layer 193, an inner layer 194, and a breakable diaphragm 54 disposed between the outer layer and the inner layer. The space between the outer layer and the breakable diaphragm constitutes the water chamber 44, and the space between the breakable diaphragm and the inner layer 194 constitutes the main reactant chamber 28. Outer layer 192 and inner layer 194 are flexible and constitute a bistable layer having a first stable position of the flat structure shown in FIG. 29A.

  FIG. 29B shows the wine cooler 192 in a second bistable position forming a circular sleeve shape, with the outer layer 193 facing outward and the inner layer 194 facing inward. The second stable position can be achieved by applying a weak bending force to the wine cooler 192. Taking the second structure, i.e. the circular structure, breaks the breakable diaphragm 54 so that water and reactants are mixed and cooling begins.

  FIG. 29C shows a perspective view of the wine cooler 192.

  FIG. 29D shows the wine cooler 192 attached to the outside of the beverage bottle 164. Therefore, the beverage in the beverage bottle 164 is efficiently cooled to the drinking temperature.

  The efficiency of the self-cooling vessel and the cooling device is considered to strongly depend on the heat transfer characteristics (heat transfer factor) of the cooling device. The heat transfer factor can be changed by changing the shape of the cooling device, especially the surface area in contact with the beverage, for example by providing metal fins in the cooling device to increase the heat transfer factor and increase the cooling efficiency Can do. Subsequently, for example, by enclosing the cooling device in foamed styrene or a hydrophobic material, the heat transfer factor can be reduced, i.e. the cooling efficiency can be reduced. Alternatively, a catalyst can be used to increase the efficiency of the cooling chemical reaction, and a selective absorption control agent can be used to decrease the efficiency of the cooling chemical reaction.

  It is further contemplated that the entire cooling device can be formed from a flexible material such as rubber or plastic, and that the cooling device itself constitutes a flexible diaphragm.

  A modification of the cooling device can be activated by pulling a string connected to the mixing member through the cooling device.

  The cooling device is a reaction compartment in the space between the inner and outer tubes and is formed as a tube in the tube to cool the beverage flowing through the inner tube.

  The cooling device is configured so that it can be mounted around the tap line to cool the beverage flowing through the tap line.

  The cooling device can have a breakable seal to avoid accidental actuation.

  The cooling device includes an arming device having a membrane that is permeable to beverage, a saturated salt solution, and a non-permeable membrane that separates the salt solution from the interior of the cooling device. When the cooling device is submerged in the container, the moisture of the beverage enters the saturated salt solution through the permeable membrane by osmotic action and increases the volume, which puts pressure on the membrane, which pressure is inside the cooling device. As a result, the internal pressure increases and this pressure increase can be used to initiate the reaction as described above.

  FIG. 30 shows a simple cubic crystal 195 produced as an insoluble product of an irreversible entropy enhancement reaction according to the present invention. Crystal 195 comprises a total of six crystal planes, one of which is indicated by reference numeral 196. In addition, crystal 195 defines a total of eight corners, one of which is indicated by reference numeral 198. There is growth on face 196 of crystal 195, one of which is indicated by reference numeral 197. At corner 198, crystal growth is inhibited by the precipitate, one of which is indicated by reference numeral 199. The precipitate is formed from a selective absorbent that selectively adheres to the corner 198 of the crystal 195. The use of selective absorbents to prevent crystal growth has been demonstrated in reactions where the insoluble product can be encapsulated with the remaining reactants to stop the process as the insoluble product is formed. .

  FIG. 31 shows a dispensing / refrigeration system according to the present invention, indicated generally by the reference numeral 200. The system includes a refrigerated cabinet 202 having a cabinet in which an interior space is defined as illustrated in the lower right portion of FIG. In FIG. 31, the refrigerated cabinet 202 is broken to illustrate a plurality of beverage cans, one of the beverage cans is indicated by the reference numeral 204, and the beverage can is supported by a beverage can sliding chute, one of which is a sliding chute. , Indicated by reference numeral 206 and supporting a total of eight beverage cans 204. A refrigeration unit 208 and a heating unit 210 are accommodated in the refrigeration cabinet 202. The refrigeration unit 208 and the heating unit 210 each bring the inner chamber of the refrigeration cabinet 202 to a predetermined preset thermostat control temperature, for example, 16 ° C. to 20 ° C., particularly slightly higher or slightly lower than ambient temperature. Therefore, the cooling and heating functions of the inner chamber of the refrigerator cabinet 202 are achieved.

