Patent Application
20130174581
Not Applicable
Beverage cans and beverage bottles have been used for decades for storing beverages, such as carbonated beverages, including beer, cider, sparkling wine, carbonated mineral water or various soft drinks, or alternatively non-carbonated beverages, such as non-carbonated water, milk products such as milk and yoghurt, wine or various fruit juices. The beverage containers, such as bottles and in particular cans, are typically designed for accommodating a maximum amount of beverage, while minimising the amount of material used, while still ensuring the mechanical stability of the beverage container.
Most beverages have an optimal serving temperature significantly below the typical storage temperature. Beverage containers are typically stored at room temperatures in supermarkets, restaurants, private homes and storage facilities. The optimal consumption temperature for most beverages is around 5° C. and therefore, cooling is needed before serving the beverage. Typically, the beverage container is positioned in a refrigerator or a cold storage room or the like well in advance of serving the beverage so that the beverage may assume a temperature of about 5° C. before serving. Persons wishing to have a beverage readily available for consumption must therefore keep their beverage stored at a low temperature permanently. Many commercial establishments such as bars, restaurants, supermarkets and petrol stations require constantly running refrigerators for being able to satisfy the customers' need of cool beverage. This may be regarded a waste of energy since the beverage can may have to be stored for a long time before being consumed. In the present context, it should be mentioned that the applicant company alone installs approximately 17000 refrigerators a year for providing cool beverages, and each refrigerator typically has a wattage of about 200 W.
As discussed above, the cooling of beverage containers by means of refrigeration is very slow and constitutes a waste of energy. Some persons may decrease the time needed for cooling by storing the beverage container for a short period of time inside a freezer or similar storage facility having a temperature well below the freezing point. This, however, constitutes a safety risk because if the beverage container is not removed from the freezer well before it freezes, it may cause a rupture in the beverage can due to the expanding beverage. Alternatively, a bucket of ice and water may be used for a more efficient cooling of beverage since the thermal conductivity of water is significantly above the thermal conductivity of air.
It would be advantageous if the beverage container itself contains a cooling element, which may be activated shortly before consuming the beverage for cooling the beverage to a suitable low temperature. Within the beverage field of packaging, a particular technique relating to cooling of beverage cans and self-cooling beverage cans have been described in among others U.S. Pat. No. 4,403,567, U.S. Pat. No. 7,117,684, EP0498428, U.S. Pat. No. 2,882,691, GB2384846, WO2008000271, GB2261501, U.S. Pat. No. 4,209,413, U.S. Pat. No. 4,273,667, U.S. Pat. No. 4,303,121, U.S. Pat. No. 4,470,917, U.S. Pat. No. 4,689,164, US20080178865, JP2003207243, JP2000265165, U.S. Pat. No. 3,309,890, WO8502009, U.S. Pat. No. 3,229,478, U.S. Pat. No. 4,599,872, U.S. Pat. No. 4,669,273, WO2000077463, EP87859 (fam U.S. Pat. No. 4,470,917), U.S. Pat. No. 4,277,357, DE3024856, U.S. Pat. No. 5,261,241 (fam EP0498428), GB1596076, U.S. Pat. No. 6,558,434, WO02085748, U.S. Pat. No. 4,993,239, U.S. Pat. No. 4,759,191, U.S. Pat. No. 4,752,310, WO0110738, EP1746365, U.S. Pat. No. 7,117,684, EP0498428, U.S. Pat. No. 4,784,678, U.S. Pat. No. 2,746,265, U.S. Pat. No. 1,897,723, U.S. Pat. No. 2,882,691, GB2384846, U.S. Pat. No. 4,802,343, U.S. Pat. No. 4,993,237, WO2008000271, GB2261501, US20080178865, JP2003207243, U.S. Pat. No. 3,309,890, U.S. Pat. No. 3,229,478, WO2000077463, WO02085748.
The above-mentioned documents describe technologies for generating cooling via a chemical reaction, alternatively via vaporisation. For using such technologies as described above, an instant cooling can be provided to a beverage and the need of pre-cooling and consumption of electrical energy is avoided. Among the above technologies, the cooling device is large in comparison with the beverage container. In other words, a large beverage container has to be provided for accommodating a small amount of beverage resulting in a waste of material and volume. Consequently, there is a need for cooling devices generating more cooling and/or occupying less space within the beverage container.
An object of the present invention is to provide a cooling device which may be used inside a beverage container for reducing the temperature of a beverage from about 22° C. to about 5° C., thereby eliminating or at least substantially reducing the need of electrical powered external cooling.
A further advantage according to the present invention is that the beverage container and the cooling device may be stored for an extended time such as weeks, months or years until shortly before the beverage is about to be consumed at which time the cooling device is activated and the beverage is cooled to a suitable consumption temperature. It is therefore a further object of the present invention to provide activators for activating the cooling device shortly before the beverage is about to be consumed.
The above objects together with numerous other objects which will be evident from the below detailed description of preferred embodiments of the cooling device according to the present invention and are according to a first aspect of the present invention obtained by a container for storing a beverage, the container having a container body and a closure and defining an inner chamber, the inner chamber defining an inner volume and including a specific volume of the beverage,
the container further including a cooling device having a housing defining a housing volume not exceeding approximately 33% of the specific volume of the beverage and further not exceeding approximately 25% of the inner volume,
the cooling device including at least two separate, substantially non-toxic reactants causing when reacting with one another a non-reversible, entropy-increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor 3, preferably at least a factor 4, more preferably at least a factor 5 larger than the stoichiometric number of the reactants,
the at least two separate substantially non-toxic reactants initially being included in the cooling device separated from one another and causing, when reacting with one another in the non-reversible, entropy-increasing reaction, a heat reduction of the beverage of at least 50 Joules/ml beverage, preferably at least 70 Joules/ml beverage, such as 70-85 Joules/ml beverage, preferably approximately 80-85 Joules/ml, within a period of time of no more than 5 min. preferably no more than 3 min., more preferably no more than 2 min., and
the cooling device further including an actuator for initiating the reaction between the at least two separate, substantially non-toxic reactants.
The container is typically a small container intended for one serving having a volume of about 20 to 75 centilitres of beverage. In some cases, however, it may be decided to use a cooling device with a larger container, such as a large bottle or vessel, which may accommodate one litre of beverage or a keg, which may accommodate five litres or more of beverage. In such cases, a cooling device is intended to give the beverage an instant cooling to suitable consumption temperature for the first serving of beverage, where after the beverage may be kept in a refrigerator for subsequent servings. The container is preferably made of aluminium, which is simple to manufacture, i.e. by stamping, and which may be recycled in an environmentally friendly way by melting of the container. Alternatively, collapsible or non-collapsible containers may be manufactured in polymeric materials such as PET plastics. Yet alternatively, the container may be a conventional glass bottle.
The cooling device is preferably fixated to the beverage container, such as fixated to the bottom of the container or the lid of the container. The cooling device should have a housing for separating the beverage and the reactant. The cooling device should not require a too large portion of the inner volume of the beverage container, since a too large cooling device will result in a smaller amount of beverage being accommodated in the beverage container. This would require either larger beverage containers or alternatively more beverage containers being produced for accommodating the same amount of beverage, both options being ecologically and economically undesired due to more raw material being used for manufacturing containers and more storage and transportation volume. It has been contemplated that a cooling device housing volume of about 33% of the beverage volume and 25% of the total inner volume of the beverage container would be still acceptable trade off between cooling efficiency and accommodated beverage volume. A too small cooling device would not be able to cool the beverage to sufficiently low temperatures.
The two reactants used in the cooling device should be held separately before activation of the cooling device and when the cooling device is activated, the two reactants are caused to react with one another. The reactants may be held separately by for instance being accommodated in two separated chambers or alternatively, one or both of the reactants may be provided with a coating preventing any reaction to start until activation. The two reactants should be substantially non-toxic, which will be understood to mean non-fatal if accidentally consumed in the relevant amounts used in the cooling device. It is further contemplated that there may be more than two reactants, such as three or more reactants. The reaction should be an entropy increasing reaction, i.e. the number of reaction products should be larger than the number of reactants. In the present context it has surprisingly been found out that an entropy increasing reaction producing products of a stoichiometric number of at least three, preferably four or more, preferably five larger than the stoichiometric number of the reactants will produce a more efficient cooling than a smaller stoichiometric number. The stoichiometric number is the relationship between the number of products divided with the number of reactants. The reaction should be non-reversible, i.e. understood to mean it should not without significant difficulties be possible to reverse the reaction, which would cause a possible reheating of the beverage. The temperature of the beverage should be reduced by at least 15° C. or preferably 20° C., which for a water-based beverage corresponds to a heat reduction of the beverage of about 50 to 85 joules per liter of beverage. Any smaller temperature or heat reduction would not yield a sufficient cooling to the beverage, and the beverage would be still unsuitably warm when the chemical reaction has ended and the beverage is about to be consumed. Preferably, the chemical reaction produces a heat reduction of 120-240 J/ml of reactants, or most preferably 240-330 J/ml of reactants. Such cooling efficiency is approximately the cooling efficiency achieved by melting of ice into water. The chemical reaction should preferably be as quick as possible, however still allowing some time for the thermal energy transport for avoiding ice formation near the cooling device. It has been contemplated that preferably the heat or temperature reduction is accomplished within no more than five minutes or preferably no more than two minutes. These are time periods which are acceptable before beverage consumption. In the present context it may be noted that carbonated beverages typically allow a lower temperature of the cooling device compared to non-carbonated beverages since the formation of CO2 bubbles rising in the beverage will increase the amount of turbulence in the beverage and therefore cause the temperature to equalize faster within the beverage.