  When the ambient temperature is substantially constant and higher than a certain lower limit, the heating chamber 210 can be omitted because the inner chamber of the refrigeration cabinet 202 is always cooled to a temperature slightly lower than the ambient temperature. Since the internal temperature of the refrigerated cabinet 202 is set to a certain thermostat control temperature, each beverage can 204 can be dispensed with a beverage can within a fairly short period of time, for example within a few minutes of 1-5 minutes, preferably about 2 minutes. A cooling device may be provided that is implemented in accordance with the teachings of the present invention to cool from a temperature stored in the refrigerated cabinet 202 to a cooling temperature, eg, 5 ° C.

  The refrigeration cabinet 202 shown in FIG. 31 includes a dispensing opening 212 to which a dispenser chute is connected, which is indicated by reference numeral 216. The system 200 shown in FIG. 31 advantageously utilizes additional known elements or components provided in the refrigerated cabinet 202 for operating the dispensing mechanism, such as a coin acceptor, card reader, or chip reader. These control the dispensing of one beverage can 204 from the system 200 at a time upon confirmation of payment or receipt of a certain amount of remittance.

  Total consumption of electrical energy from the main power supply by providing a thermostatically controlled refrigeration cabinet 202 in which individual beverage cans 204 are stored at a preset constant temperature, preferably slightly below ambient temperature Is significantly reduced compared to a conventional beverage can dispenser that provides the user with a moderately chilled beverage can, ie, all beverage cans are cooled to a temperature of, for example, + 5 ° C. By reducing cooling to ambient temperature or slightly below it, only a fraction of the power consumption is in accordance with the present invention shown in FIG. 31 compared to a conventional beverage can refrigeration / dispensing system. Not used by beverage dispensing system. Conventional beverage can dispenser / refrigeration systems have to cool beverage cans from, for example, 25 ° C. or higher ambient temperature to 5 ° C., but the system 200 according to the present invention is for example up to a temperature of 20 ° C. Since it only serves to cool the beverage can, an energy consumption of approximately at least 80% is reduced when compared to an equivalent conventional dispenser / refrigeration system that cools the beverage can to 25 ° C to 5 ° C.

In Figure 32, there is shown a refrigeration system according to the invention, generally indicated by reference numeral 200 ^I. Beverage dispensing system 200 shown in FIG. 31 can be changed to a conventional fridge (fridge) or a refrigerator having the openable front door 203 ^I. The previous can be put individual beverage can 204 from the door over a series of shelves 206 ^I, beverage can 204 is supported on these shelves. The user can retrieve the beverage can 204 from these shelves open the refrigerator of the front door 202 ^I.

The refrigeration system 200 ^I is similar to the refrigeration system 200 of FIG. 31 except that it includes an openable cabinet 203 ^I to show the inside of the refrigerator cabinet. A plurality of beverage bottles, one indicated by reference numeral 204 ^I and a keg, one indicated by 204 ^II , are placed on a shelf of beverage cans, one indicated by reference numeral 206 ^I Yes. Shelf 206 ^I is a place of chute system described in connection with FIG. 31. The refrigerated cabinet 202 within ^I, refrigeration unit 208 and the heating unit 210 is housed. The refrigeration unit and the heating unit respectively bring the inner chamber of the refrigeration cabinet 202 ^I to a predetermined preset thermostat control temperature, for example, 16 ° C. to 20 ° C., in particular slightly higher or slightly lower than ambient temperature. Therefore, it fulfills the functions of cooling and heating the inside of the refrigerator cabinet.

  A cooling device included in an individual beverage can implemented in accordance with the teachings of the present invention by cooling individual beverage cans stored in the refrigerated cabinet described above or in a conventional refrigerator to a predetermined preset temperature. Can be designed to provide a predetermined and precise cooling of individual beverage cans from the temperature in the refrigerated cabinet to the temperature at which the user drinks or pours the beverage cans.

  Although the present invention has been described above with reference to a number of specific advantageous embodiments such as beverage containers, beverage cans, bottles, chillers, dispense / coolers, etc., the above embodiments of self-cooled containers The present invention is in no way limited by the above disclosure of the advantageous embodiments described above, since the features of the above embodiments of the cooling device and the features of the above embodiments of the cooling device can be combined to provide another embodiment of the self-cooled container and the cooling device. Please understand that it is not. All other embodiments are also considered part of this invention. Furthermore, it is to be understood that the invention includes all structures equivalent or similar to those described above, and also includes the following features that characterize the invention and the scope limited by the following claims that define the protection scope of the present application.

Claims (20)

A container for storing a beverage, the container comprising a container body and a closure, defining an internal chamber, the internal chamber defining an internal volume, comprising a predetermined volume of the beverage;
The cooling device further comprising a housing having a housing defining a housing volume not exceeding about 33% of the predetermined volume of the beverage and not exceeding about 25% of the internal volume;
The cooling device comprises at least two separate substantially non-toxic reactants, and when the reactants react with each other, at least 3, preferably at least 4, more preferably at least at least the stoichiometric amount of the reactants. Initiating an irreversible entropy increasing reaction to produce a substantially non-toxic product of 5 large stoichiometry,
When the at least two separate substantially non-toxic reactants are initially separated from each other and held in the cooling device and react with each other in the irreversible entropy increasing reaction, not more than 5 minutes, preferably not more than 3 minutes, More preferably, within a period of 2 minutes or less, said beverage of at least 50 joules per ml of beverage, preferably at least 70 joules per ml of beverage, for example 70-85 joules per ml of beverage, preferably about 80-85 joules per ml of beverage The amount of heat decreases,
The container wherein the cooling device further comprises an actuator for initiating the reaction between the at least two separate substantially non-toxic reactants.   The actuator transmits a pressure increase in the internal chamber to the cooling device to initiate the reaction or a pressure transmission to transmit a pressure drop in the internal chamber to the cooling device to initiate the reaction. A device, for example comprising a gas permeable membrane or a flexible membrane, or the actuator comprises a mechanical actuator for initiating the reaction between the at least two separate substantially non-toxic reactants, The container according to claim 1.   Separate compartments in the cooling device where the reactants are separated by a breakable, dissolvable, or breakable membrane that is broken, melted, or broken by the actuator, or separated by a replaceable plug Held in, or the actuator comprises a membrane disruption device or membrane penetration device for breaking or piercing the membrane, and / or the actuator is accessible from outside the container, preferably A container according to claim 1 or 2, wherein is actuated by the closure.   The irreversible entropy increasing response is less than ± 5%, such as preferably less than ± 4%, more preferably less than ± 5%, from the at least two separate substantially non-toxic reactants to the substantially non-toxic product. The volume change is less than ± 3% or the cooling device is in communication with the atmosphere so that any excess gas reduced by the irreversible entropy increasing reaction can be released to the atmosphere. The container of any one of 1-3.   The at least two separate substantially non-toxic reactants are present as separate granules, at least one granule and at least one liquid, or as a separate liquid, preferably the granule or the plurality of granules Is prevented from reacting by one or more external coatings, such as starch coatings or soluble plastic coatings, which can be dissolved by liquids such as water or organic solvents, preferably water-soluble coatings The container according to any one of claims 1 to 4, wherein the granules or the plurality of granules are enclosed in a soluble gel or foam to prevent a reaction.   The cooling device further comprises a chemical activator such as water, an organic solvent such as alcohol, propylene glycol, or acetone, and the liquid activator is preferably a reaction such as a selective absorption control agent or a delayed temperature setting agent. The container according to any one of claims 1 to 5, which functions as a control agent.   2. The at least two separate substantially non-toxic reactants comprise one or more salt hydrates, preferably inorganic salt hydrates, that liberate into a number of free water molecules in the irreversible entropy increasing reaction. The container of any one of -6.   The at least two separate substantially non-toxic reactants include a first reactant, a second reactant, and a third reactant, wherein the second reactant and the third reactant The reactants are present as separate granules and the first reactant is used as a coating over the granules of the second reactant and the third reactant. The system according to any one of the above.   