Further, the term non-reversible should be considered to be synonymous with the word irreversible. The term non-reversible reaction should be understood to mean a reaction in which the reaction products and the reactants do not form a chemical equilibrium which is reversible by simply changing the proportions of the reactants and/or the reaction products and/or the external conditions such as pressure, temperature etc. Examples of non-reversible reactions include reactions in which the reaction products constitute a complex, a precipitation or a gas. Chemical reactions, such as reactions involving dissolving of a salt in a liquid such as water and disassociation of the salt into ions, which form an equilibrium, will come to a natural stop when the forward reaction and the backward reaction proceed at equal rate. E.g. in most solutions or mixtures the reaction is limited by the solubility of the reactants. A non-reversible reaction as defined above will continue until all of the reactants have reacted.
German published patent application DE 21 50 305 A1 describes a method for cooling beverage bottles or cans. A cooling cartridge including a soluble salt is included in the bottle or can. By dissolving the salt in a specific volume of water a cooling effect is obtained by utilizing the negative solution enthalpy. However, by using the negative solution enthalpy as proposed, the lowest temperature achieved was about 12° C., assuming an initial temperature of 21° C. None of the examples of embodiments achieves the sought temperature of about 5° C. By calculating the heat reduction in the beverage (Q=c*m*ΔT), the example embodiments achieve heat reductions of only about 15-38 J/ml of beverage. All of the examples of embodiments also require reactants having a total volume exceeding 33% of the beverage volume. Further, all of the reactions proposed in the above-mentioned document are considered as reversible, since the reactions may be reversed by simply removing the water from the solution. By removing the water, the dissolved salt ions will recombine and form the original reactants.
The German utility model DE 299 11 156 U1 discloses a beverage can having an external cooling element. The cooling element may be activated by applying pressure to mix two chemicals located therein. The document only describes a single chemical reaction including dissolving and disassociation of potassium chloride, saltpeter and salmiac salt in water which is stated to reach a temperature of 0° C. or even −16° C. of the cooling element, although the description is silent about the starting temperature of the cooling element. The description is also silent about the dimensions used for the cooling element and which volumes of beverage and reactants are used.
Many non-reversible entropy increasing reactions are known as such. One example is found on the below internet URL:
http://web.archive.org/web/20071129232734/http://chemed.chem.purdue.edu/demo/de mosheets/5.1.html. The above reference suggests the below reaction:
Ba(OH)2.8H2O(s)+2NH4SCN(s)→Ba(SCN)2+2NH3(g)+10H2O(l)
The above reference suggests that the reaction above is endothermal and entropy increasing and generates a temperature below the freezing temperature of water. However, there is no indication that the above reaction may be used in connection with the cooling of beverage, nor is any information about the amounts of reactants required available, nor the use of an actuator to initiate the reaction.
Different from most solution reactions, it should be noted that the above reaction may be initiated without the addition of any liquid water. Some other non-reversible entropy increasing reactions require only a single drop of water to initiate.
The use of ammonia is in the present context not preferred, since ammonia may be considered toxic, and will, in case it escapes into the beverage, yield a very unpleasant taste to the beverage. Preferably, all reactants as well as reaction products should in addition to being non-toxic have a neutral taste in case of accidental release into the beverage.
An actuator is used for activating the chemical reaction between the reactants. A reactant may include a pressure transmitter for transmitting a pressure increase, or alternatively a pressure drop, from within the beverage container to the cooling device for initiating the reaction. The pressure drop is typically achieved when the beverage container is open, thus the cooling device may be arranged to activate when the beverage container is being opened, alternatively, a mechanical actuator may be used to initiate the chemical reaction. The mechanical actuator may constitute a string or a rod or communicate with the outside of the beverage container for activating the chemical reaction. Alternatively, the mechanical actuator may be mounted in connection with the container closure so that when the container is opened, a chemical reaction is activated. The activation may be performed by bringing the two reactants in contact with each other, i.e. by providing the reactants in different chambers provided by a breakable, dissolvable or rupturable membrane, which is caused to break, dissolve or rupture by the actuator. The membrane may for instance be caused to rupture by the use of a piercing element. The reaction products should, as well as the reactants be substantially non-toxic.
One kind of activator is disclosed in the previously mentioned DE 21 50 305 A1, which uses a spike to penetrate a membrane separating the two chemicals. US 2008/0016882 shows further examples of activators having the two chemicals separated by a peelable membrane or a small conduit.
The volume of the products should not substantially exceed the volume of the reactants, since otherwise, the cooling device may be caused to explode during the chemical reaction. A safety margin of 3 to 5%, or alternatively a venting aperture, may be provided. A volume reduction should be avoided as well. The reactants are preferably provided as granulates, since granulates may be easily handled and mixed. The granulates may be provided with a coating for preventing reaction. The coating may be dissolved during activation by for instance a liquid entering the reaction chamber and dissolving the coating. The liquid may be referred to as an activator and may constitute e.g. water, propylene glycol or an alcohol. It is further contemplated that a reaction controlling agent, such as a selective adsorption controlling agent or a retardation temperature setting agent may be used for reducing the reaction speed, alternatively, a catalyst may be used for increasing the reaction speed. It is further contemplated that a container may comprise guiding elements for guiding the flow of beverage towards the cooling device for increasing the cooling efficiency. The present cooling device may also be used in a so-called party keg, which is a beverage keg having internal pressurization and dispensing capabilities. In this way, the comparatively large party kegs must not be pre-cooled before being used. The cooling device may alternatively be provided as a widget which is freely movable within the container. This may be suitable for glass bottles where it may be difficult to provide a fixated cooling device.
According to a further embodiment of the first aspect of the present invention, the two separate reactants comprise one or more salt hydrates. Salt hydrates are known for producing an entropy increasing reaction by releasing water molecules. In the present context, a proof-of-concept has been made by performing a laboratory experiment. In the above-mentioned laboratory experiment, a dramatic energy change has been established by causing two salts, each having a large number of crystal water molecules added to the structure, to react and liberate the crystal water as free water.
In the present laboratory experiment, the following chemical reaction has been tried out: Na2SO4, 10H2O+CaCl2, 6H2O→2NaCl+CaSO4, 2H2O+14H2O. The left side of the reaction scheme includes a total of two molecules, whereas the right side of the reaction schemes includes twenty molecules. Therefore, the entropy element—TΔS becomes fairly large, as ΔS is congruent to k×ln 20/2.
The above chemical reaction produces a simple salt in an aqueous solution of gypsum. It is therefore evident that all constituents in this reaction are non-toxic and non-polluting. In the present experiment, 64 grams of Na2SO4 and 34 grams of CaCl2, the reaction has produced a temperature reduction of 20° C., which has been maintained stable for more than two hours. A prototype beer can has been manufactured having a total volume of 450 ml including 330 ml of beer and a bottle of 100 ml including the two reactants. After the opening of the can, the reactants were allowed to react resulting in a dramatic cooling of the beer inside the beverage can.
According to the present invention, a cooling device is provided based on a chemical reaction between two or more reactants. The chemical reaction is a spontaneous non-reversible endothermic reaction driven by an increase in the overall entropy. The reaction absorbs heat from the surroundings resulting in an increase in thermodynamic potential of the system. ΔH is the change in enthalpy and has a positive sign for endothermic reactions. The spontaneity of a chemical reaction can be ascertained from the change in Gibbs free energy ΔG.
At constant temperature ΔG=ΔH−T*ΔS. A negative ΔG for a reaction indicates that the reaction is spontaneous. In order to fulfill the requirements of a spontaneous endothermic reaction the overall increase in entropy ΔS for the reaction has to overcome the increase in enthalpy ΔH.
According to a further embodiment of the first aspect of the present invention at least two separate, substantially non-toxic reactants comprise a first reactant, a second reactant and a third reactant, the second and third reactants being present as separate granulates and the first reactant being applied as a coating covering the granulates of the second and third reactants. By coating the second and the third reactants by the first reactant it can be ensured that the three reactants are held separated although the three reactants are mixed, since the second and the third reactants are prevented from reacting by the first reactant. In this way accidental activation of the chemical reaction may be avoided, e.g. by shock or in case a small amount of water enters the reaction chamber, the reaction will not be initiated since the coating will protect the second and third reactants. It is preferred to use the first reactant as the coating, since a non-reacting coating would constitute a waste of volume and thereby necessitate a larger cooling device.
According to a further embodiment of the first aspect of the present invention the second and third reactants generate a first non-reversible entropy increasing reaction producing an intermediate reaction product, and the third reactant reacting with the intermediate reaction product generating a second non-reversible entropy increasing reaction. In case the intermediate reaction products are toxic or otherwise unpleasant, such as bad smelling, the negative effect of the intermediate products may be avoided by allowing them to react with the third reactant and create an end product which is safe and which does not have any of the drawbacks of the intermediate reaction products.
According to a further embodiment of the first aspect of the present invention the intermediate product is a gas and the second non-reversible entropy increasing reaction generates a complex or a precipitate. For instance, the intermediate product may be a toxic or smelly gas, which may be unsuitable for use in the present context. The gas may then be pacified by reacting with the third reactant to form a complex or a precipitate which is safe.
According to a further embodiment of the first aspect of the present invention the first reactant is dissolvable by water or an organic solvent preferably a liquid such as water, the first, second and third reactants being prevented from reacting through the coating. Upon initiation, a sufficient amount of water to at least partially dissolve the coating is introduced into the cooling device, thereby allowing all three reactants to dissolve and react with each other.
According to a further embodiment of the first aspect of the present invention the cooling device is accommodated within the container. To ensure that a high percentage of the cooling energy is used for cooling the beverage and not lost to the surroundings, the cooling device may be located within the container, preferably in direct contact with the beverage and more preferably completely surrounded by beverage.
The cooling device according to the present invention includes at least two separate, substantially non-toxic reactants causing with one another a non-reversible entropy increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor 3, preferably a factor 4, more preferably a factor 5 larger than the stoichiometric number of the reactants.
The reactants are preferably solids but solid-liquid, liquid-liquid and solid-solid-liquid reactants are contemplated also to be relevant in the present context i.e. in the context of implementing a cooling device for use in a beverage container. Solid reactants may be present as powder, granules, shavings, etc.
The reactants and products are substantially non-toxic.
In the context of the present invention non-toxic is not to be interpreted literally but should be interpreted as applicable to any reactant or product which is not fatal when ingested in the amounts and forms used according to the present invention. Suitable reactants form products which are a) easily soluble in the deliberated crystal water or b) insoluble in the deliberated crystal water. A list of easily soluble vs less soluble salt products is given below:
Further suitable reactants are the following:
NaAl(SO4)2.12H2O
NH4Al(SO4)2.12H2O
LiOHH2O
Na2SiO3
Na2SiO3.xH2O, x=5-9
Na2O.xSiO2, x=3-5
Na4SiO4
Na6Si2O7
Li2SiO3
Li4SiO4
Additional reactants and sets of reactants are listed in the below Table 1 and Table 2.
The salt product is preferably an easily soluble salt although less soluble products are preferable for salt products which are toxic to render them substantially non-toxic.
The volumetric change during the non-reversible entropy-increasing reaction is no more than ±5%, preferably no more than ±4%, further preferably no more than ±3%, or alternatively the cooling device being vented to the atmosphere for allowing any excess gas produced in the non-reversible entropy-increasing reaction to be vented to the atmosphere.
Suitable solid reactants according to the present invention are salt hydrates and acid hydrates. The salt hydrates according to the invention are organic salt hydrates or inorganic salt hydrates, preferably inorganic salt hydrates. Some of the below salts are contemplated to be present only in trace amounts for controlling selective adsorption. Suitable organic salt hydrates may include Magnesium picrate octahydrate Mg(C6H2(NO2)3O)2.8H2O, Strontium picrate hexahydrate Sr(C6H2(NO2)3O)2.6H2O, Sodium potassium tartrate tetrahydrate KNaC4H4O6.4H2O, Sodium succinate hexahydrate Na2(CH2)2(COO)2.6H2O, Copper acetate monohydrate Cu(CH3COO)2.H2O etc. Suitable inorganic salt hydrates according to the invention are salt hydrates of alkali metals, such as lithium, sodium and potassium, and salt hydrates of alkaline earth metals, such as beryllium, calcium, strontium and barium, and salt hydrates of transition metals, such as chromium, manganese, iron, cobalt, nickel, copper, and zinc, and aluminium salt hydrates and lanthanum salt hydrates. Suitable alkali metal salt hydrates are for example LiNO3.3H2O, Na2SO4.10H2O (Glauber's salt), Na2SO4.7H2O, Na2CO3.10H2O, Na2CO3.7H2O, Na3PO4.12H2O, Na2HPO4.12H2O, Na4P2O7.10H2O, Na2H2P2O7.6H2O, NaBO3.4H2O, Na2B4O7.10H2O, NaClO4.5H2O, Na2SO3.7H2O, Na2S2O3.5H2O, NaBr.2H2O, Na2S2O6.6H2O, K3PO4.3H2O etc, preferably suitable alkaline earth metal salt hydrates are for example, MgCl2.6H2O, MgBr2.6H2O, MgSO4.7H2O, Mg(NO3)2.6H2O, CaCl2.6H2O, CaBr2.6H2O, Ca(NO3)2.4H2O, Sr(NO3)2.4H2O, Sr(OH)2.8H2O, SrBr2.6H2O, SrCl2.6H2O, SrI2.6H2O, BaBr2.2H2O, BaCl2.2H2O, Ba(OH)2.8H2O, Ba(BrO3)2.H2O, Ba(ClO3)2.H2O etc. Suitable transition metal salt hydrates are for example, CrK(SO4)2.12H2O, MnSO4.7H2O, MnSO4.5H2O, MnSO4.H2O, FeBr2.6H2O, FeBr3.6H2O, FeCl2.4H2O, FeCl3.6H2O, Fe(NO3)3.9H2O, FeSO4.7H2O, Fe(NH4)2(SO4)2.6H2O, FeNH4(SO4)2.12H2O, CoBr2.6H2O, CoCl2.6H2O, NiSO4.6H2O, NiSO4.7H2O, Cu(NO3)2.6H2O, Cu(NO3)2.3H2O, CuSO4.5H2O, Zn(NO3)2.6H2O, ZnSO4.6H2O, ZnSO4.7H2O etc. Suitable aluminium salt hydrates are for example Al2(SO4)3.18H2O, AlNH4(SO4)2.12H2O, AlBr3.6H2O, AlBr3.15H2O, AlK(SO4)2.12H2O, Al(NO3)3.9H2O, AlCl3.6H2O etc. A suitable lanthanum salt hydrate is LaCl3.7H2O.
Suitable acid hydrates according to the invention are organic acid hydrates such as citric acid monohydrate etc.
A salt or acid hydrate is preferably reacted with another salt or acid hydrate, it can however also be reacted with any non-hydrated chemical compound as long as crystal water is deliberated in sufficient amounts to drive the endothermic reaction with respect to the entropy contribution.
Suitable non-hydrated chemical compounds according to the invention may include acids, alcohols, organic compounds and non-hydrated salts. The acids may be citric acid, fumaric acid, maleic acid, malonic acid, formic acid, acetic acid, glacial acetic acid etc. The alcohols may be mannitol, resorcinol etc. The organic compounds may be urea etc. The non-hydrated salts according to the present invention may be such as anhydrous alkali metal salts, anhydrous alkaline earth metal salts anhydrous transition metal salts anhydrous aluminium salts and anhydrous tin salts and anhydrous lead salt and anhydrous ammonium salts and anhydrous organic salts. Suitable anhydrous alkali metal salt hydrates are for example NaClO3, NaCrO4, NaNO3, K2S2O6, K2SO4, K2S2O6, K2S2O3, KBrO3, KCl, KClO3, KIO3, K2Cr2O7, KNOB, KClO4, KMnO4, CsCl etc. Suitable anhydrous alkaline earth metal salts are for example CaCl2, Ca(NO3)2, Ba(BrO3)2, SrCO3, (NH4)2Ce(NO3)6 etc. Suitable anhydrous transition metal salts are for example NiSO4, Cu(NO3)2. Suitable anhydrous aluminium salts are Al2(SO4)3 etc. Suitable anhydrous tin salts are SnI2(s), SnI4(g) etc. Suitable anhydrous lead salts are PbBr2, Pb(NO3)2 etc. Suitable ammonium salts are NH4SCN, NH4NO3, NH4Cl, (NH4)2Cr2O7 etc. Suitable anhydrous organic salts are for example urea acetate, urea formate, urea nitrate and urea oxalate etc.
It is further contemplated that the anhydrous form of any hydrated salt or hydrated acid as listed above may be used as a non-hydrated chemical compound in a reaction according to the present invention.
A liquid reactant according to the present invention may be a liquid salt such as PBr3, SCl2, SnCl4, TiCl4, VCl4 or a liquid organic compound such as CH2Cl2 etc.
The number of reactants participating in the reaction is at least two. Some embodiments may use three or more reactants.
One possible reaction according to the present invention is
Na2SO4.10H2O(s)+CaCl2.6H2O(s)→2Na+(aq)+2Cl−(aq)+CaSO4.2H2O(s)+14H2O(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=298 K)
ΔG=ΔH−T*ΔS=94 kJ/mol−298 K*0.447 kJ/K*mol=−39 kJ/mol
The negative sign indicates that the reaction is spontaneous.
The stoichiometric number of products to reactants is 19/2=9.5:1
Another possible reaction according to the present invention is
Na2SO4.10H2O(s)+Ba(OH)2.8H2O(s)→BaSO4(s)+2Na+(aq)+20H−(aq)+18H2O(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 at room temperature (T=298 K) for this reaction can be directly calculated:
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
Thus this reaction is spontaneous. The stoichiometric number of products to reactants is 23/2=11.5:1
A further possible reaction according to the present invention is
Ba(OH)2.8H2O(s)+2NH4SCN(s)→Ba(SCN)2+2NH3(g)+10H2O(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
The reaction is spontaneous. The stoichiometric number of products to reactants is 13/3=4.33:1
Examples of further reactions are
Ba(OH)2.8H2O(s)+2NH4NO3(s)→Ba(NO3)2+2NH3(g)+10H2O(l) a)
Ba(OH)2.8H2O(s)+2NH4Cl(s)→BaCl2+2NH3(g)+10H2O(l) b)
The reaction is preferably activated by the addition of a polar solvent, such as water, glycerin, ethanol, propylene glycol, etc but the reaction may also be activated simply by contacting the reactants.
In some reactions the reactants may be non-reactive when contacted or being mixed. For these reactions a suitable catalyst may be used to enable the reaction.
In some embodiments the solid reactants are coated or microencapsulated. Suitable external coatings are heat resistant but dissolvable upon contact with an activation fluid capable of dissolving the coating. Suitable coatings include carbohydrates such as starch and cellulose, polyethers such as polyethylene glycol (PEG) but also shellac or plastics. Suitable activation fluids include water alcohols, organic solvents, acids. As an alternative to a coating, the solid reactants may be embedded in a soluble gel or foam.