The second reactant and the third reactant provide a first irreversible entropy increasing reaction that produces an intermediate reaction product, and the third reactant reacts with the intermediate reaction product to generate a first reaction. 9. The system of claim 8, wherein the system results in an irreversible entropy increasing response of two.   The system of claim 9, wherein the intermediate product is a gas and the second irreversible entropy increasing reaction produces a complex or precipitate.   The first reactant is dissolved in a liquid such as water or an organic solvent, preferably water, and the first reactant, the second reactant, and the third reactant are in the coating. The system according to any one of claims 8 to 10, wherein the reaction is prevented by.   The system according to claim 1, wherein the cooling device is housed in the container. A cooling device used in or in combination with a container for storing a beverage, the container comprising a container body and a closure, defining an internal chamber, the internal chamber comprising: Defining an internal volume, including a predetermined volume of the beverage;
The cooling device has a housing defining a housing volume not exceeding about 33% of the predetermined volume of the beverage and not exceeding about 25% of the internal volume;
The cooling device comprises at least two separate substantially non-toxic reactants, and when the reactants react with each other, at least 3, preferably at least 4, more preferably at least at least the stoichiometric amount of the reactants. Initiating an irreversible entropy increasing reaction to produce a substantially non-toxic product of 5 large stoichiometry,
When the at least two separate substantially non-toxic reactants are initially separated from each other and held in the cooling device and react with each other to initiate the irreversible entropy increasing reaction, preferably less than 5 minutes, preferably 3 Within a period of less than minutes, more preferably less than 2 minutes, at least 50 joules per ml beverage, preferably at least 70 joules per ml beverage, for example 70-85 joules per ml beverage, preferably about 80-85 joules per ml beverage The amount of heat in the beverage decreases,
The cooling device, further comprising an actuator for initiating the reaction between the at least two separate substantially non-toxic reactants.   The actuator transmits a pressure increase in the internal chamber to the cooling device to initiate the reaction or a pressure transmission to transmit a pressure drop in the internal chamber to the cooling device to initiate the reaction. A device, for example comprising a gas permeable membrane or a flexible membrane, or the actuator comprises a mechanical actuator for initiating the reaction between the at least two separate substantially non-toxic reactants, The cooling device according to claim 13.   Separate compartments in the cooling device where the reactants are separated by a breakable, dissolvable, or breakable membrane that is broken, melted, or broken by the actuator, or separated by a replaceable plug Held in, or the actuator comprises a membrane disruption device or membrane penetration device for breaking or piercing the membrane, and / or the actuator is accessible from outside the container, preferably 15. A cooling device according to claim 13 or 14, wherein said cooling device is actuated by said closure.   The irreversible entropy increasing response is less than ± 5%, such as preferably less than ± 4%, more preferably less than ± 5%, from the at least two separate substantially non-toxic reactants to the substantially non-toxic product. The volume change is less than ± 3% or the cooling device is in communication with the atmosphere so that any excess gas reduced by the irreversible entropy increasing reaction can be released to the atmosphere. The cooling device according to any one of 13 to 15.   The at least two separate substantially non-toxic reactants are present as separate granules, at least one granule and at least one liquid, or as a separate liquid, preferably the granule or the plurality of granules Is prevented from reacting by one or more external coatings, such as starch coatings or soluble plastic coatings, which can be dissolved by liquids such as water or organic solvents, preferably water-soluble coatings The cooling device according to any one of claims 13 to 16, wherein the granules or the plurality of granules are enclosed in a soluble gel or foam to prevent a reaction.   The cooling device further comprises a chemical activator such as water, an organic solvent such as alcohol, propylene glycol, or acetone, and the liquid activator is preferably a reaction such as a selective absorption control agent or a delayed temperature setting agent. The cooling device according to any one of claims 13 to 17, which functions as a control agent.   14. The at least two separate substantially non-toxic reactants comprise one or more salt hydrates, preferably inorganic salt hydrates, that are released into a number of free water molecules in the irreversible entropy increasing reaction. The cooling apparatus of any one of -18.   The device is configured as a cooling stick arranged in a beverage bottle or the like, configured as a cooling box containing a number of containers containing beverages, configured as a metal can of the size of a beverage can A part, for example a bottle neck or a metal can or a sleeve arranged to surround a part of the body of the bottle, or a part of a closure or a bottle cap. The cooling device according to any one of the above.

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