By use of a coating the reactants can be premixed in order to increase the reaction rate. Furthermore, coating of reactants prevents premature activation of the cooling effect due to storage conditions or heat treatment of the beverage. In some embodiments a part of the reactant mass is coated with a thicker coating in order to slow down the reaction and prolong the cooling provided by the reaction. In other embodiments more than one coating may be applied to the reactants or different coatings may be applied to different reactants or parts of the reactant mass. Instead of a coating the reactants can be suspended in a non-aqueous fluid such as an organic solvent.
A retardation temperature setting agent having a suitable melting temperature may be used with the current invention. A suitable melting temperature may be such a temperature that the retardation temperature setting agent is liquid at temperatures above a freezing point or any desirable temperature yielding a desired cooling of the beverage to be cooled and solidifies as the temperature descends below this point thus retarding the reaction in order to prevent freezing of the beverage in the beverage container. The retardation temperature setting agent may be any chemical compound with a suitable melting temperature above the freezing temperature of water such as a temperature between 0° C. to +10° C. such as 2° C. to 6° C. such that the solidified form of the retardation temperature setting agent decreases the reaction rate of the reaction according to the present invention. Examples of suitable retardation temperature setting agents include polyethylene glycol, a fatty acid, or a polymer.
The reactants can be in the form of granulates of varying sizes to tailor the reaction rate to the specific application. The granules may also be coated as described above.
For some reactions it is preferable to add a solvent such as glycerol or a trace contaminant to prevent the formation of crystals of a product from coating remaining reactants thus inhibiting further reaction. An adsorbent can be used to selectively adsorb a product in order to control the reaction rate and/or ensure complete reaction.
For some reactions the liquid activator used to initiate the reaction may also serve as a selective adsorption-controlling agent to control the reaction.
In reactions producing acidic or basic products a pH-regulating buffer may be included. The buffer may also be used to promote the dissolution of products in form of gas.
It is contemplated that one or more reactants may be formed in situ from precursors. This can be advantageous for preventing premature activation or preactivation of the cooling device after it has been placed in the container.
It is further contemplated that the following additives may be relevant for some reactions in the context of controlling the reaction: 3,7-diamino-5-phenothiazinium acetate, 18 crown 6 ether, 1,3-dimethyl-2-imidazolidinone.
The presently preferred reaction is a reaction between strontium hydroxide octahydrate and ammonium nitrate. To make the end product safe, magnesium nitrate hexahydrate is added as a third reactant. Most preferably, the magnesium nitrate hexahydrate is used as a coating for separating the strontium hydroxide octahydrate and ammonium nitrate. The above reactants react in a primary reaction and a NH3 pacification reaction. The primary reaction having a high cooling efficiency is as follows:
3Sr(OH)2.8H2O(s)+6NH4NO3(s)→3Sr2++6NO3−+6NH3+30H2O
Since NH3 may be considered as toxic, or at least not pleasantly smelling, it has to be pacified by a further reaction. The NH3 pacification reaction has a cooling efficiency which is lower than the cooling efficiency of the primary reaction:
3Sr2++6NO3−+6NH3+30H2O+Mg(NO3)2.6H2O(s)→3Sr2++8NO3−+Mg(NH3)62++36H2O
The end product is a white gel that smells slightly of ammonia and which is completely safe.
88 ml of the above reactants are required to cool down 330 ml of beverage by 20 degrees centigrade. Thus, a common 440 ml beverage can may be used for accommodating 330 ml of beverage and 88 ml of reactants.
Dependent on the reaction used, the heat capacity of the reaction mixture and the beverage, the initial temperature of the beverage and the amounts of beverage and reactants, respectively, a wide range of cooling effects may be obtained.
A cooling device according to the present invention may contain any amount of reactant as long as the volume of the cooling device does not exceed 30% of the container volume.
The cooling effect of the cooling device in the beverage container should be sufficient to cool a volume of beverage at least 10° C. within a period of time of no more than 5 min., preferably no more than 2 min.
For a beverage consisting mainly of water the specific heat capacity can be approximated with the specific heat capacity for liquid water: 4.18 kJ/kg·K. The cooling effect q needed for cooling the beverage is given by the equation: q=m·ΔT·Cp. Thus in order to cool 1 kg of beverage 20° C. the cooling device must absorb 83.6 kJ of heat from the beverage to be cooled. Thus in the present invention a heat reduction of the beverage should be at least 50 Joules/ml beverage, preferably at least 70 Joules/ml beverage such as 70-85 Joules/ml beverage preferably approximately 80-85 Joules/ml beverage within a time period of no more than 5 min, preferably no more than 3 min, more preferably no more than 2 min.
According to further embodiments, the container body may comprise a beverage keg of polymeric or metallic material having a volume of 3-50 liters, the keg being either collapsible or rigid, and the closure being a keg coupling. Alternatively, the container body may comprise a bottle of glass or polymeric material, the bottle having a volume of 0.2-3 liters, and the closure being a screw cap, crown cap or stopper. Yet alternatively, the container body may comprise a beverage can and a beverage lid of metallic material, preferably aluminum or an aluminum alloy, the can having a volume of 0.2-1 liters, and the closure being constituted by an embossing area of the beverage lid. Yet alternatively, the container may comprise a bag, preferably as a bag-in-box, bag-in-bag or bag-in-keg.
According to further embodiments, the container comprises guiding elements for guiding the flow of beverage from the container body. The guiding elements may serve to guide the flow of the beverage via the cooling device towards the closure. The cooling device may be located within the container, or alternatively the cooling device is located outside the container. The container body may constitute a double walled container constituting an inner wall and an outer wall, and the cooling device may be located between the inner and outer wall.
According to further embodiments, the container may comprise a pressure generating device either accommodated within the container or connected to the container via a pressurization hose. The pressure generating device preferably comprises a carbon dioxide generating device for pressurization of the beverage in the beverage container.
According to further embodiments, the container may comprise a tapping line and a tapping valve for selectively dispensing beverage from the beverage container. The beverage container may be filled with carbonated beverage such as beer, cider, soft drink, mineral water, sparkling wine, or alternatively non-carbonated beverage such as fruit juice, milk products such as milk and yoghurt, tap water, wine, liquor, ice tea, or yet alternatively a beverage constituting a mixed drink.
According to further embodiments, the cooling device forms an integral part of the beverage container or a part of the top of the beverage container, alternatively a part of the wall or bottom of the beverage container. The cooling device is fastened onto the base of the beverage container, alternatively the wall of the container, yet alternatively the top of the container, or alternatively the cooling device constitutes a widget, which is freely movable within the container.
According to a further embodiment, the cooling device may be configured as a metal can of the size of a beverage can, or configured as a cooling box for receiving a number of beverage containing containers, or configured as a cooling stick to be positioned in a beverage bottle or the like, or configured as a sleeve to be positioned encircling a part of a container, e.g. the neck of a bottle or the body part of a metal can or bottle or configured as a part of the closure or cap of a bottle.
A problem in relation to the cooling of water based beverages by including a cooling device in contact with the beverage is the relatively low thermal conductivity and the relatively high heat capacity of water. This means that water may be considered to be a thermal insulator. Concerning carbonated beverages the carbon dioxide gas bubbles generated in the beverage will further reduce the thermal conductivity of the carbonated beverage compared to a non-carbonated beverage. Thus, although the cooling device is capable of cooling the beverage immediately adjacent the cool walls of the cooling device, any beverage located further away from the cooling device will remain warm. The main cooling effect in a beverage container is provided by conductive cooling and convective cooling. The convective cooling may be increased in case the beverage container is shaken to allow the cool beverage near the walls of the cooling device to be substituted by warmer beverage further away from the cooling device, however, shaking a beverage container containing carbonated beverage is not advisable since it will generate excessive carbon dioxide bubble formation within the beverage. The bubble formation will apart from causing the beverage to erupt during opening of the beverage container, further worsen the conducive cooling, since the carbon dioxide bubbles are excellent thermal insulators. There is therefore a need to improve the conductive cooling of carbonated beverages using a cooling device.
It is therefore a further object of the present invention to provide a cooling device capable of cooling the carbonated beverage to an optimal serving temperature within a short time period.
The above objects together with numerous other objects which will be evident from the below detailed description of preferred embodiments of the cooling device according to the present invention are according to a above aspect of the present invention obtained by_a container for storing a beverage, the container having a container body and a closure and defining an inner chamber, the inner chamber defining an inner volume and including a specific volume of the beverage,
The applicant has surprisingly found out that the conductive cooling within the beverage may be improved by reforming the outer surface of the cooling device. At the same time, the convective cooling plays a minor role due to the small volume of the beverage container. The temperature of the outer cooling surface will sink rapidly to a temperature only slightly above freezing just after activation of the cooling device. The beverage located adjacent the outer cooling surface of the cooling device will therefore assume a low temperature quickly. The heat transfer between the cool beverage adjacent the outer cooling surface of the cooling device and the beverage located furthest away in relation to the outer cooling surface is considerably slower and is determined by the temperature gradient. In order to maximize the heat transfer the temperature gradient should be maximized as well. The temperature gradient may be maximized by minimizing the distance between the outer cooling surface of the cooling device and the beverage located furthest away in relation to the outer cooling surface. Various shapes of the outer cooling surface, such as the shapes described herein, may be contemplated in order to achieve a small distance between the outer cooling surface of the cooling device and the beverage located furthest away in relation to the outer cooling surface, however, much material will be required and the dispensing or pouring behaviour of the beverage will be influenced by the additional flow resistance caused by the outer cooling contact surface. The flow resistance may e.g. cause significantly slower pouring of the beverage or may even cause some beverage to be trapped within the outer surface and remain inside the beverage container. Such beverage will be lost for the consumer.
The applicant has thereby determined by conducting laboratory experiments that a maximum distance between any point within the top half space to an adjacent point on the outer cooling surface should be of the order of 0.5 cm-2.0 cm to achieve a quick cooling and at the same time allow a suitable dispensing behaviour of the complete beverage in the beverage container.
Further, the convective heat transfer may be improved without the need to shake the beverage container by locating the cooling device near the top of the beverage container. In this way the beverage near the top of the beverage container, i.e. in the upper half space of the beverage container, will be slightly cooler than the beverage near the bottom of the beverage container, i.e. in the bottom half space of the beverage container. As cool beverage has a higher density than warm beverage, the cool beverage at the top will sink towards the bottom, substituting the warm beverage at the bottom, which warm beverage will rise towards the top of the beverage container. Top and bottom should in the present context be understood in relation to the normal resting position of the beverage container, e.g. for typical beverage containers such as cans having the top near the opening of the beverage container. Having the cooling device near the opening of the beverage container has the additional benefit of further cooling the beverage which is about to be consumed or dispensed.
According to a further embodiment of the above aspect of the present invention, any point within the bottom half space defining the maximum distance A to an adjacent point on the outer cooling surface, or, preferably, wherein any point within the inner chamber defining the maximum distance A to an adjacent point on the outer cooling surface. Since the convective cooling plays a minor role in the cooling of the beverage, the outer cooling surface of the cooling device may extend into the lower half space of the beverage container as well for improving the conductive cooling in the complete beverage container. Preferably, the outer cooling surface of the cooling device extends outside the beverage space, such as into the head space, in order to improve the conductive cooling of the beverage also when the beverage container is stored in an arbitrary position or orientation different from the normal vertical orientation, such as when the beverage container is stored in a horizontal position.
According to a further embodiment of the above aspect of the present invention, the inner chamber defines an inner surface, the outer cooling surface defining an area being at least 3 times the area of the inner surface, preferably at least 4 times the area of the inner surface, such as 5 times the area of the inner surface. The conductive cooling may be increased significantly by increasing the area of the outer cooling surface in relation to the inner surface of the inner chamber of the beverage container. The inner surface defines the volume of the inner chamber and thereby the amount of beverage to be cooled.
According to a further embodiment of the above aspect of the present invention, the cooling device defining an interior beverage space at least partly enclosed by the outer cooling surface, the interior beverage space defining a transversal dimension between adjacent points of the outer surface, the transversal dimension defining a maximum distance of 2 A. It is contemplated that the cooling device may comprise holes or gaps defining interior beverage spaces. The distance between opposing wall parts of such interior beverage spaces should be such that the distance between adjacent or opposing points on the outer surface should not exceed 2 A, i.e. should be in the order of 1.0 cm-4.0 cm, such as 1.0 cm-3.0 cm, preferably approximately 2.0 cm. In this way be above maximum distance is fulfilled and the temperature gradient is kept high.
According to a further embodiment of the above aspect of the present invention, the outer surface of the cooling device defines a top surface, a bottom surface and a substantially cylindrical surface enclosing the top and bottom surfaces. A cylindrical surface may be preferred due to the simple manufacturing of such surfaces. A cylindrical surface may e.g. be manufactured from a flat cooling device by joining opposing edges to form a tube.
According to a further embodiment of the above aspect of the present invention, the outer surface of the cooling device defines a top surface, a bottom surface and a corrugated surface enclosing the top and bottom surfaces. A corrugated surface, such as a surface having a star shape, will yield a larger outer cooling surface compared to a cylindrical surface. Such corrugated surfaces may be manufactured by folding a flat cooling device.
According to a further embodiment of the above aspect of the present invention, the outer surface of the cooling device defines a top surface, a bottom surface and an intermediate surface enclosing the top and bottom surfaces, the intermediate surface having an annular shape, a helical shape, a helicoid shape or a spiral-shape. Further shapes may have an even larger outer contact cooling surface, however, the manufacturing of such cooling devices may involve some more steps compared to the earlier embodiments. In particular, the last three shapes above involve 3D shaping of the cooling device.
According to a further embodiment of the above aspect of the present invention, the at least two separate substantially non-toxic reactants initially being included in the cooling device are separated from one another by a water soluble membrane and the actuator including a first actuator chamber being filled by water or an aqueous solution equivalent to the beverage. Water is preferred as a constituent of the actuator, since water is non-toxic and cheap. Water will also aid in the mixing of the reactants after activation and thereby allow the reaction to start more quickly than it would without water. Water is also produced as a reaction products of several of the entropy increasing reactions presented herein, and any part of the water soluble membrane not dissolved by the water of the actuator will at least be dissolved by the water being produced as reaction product. The first actuator chamber should initially be separated from the water soluble membrane and from the reactants. The water soluble membrane should be rigid when kept dry and deteriorates when contacting water and may be e.g. starch. Further embodiments are described in the detailed description.
According to a further embodiment of the above aspect of the present invention, the first actuator chamber is flexible, deformable and separated from the water soluble membrane by a pressure activated seal, the cooling device initially being kept at a low pressure and the reaction being initiated when the pressure activated seal being ruptured when the pressure inside the first actuator chamber is increased above a specific high pressure, the low pressure typically being atmospheric pressure or below, the specific high pressure typically being atmospheric pressure or above. The present embodiment is preferred for manual activation, i.e. when the water of the first actuator chamber is being forced into contact with the water soluble membrane by compressing the first actuator chamber. Alternatively, the present embodiment may be used in connection with vacuum containers, which when being opened will be subjected to an increased pressure. Pressure activated seals open when the pressure difference across the seal exceeds a specific value.
According to a further embodiment of the above aspect of the present invention, the first actuator chamber is capable of withstanding pressure variations while the first actuator chamber is closed, the actuator further including a second actuator chamber being filled with a foam generating material, the second actuator chamber being located between the first actuator chamber and the water soluble membrane and separated from the first actuator chamber by a pressure activated seal, the second actuator chamber preferably being separated from the water soluble membrane by one or more pressure activated seals. Capable of withstanding pressure variations should be interpreted to mean that the pressure activated seal should open before any significant deformation of the first actuator chamber occurs. The foam generator allows the water to reach the water soluble membrane independently of the orientation of the actuator since the foam will fill the complete first and second actuator chambers and propagate towards the water soluble membrane. The foam is aqueous and will thus dissolve the water soluble membrane. Preferably, a weaker pressure activated seal is used between the foam generator and the water soluble membrane, which seal will break at least by the pressure generated by the foam.
According to a further embodiment of the above aspect of the present invention, the beverage is a carbonated beverage and the first actuator chamber is filled by gasified water or a gasified aqueous solution equivalent to the beverage, typically constituting carbonated water, the cooling device initially being kept at a high pressure and the reaction being initiated when the pressure activated seal being ruptured when the pressure outside of the first actuator chamber is decreased below a specific low pressure, the high pressure typically being the pressure of the carbonated beverage such as 2-3 bars whereas the specific low pressure typically being atmospheric pressure. The present embodiment is preferred for automatic activation when opening containers containing carbonated beverage, i.e. when the water of the first actuator chamber is being forced into contact with the water soluble membrane by releasing a pressure initially subjected to the first actuator chamber. Gasified water, and in particular carbonated water having the same carbonisation as the beverage, will respond to temperature variation in a similar way as the beverage. In this way it is avoided that the actuator is activated by temperature variations. When the beverage container is opened the pressure inside the container decreases while the pressure inside the first actuator chamber remains constant, thus causing the pressure activated seal to open.
According to a further embodiment of the above aspect of the present invention, the first actuator chamber comprises a substantially rigid ampoule being encapsulated within the second actuator chamber. The first actuator chamber may preferably be a substantially rigid ampoule being capable of withstanding pressure variations and which ampoule is completely contained within the second actuator chamber. The ampoule may e.g. be made of thin glass.
According to a further embodiment of the above aspect of the present invention, the pressure activated seal comprises a burst membrane or alternatively a plug, advantageously a plug of liquid metal such as alloys including Gallium and/or Indium. A small plug of Gallium and/or Indium alloys may be used to ensure a proper seal between the first and second actuator chambers.
According to a further embodiment of the above aspect of the present invention, the water soluble membrane is configured in a layered structure or alternatively in a honeycomb structure or yet alternatively as a coating. It may be preferred to arrange the reactants in an pre-mixed configuration in order for the entropy increasing reaction to start quicker.
According to a further embodiment of the above aspect of the present invention, the cooling device is manufactured at least partly of plastic foils. It is currently preferred to make the cooling device at least partly of plastic foils, preferably laminated plastic foils. In this way the cooling device may be deformed in order to achieve a suitable outer cooling surface fitting within the beverage container.
The above objects together with numerous other objects which will be evident from the below detailed description of preferred embodiments of the cooling device according to the present invention are according to a first aspect of the present invention obtained by a cooling device, preferably a cooling bag, cooling rod or cooling container,
It is contemplated that the above cooling device may be provided as a stand-alone part which may be used as a cooling bag or cooling stick for cooling a variety of different objects, some of which are mentioned in the appending points. Such cooling bag may constitute an alternative to the use of ice cubes, since the cooling efficiency of the cooling device will be approximately that of ice.
The above objects together with numerous other objects which will be evident from the below detailed description of preferred embodiments of the cooling device according to the present invention are according to a further aspect of the present invention obtained by a method of producing a cooling device according to any of the points 52-78 including the steps of arranging:
It is contemplated that the above method may be used to produce the cooling device according to the present invention in a continuous process. It is understood by the skilled person that the above method may be varied according to the specific embodiments described below.
The above objects together with numerous other objects which will be evident from the below detailed description of preferred embodiments of the cooling device according to the present invention are according to a further aspect of the present invention obtained by a cooling device, preferably a cooling bag, cooling rod or cooling container,
The above cooling device is capable of assuming three stages with a two step activation procedure being a non-armed state, an armed state and an activated state. Initially, the cooling device is assuming the non-armed state. In the non-armed state the cooling device may be handled in the normal working environment, i.e. about 20 degrees centigrade at atmospheric pressure, without being activated. In this way the cooling device may be manufactured at a remote location and shipped to the location in which it is to be installed, e.g. the brewery. During installation of the cooling device in a beverage container, e.g. in connection with flushing, filling, pasteurizing or any other activity being carried out after or just before capping of the beverage container, the cooling device is armed by rupturing the second membrane such that the chemical activator is pressurized, e.g. by a sudden increase in pressure. The pressurising of the chemical activator is preferably a slow chemical reaction such that a premature activation is avoided. Preferably, the chemical activator constitutes water and the constituent constitutes bicarbonate and citric acid, such that after arming the outer chamber is filled with carbonated water having the same or slightly lower pressure compared to the beverage. It is understood that the same result is achieved by having one of bicarbonate and citric acid already mixed with the water in the outer chamber. When the beverage container is opened, the pressure outside the outer chamber will fall, and the first membrane of the outer chamber will rupture to release the chemical activator, e.g. water, into the reactants which will start the entropy-increasing reaction.
The invention and its many advantages will be described in more detail below with reference to the accompanying schematic drawings, which for the purpose of illustration show some non-limiting embodiments and in which:
The figures illustrate numerous exemplary embodiments of a cooling device according to the present invention.
The pressure space 32 is separated from the water chamber 44 by a flexible diaphragm 30. The flexible diaphragm 30 has a funnel shape and extends from a rounded circumferential reinforcement bead 34 constituting the periphery of the flexible diaphragm 30 to a circular wall 40 constituting the centre of the flexible diaphragm 30. The circular wall 40 separates the pressure space 32 from the main reactant chamber 28. The rounded circumferential reinforcement bead 34 is positioned juxtaposed to a washer 36, which seals the rounded circumferential reinforcement bead to the top 24. The water chamber 44 is separated from the main reactant chamber 28 by a rigid cup-shaped wall 38 extending from the top 24 inwards and downwards. The flexible diaphragm 30 comprises a circumferential gripping flange 42 extending downwards at the circular wall 40. The circumferential gripping flange 42 grips around the end of the cup-shaped wall 38, thus sealing the water chamber 44 from the main reactant chamber 28.
The cooling device 20I is prepared by filling the main reactant chamber 28 with the granulate reactants 29 and filling the water chamber 44 with water, then the top 24 is attached and sealed to the cooling device 20I. Subsequently, the beverage can 12 is filled with beverage, pressurised and sealed by the lid 16. The pressure in the beverage can 12 ensures that the cooling device 20I is not activated, since equal pressure is maintained inside the beverage can 12 and inside the cooling device 20I.
The granulate reactants 29 have a core and a coating which is completely covering the core. The granulate reactants 29 are divided up in two types: one type granulate reactants 29 has a coating of a first reactant designated 29A and a core of a second reactant designated 29B, and another type granulate reactants 29 has a coating of the first reactant designated 29A and a core of a third reactant designated 29C.
In the second close-up view showing the lower part of the reactant chamber 28 the chemical reaction cannot initiate, since the cores 29B and 29C cannot interact with each other. In the first close-up view showing the upper part of the reactant chamber 28 the granulate reactants 29 are subjected to water, and the coating 29C begins to deteriorate causing all three reactants 29ABC to mix and react with each other.
The reactant B and C may initially react and produce a reaction product which is pacified by reacting with reactant A.
The gripping member 83 and the separation element 84 are preferably made of substantially rigid plastics. The gripping member 83 comprise gripping elements which may interlock with corresponding beads on the separation element 83.
In an alternative embodiment the above drink stick 180 may have a conical shape and being used together with an ice mould for instant manufacture of ice cubes by inserting the activated drink stick into the water filled ice mould. Alternatively, the drink stick may have a cubic shape for direct usage as an ice cube in drinks etc.
It is contemplated that the efficiency of the above self-cooling beverage containers and cooling devices are strongly dependent on the heat transfer properties (heat transfer factor) of the cooling device. The heat transfer factor may be modified by changing the geometry, in particular the surface area in beverage contact, of the cooling device, e.g. by providing metal fins onto the cooling device, the heat transfer factor may be increased, thus the cooling efficiency is increased. Consequently, by encapsulating the cooling device in e.g. Styrofoam or a hydrophobic material, the heat transfer factor may be reduced, i.e. the cooling efficiency is decreased. Alternatively, a catalyser may be used for increasing the efficiency of the chemical cooling reaction, or an selective adsorption-controlling agent may be used for reducing the efficiency of the chemical cooling reaction.
It is further contemplated that the entire cooling device may be of flexible material, such as rubber or plastics, and itself constitute a flexible diaphragm.
A variant of the cooling device may be activated by pulling a string connected to a mixing member through the cooling device.
The cooling device shaped as a pipe within a pipe to cool a beverage flowing through the inner pipe with reaction compartments in the space between the inner pipe and the outer pipe.
The cooling device shaped so as to be mountable around a tapping line for cooling beverage running through the tapping line.
The cooling device may have a breakable seal to avoid accidental activation.
The cooling device containing an arming device, the arming device comprising a membrane permeable to the beverage, a saturated salt solution and a non-permeable membrane separating the salt solution from the interior of the cooling device. Upon submersion of the cooling device in the container the water from the beverage enters through the permeable membrane by osmosis into the saturated salt solution which increases in volume thus exerting pressure on the membrane which is transmitted to the interior of the cooling device which results in increased interior pressure which can be used to activate the reaction as described above.
In
Provided the ambient temperature is substantially constant and above a certain lower limit, the heater unit 210 may be omitted, as the inner chamber of the refrigerator cabinet 202 is permanently cooled to a temperature slightly below the ambient temperature. As the inner temperature of the refrigerator cabinet 202 is set at a specific thermostatically controlled temperature, each of the beverage cans 204 may contain a cooling device implemented in accordance with the teachings of the present invention for providing a cooling within a fairly short period of time, such as a period of time of a few minutes, e.g. 1-5 min., preferably approximately 2 min. from the temperature at which the beverage cans are stored within the refrigerator cabinet 202 to a specific cooling temperature, such as a temperature of 5° C.
The refrigerator cabinet 202 shown in
By the provision of a thermostatically controlled refrigerator cabinet 202, in which the individual beverage cans 204 are stored at a preset and constant temperature, preferably slightly below the ambient temperature, the overall consumption of electrical energy from the main supply is dramatically reduced as compared to a conventional beverage can dispenser, in which the beverage cans are all cooled to the specific low temperature of use, i.e. a temperature of e.g. +5° C. for providing to the user a beverage can of a convenient cooled beverage. By the reduction of the cooling to a temperature at or slightly below the ambient temperature, only a fraction of the electrical power consumption is to be used by the beverage dispensing system according to the present invention as shown in
In
The refrigerator system 200′ is similar to the refrigerator system 200 of
By cooling the individual beverage cans contained within the refrigerator cabinet or within a conventional fridge as described above to a specific and preset temperature, the cooling device included in the individual beverage can and implemented in accordance with the teachings of the present invention may be designed to provide a preset and accurate cooling of the individual beverage can from the temperature within the refrigerator cabinet to the temperature at which the user is to drink or pour the beverage from the beverage can.
The following
The cooling deviceI further comprises an actuator 312. The actuator 312 comprises a first actuator chamber 314 and a second actuator chamber 318. The walls of the first actuator chamber 314 should be non-flexible, i.e. capable of withstanding pressure variations generated by temperature variations without deforming. The first actuator chamber 314 is filled with carbonated water 316 having a carbonization level corresponding to the carbonization of the beverage inside the beverage container. The beverage is consequently a carbonate beverage such as beer, soda, cola, tonic or the like. The pressure inside the first actuator chamber 314 should correspond to the pressure inside the filled and sealed beverage container together with which the cooling device 300I is to be used. The pressure inside the first actuator chamber 314 therefore is about 2-3 bar in room temperature. The first actuator chamber 314 is located adjacent the second actuator chamber 318. The second actuator chamber 318 is separated from the first actuator chamber 314 by a burst membrane 322. The burst membrane 322 may be a film of plastic or metal which is intended to break or rupture when the pressure difference across the membrane exceeds a predetermined value. The second actuator chamber is filled by a foam generator 320. The foam generator 320 is preferably provided in the form of a granulate. The foam generator 320 should be a substance which when mixed with water generates a substantial amount of aqueous foam. Example of such material is NaC12H23SO4. Further examples are NaC12H23SO3 and NaC12H23C6H4SO3. The first actuator chamber 314 and the second actuator chamber 318 have the same elevated pressure. The carbonate water 316 should be in equilibrium with the beverage. The second reactant chamber 306 is located adjacent the first reactant chamber 302 and the second reactant chamber 308. The second actuator chamber 318 further comprises an optional separation membrane 324 which is located adjacent the water soluble membrane 310. The separation membrane 324 separates the second actuator chamber 318 and the first and second reactant chambers 302, 306 and thereby prevents any mixing of the reactants 304, 308 and the foam generator 320. The separation membrane 324 is a burst membrane which may be weaker than the above-mentioned burst membrane 322. In alternative embodiments the separation membrane 324 is a water soluble membrane similar to the water soluble membrane 310. It is contemplated that in some embodiments the water soluble membrane 310 and the separation membrane 324 may be constituted by a single common water soluble membrane.
The cooling device 300I shown in
The two reference numerals 300 and 301 for the cooling device are merely used to distinguish between the aspects relating to the internal working principle of the cooling device and the outer contact cooling surface of the cooling device, respectively.
It is contemplated that all of the cooling devices 300 may be provided in all of the above-mentioned cooling device shapes 301.
Inside the filling station 354 a cooling device 300 is located fixated within a guide tube 356. The guide tube 356 holds the legs of the support in a contracted state, which corresponds to the width of the opening of the beverage container 334. A lid 336 is located above the cooling device 300.
The actuator 312 is located near one edge of the cooling device 300I, at which end no reactants are provided. The first foil 358 and the second foil 360 also cover the actuator 312 located near one edge of the cooling device 300I. The actuator 312 comprises the second actuator chamber 318 which is filled by foam generator 320. The second actuator chamber 318 is separated from the first and second reactants 304, 308 and from the water soluble membrane 310 by a separation membrane 324, constituting a weak burst membrane. The second actuator chamber is further separated from the first actuator chamber 314 by a burst membrane 322. The first actuator chamber 314 is filled by carbonated water 316 having a carbonization pressure substantially being equal to that of carbonated beverage. The first actuator chamber 314 is covered by a first reinforcing foil and an opposite second reinforcing foil 462, 464 in order to increase the stiffness of the first actuator chamber 314 such that the first actuator chamber 314 is less flexible and may withstand higher pressures without deforming compared to the rest of the cooling device 300I.
The burst membranes may be achieved by allowing the welds between the first and second activator chambers 314, 318 and between the second activator chamber 318 and the water soluble membrane 310 will have predetermined breaking points which will open during activation. Such predetermined breaking points may be achieved by welding of two materials which are not fully compatible, i.e. which form a weld having less strength than the surrounding foil material. A first reinforcing foil and a second reinforcing foil may optionally be put on top of the first foil 358 and the second foil 360. Alternatively, the foils 358360 may be pre-reinforced at the location of the first actuator chamber.
The cooling device 300V further comprises an actuator 312IV. The actuator 312IV comprises a first actuator chamber 314IV and a second actuator chamber 31e. The first actuator chamber 314IV is separated from the common reaction chamber 380 by a wall having a predetermined breaking point 386, or alternatively a wall having a burst membrane. The first actuator chamber 314IV is filled with non carbonated water 316′ and may optionally include a foam generator 320 such as a surfactant. The foam generator 320 should be a substance which, when mixed with water generates, a substantial amount of aqueous foam. Example of such material is NaC12H23SO4. Further examples are NaC12H23SO3 and NaC12H23C6H4SO3. The water 316 may further include a gelling agent, a coating or a constituent exhibiting low solubility in water in order to slow down the reactions and/or solution of the chemical constituents included in the cooling device. Constituents exhibiting low solubility in water agents are: one of calcium carbonate, iron carbonate, strontium carbonate and an acid exhibiting low solubility such as propanoic acid, buten acid, penten acid, alanine, leucine. Gelling agents may include carboxymethyl cellulose (CMC), hydroxyethyl cellulose (HEC), hydroxypropylmethyl cellulose (HPMC), methylcellulose (MC), gelatine, locust, bean gum, possibly combined with xanthangum.
The second actuator chamber 318IV is separated from the first actuator chamber 314IV by a piercable burst membrane 322′. The piercable burst membrane 322′ may be a film of plastic or metal which is intended to break or rupture when the pressure difference across the membrane exceeds a predetermined value. Optionally, the second actuator chamber 318IV comprises a piercing element 382 directed towards the piercable burst membrane 322′ in the form of a sharp point which is intended to be driven into the piercable burst membrane 322′ when difference across the membrane exceeds a predetermined value. It is understood that any of the previous actuators 312′-312′″ may comprise a piercing element as well in order to achieve a more secure and predetermined breaking pressure of any burst membrane. The second actuator chamber is filled by a CO2 generating constituent 384, such as a mixture of citric acid and bicarbonate. Optionally, the above mentioned gelling agent and/or foam generator is included in the second actuator chamber 318IV.
A hot roller designated the reference numeral 370′ is thereafter welding the first and second foils 358′, 360′ together to form an enclosed package. The roller 370′ is shaped in order to not put an excessive pressure onto the actuator 312V in order to avoid a premature activation of the cooling device. Optionally, a cutter 396 is cutting the foils into strips each constituting a set of cooling devices 388.
Although the invention has above been described with reference to a number of specific and advantageous embodiments of beverage containers, beverage cans, bottles, cooling devices, dispensing and cooling systems etc., it is to be understood that the present invention is by no means limited to the above disclosure of the above described advantageous embodiments, as the features of the above-identified embodiments of the self-cooling container and also the features of the features of the above described embodiments of the cooling device may be combined to provide additional embodiments of the self-cooling container and the cooling device. The additional embodiments are all construed to be part of the present invention. Furthermore, the present invention is to be understood encompassed by any equivalent or similar structure as described above and also to be encompassed by the scope limited by the below points characterising the present invention and further the below claims defining the protective scope of the present patent application. It is understood by the skilled person that any of the actuator 314-314IV may be used together with any of the cooling devices 300I-300V. Further, it is contemplated that other reactants that those described above may be used, such as a reaction between strontiumhydroxide, hexamethyltetramin and optionally urea, or, strontium hydroxide, guanidine and urea. Further it is contemplated that other additives that those described above may be used.
1. A container for storing a beverage, said container having a container body and a closure and defining an inner chamber, said inner chamber defining an inner volume and including a specific volume of said beverage,
2. The container according to point 1, said actuator including a pressure transmitter e.g. a gas permeable membrane or a flexible membrane for transmitting a pressure increase within said inner chamber to said cooling device for initiating said reaction or alternatively for transmitting a pressure drop within said inner chamber to said cooling device for initiating said reaction.
3. The container according to point 1, said actuator including a mechanical actuator for initiating said reaction between said at least two separate, substantially non-toxic reactants.
4. The container according to any of the points 1-3, said reactants being contained within separate compartments within said cooling device separated by a breakable, dissolvable or rupturable membrane caused to be broken, dissolved or ruptured by said actuator, or alternatively separated by a displaceable plug.
5. The container according to point 4, said actuator including a membrane breaker or piercer for breaking or piercing said membrane.
6. The container according to any of the points 3-5, said actuator being accessible from the outside relative to said container and preferably being activated through said closure.
7. The container according to any of the points 1-6, said non-reversible, entropy-increasing reaction producing a volumetric change from said at least two separate, substantially non-toxic reactants to said substantially non-toxic products, a volumetric change of no more than ±5%, such as preferably no more than ±4%, further preferably no more than ±3%, or alternatively said cooling device being vented to the atmosphere for allowing any access gas reduced in said non-reversible, entropy-increasing reaction to be vented to the atmosphere.
8. The container according to any of the points 1-7, said at least two separate, substantially non-toxic reactants being present as separate granulates or present as at least one granulate and at least one liquid or present as separate liquids.
9. The container according to point 8, said granulate or said granulates being prevented from reacting through one or more external coatings such as a coating of starch, a soluble plastics coating or the like, said one or more external coatings being dissolvable by water or an organic solvent preferably a liquid such as a water soluble coating, or alternatively said granulate or said granulates being prevented from reacting by being embedded in a soluble gel or foam.
10. The container according to any of the points 1-9, said cooling device further including a chemical activator such as water, an organic solvent, such as alcohol, propylene glycol or acetone.
11. The container according to point 9, said liquid activator further serving as a reaction-controlling agent such as a selective adsorption-controlling agent, or a retardation temperature setting agent.
12. The container according to any of the preceding points, said container body comprising a beverage keg of polymeric or metallic material having a volume of 3-50 litres, said keg being either collapsible or rigid, and said closure being a keg coupling.
13. The container according to any of the preceding points, said container body comprising a bottle of glass or polymeric material, said bottle having a volume of 0.2-3 liters, and said closure being a screw cap, crown cap or stopper.
14. The container according to any of the preceding points, said container body comprising a beverage can and a beverage lid of metallic material, preferably aluminum or an aluminum alloy, said can having a volume of 0.2-1 liters, and said closure being constituted by an embossing area of said beverage lid.
15. The container according to any of the preceding points, said container comprising a bag, preferably as a bag-in-box, bag-in-bag or bag-in-keg.
16. The container according to any of the preceding points, said container comprising guiding elements for guiding the flow of beverage from said container body.
17. The container according to point 16, said guiding elements serving to guide the flow of the beverage via said cooling device towards said closure.
18. The container according to any of the points 1-17, wherein said cooling device is located within said container.
19. The container according to any of the points 1-17, wherein said cooling device is located outside said container.
20. The container according to any of the preceding points, wherein said container body constitutes a double walled container constituting an inner wall and an outer wall, the cooling device being located between the inner and outer wall
21. The container according to any of the preceding points, said container further comprising a pressure generating device either accommodated within said container or connected to said container via a pressurization hose, said pressure generating device preferably comprise a carbon dioxide generating device for pressurization of said beverage in said beverage container.
22. The container according to any of the preceding points, said container further comprising a tapping line and a tapping valve for selectively dispensing beverage from said beverage container.
23. The container according to any of the preceding points, wherein said beverage container is filled with carbonated beverage such as beer, cider, soft drink, mineral water, sparkling wine, or alternatively non-carbonated beverage such as fruit juice, milk products such as milk and yoghurt, tap water, wine, liquor, ice tea, or yet alternatively a beverage constituting a mixed drink.
24. The container according to any of the preceding points 1-23, wherein said cooling device is accommodated inside the beverage container before filling the beverage into the beverage container.
25. The container according to any of the points 1-23, said container comprising, wherein said cooling device forms an integral part of the beverage container.
26. The container according to any of the points 1-23, wherein said cooling device constitutes a part of the top of the beverage container, alternatively a part of the wall or bottom of the beverage container.
27. The container according to any of the points 1-23, wherein said cooling device is fastened onto the base of the beverage container, alternatively the wall of the container, yet alternatively the top of the container.
28. The container according to any of the points 1-23, wherein said cooling device constitute a widget, which is freely movable within the container.
29. The container according to any of the points 1-28, said at least two separate, substantially non-toxic reactants comprising one or more salt hydrates, preferably inorganic salt hydrates deliberating in said non-reversible, entropy-increasing reaction a number of free water molecules.
30. The container according to point 29, said one or more salt hydrates being selected from salt hydrates of alkali metals, such as lithium, sodium and potassium, and salt hydrates of alkaline earth metals, such as beryllium, calcium, strontium and barium, and salt hydrates of transition metals, such as chromium, manganese, iron, cobalt, nickel, copper, and zinc, and aluminium salt hydrates and lanthanum salt hydrates, preferably LiNO3.3H2O, Na2SO4.10H2O (Glauber salt), Na2SO4.7H2O, Na2CO3.10H2O, Na2CO3.7H2O, Na3PO4.12H2O, Na2HPO4.12H2O, Na4P2O7.10H2O, Na2H2P2O7.6H2O, NaBO3.4H2O, Na2B4O7.10H2O, NaClO4.5H2O, Na2SO3.7H2O, Na2S2O3.5H2O, NaBr.2H2O, Na2S2O6.6H2O, K3PO4.3H2O, preferably MgCl2.6H2O, MgBr2.6H2O MgSO4.7H2O, Mg(NO3)2.6H2O, CaCl2.6H2O, CaBr2.6H2O, Ca(NO3)2.4H2O, Sr(OH)2.8H2O, SrBr2.6H2O, SrCl2.6H2O, Sr(NO3)2.4H2O, SrI2.6H2O, BaBr2.2H2O, BaCl2.2H2O, Ba(OH)2.8H2O, Ba(BrO3)2.H2O, Ba(ClO3)2H2O, CrK(SO4)2.12H2O, MnSO4.7H2O, MnSO4.5H2O, MnSO4.H2O, FeBr2.6H2O, FeBr3.6H2O, FeCl2.4H2O, FeCl3.6H2O, Fe(NO3)3.9H2O, FeSO4.7H2O, Fe(NH4)2(SO4)2.6H2O, FeNH4(SO4)2.12H2O, CoBr2.6H2O, CoCl2.6H2O, NiSO4.6H2O, NiSO4.7H2O, Cu(NO3)2.6H2O, Cu(NO3)2.3H2O, CuSO4.5H2O, Zn(NO3)2.6H2O, ZnSO4.6H2O, ZnSO4.7H2O, Al2(SO4)3.18H2O, AlNH4(SO4)2.12H2O, AlBr3.6H2O, AlBr3.15H2O, AlK(SO4)2.12H2O, Al(NO3)3.9H2O, AlCl3.6H2O and/or LaCl3.7H2O.
31. A method of providing a container including a beverage of a first temperature constituting a specific low temperature such as a temperature of approximately 5° C., said container having a container body and a closure and defining an inner chamber, said inner chamber defining an inner volume and including a specific volume of said beverage,
32. A system for providing a container including a beverage of a first temperature constituting a specific low temperature such as a temperature of approximately 5° C., the system comprising:
33. A cooling device for use in or in combination with a container for storing a beverage, said container having a container body and a closure and defining an inner chamber, said inner chamber defining an inner volume and including a specific volume of said beverage,
34. The cooling device according to point 33, said actuator including a pressure transmitter e.g. a gas permeable membrane or a flexible membrane for transmitting a pressure increase within said inner chamber to said cooling device for initiating said reaction or alternatively for transmitting a pressure drop within said inner chamber to said cooling device for initiating said reaction.
35. The cooling device according to point 33, said actuator including a mechanical actuator for initiating said reaction between said at least two separate, substantially non-toxic reactants.
36. The cooling device according to any of the points 33-35, said reactants being contained within separate compartments within said cooling device separated by a breakable, dissolvable or rupturable membrane caused to be broken, dissolved or ruptured by said actuator, or alternatively separated by a displaceable plug.
37. The cooling device according to point 36, said actuator including a membrane breaker or piercer for breaking or piercing said membrane.
38. The cooling device according to any of the points 33-37, said actuator being accessible from the outside relative to said container and preferably being activated through said closure.
39. The cooling device according to any of the points 33-38, said non-reversible, entropy-increasing reaction producing a volumetric change from said at least two separate, substantially non-toxic reactants to said substantially non-toxic products, a volumetric change of no more than ±5%, such as preferably no more than ±4%, further preferably no more than ±3%, or alternatively said cooling device being vented to the atmosphere for allowing any access gas reduced in said non-reversible, entropy-increasing reaction to be vented to the atmosphere.
40. The cooling device according to any of the points 33-39, said at least two separate, substantially non-toxic reactants being present as separate granulates or present as at least one granulate and at least one liquid or present as separate liquids.
41. The cooling device according to point 40, said granulate or said granulates being prevented from reacting through one or more external coatings such as a coating of starch, a soluble plastics coating or the like, said one or more external coatings being dissolvable by water or an organic solvent preferably a liquid such as a water soluble coating, or alternatively said granulate or said granulates being prevented from reacting by being embedded in a soluble gel or foam.
42. The cooling device according to any of the points 33-41, said cooling device further including a chemical activator such as water, an organic solvent, such as alcohol, propylene glycol or acetone.
43. The cooling device according to point 42, said liquid activator further serving as a reaction-controlling agent such as a selective adsorption-controlling agent, or a retardation temperature setting agent.
44. The cooling device according to any of the preceding points, said container body comprising a beverage keg of polymeric or metallic material having a volume of 3-50 liters, said keg being either collapsible or rigid, and said closure being a keg coupling.
45. The cooling device according to any of the points 33-44, said at least two separate, substantially non-toxic reactants comprising one or more salt hydrates, preferably inorganic salt hydrates deliberating in said non-reversible, entropy-increasing reaction a number of free water molecules.
46. The cooling device according to point 45, said one or more salt hydrates being selected from salt hydrates of alkali metals, such as lithium, sodium and potassium, and salt hydrates of alkaline earth metals, such as beryllium, calcium, strontium and barium, and salt hydrates of transition metals, such as chromium, manganese, iron, cobalt, nickel, copper, and zinc, and aluminium salt hydrates and lanthanum salt hydrates, preferably LiNO3.3H2O, Na2SO4.10H2O (Glauber salt), Na2SO4.7H2O, Na2CO3.10H2O, Na2CO3.7H2O, Na3PO4.12H2O, Na2HPO4.12H2O, Na4P2O7.10H2O, Na2H2P2O7.6H2O, NaBO3.4H2O, Na2B4O7.10H2O, NaClO4.5H2O, Na2SO3.7H2O, Na2S2O3.5H2O, NaBr.2H2O, Na2S2O6.6H2O, K3PO4.3H2O preferably MgCl2.6H2O, MgBr2.6H2O MgSO4.7H2O, Mg(NO3)2.6H2O, CaCl2.6H2O, CaBr2.6H2O, Ca(NO3)2.4H2O, Sr(OH)2.8H2O, SrBr2.6H2O, SrCl2.6H2O, Sr(NO3)2.4H2O, SrI2.6H2O, BaBr2.2H2O, BaCl2.2H2O, Ba(OH)2.8H2O, Ba(BrO3)2.H2O, Ba(ClO3)2.H2O, CrK(SO4)2.12H2O, MnSO4.7H2O, MnSO4.5H2O, MnSO4.H2O, FeBr2.6H2O, FeBr3.6H2O, FeCl2.4H2O, FeCl3.6H2O, Fe(NO3)3.9H2O, FeSO4.7H2O, Fe(NH4)2(SO4)2.6H2O, FeNH4(SO4)2.12H2O, CoBr2.6H2O, CoCl2.6H2O, NiSO4.6H2O, NiSO4.7H2O, Cu(NO3)2.6H2O, Cu(NO3)2.3H2O, CuSO4.5H2O, Zn(NO3)2.6H2O, ZnSO4.6H2O, ZnSO4.7H2O, Al2(SO4)3.18H2O, AlNH4(SO4)2.12H2O, AlBr3.6H2O, AlBr3.15H2O, AlK(SO4)2.12H2O, Al(NO3)3.9H2O, AlCl3.6H2O and/or LaCl3.7H2O.
47. The cooling device according to any of the points 43-46, said device being configured as a metal can of the size of a beverage can, or configured as a cooling box for receiving a number of beverage containing containers, or configured as a cooling stick to be positioned in a beverage bottle or the like, or configured as a sleeve to be positioned encircling a part of a container, e.g. the neck of a bottle or the body part of a metal can or bottle or configured as a part of the closure or cap of a bottle.
48. A container for storing a beverage, said container having a container body and a closure and defining an inner chamber, said inner chamber including a specific volume of said beverage, said container further including a cooling device defining a volume not exceeding 30% of said volume of said beverage, said cooling device including at least two separate, substantially non-toxic reactants causing when reacting with one another a non-reversible, entropy increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor 3, preferably at least a factor 4, and further preferably at least a factor 5 larger than the stoichiometric number of said reactants, said at least two separate substantially non-toxic reactants initially being included in said cooling device separated from one another and being caused to react with one another when opening said container for causing said non-reversible entropy increasing reaction and generating a cooling of said liquids by at least 20° C. within a period of time of no more than 5 min., preferably 3 min., further preferably 2 min. and providing said cooling lasting for at least 10 min. preferably at least 15 min, further preferably at least 20 min.
49. The container according to point 48, further having any of the features of the container according to any of the points 2-30.
50. A cooling device for use in or in combination with a container for storing a beverage, said container having a container body and a closure and defining an inner chamber, said inner chamber defining an inner volume and including a specific volume of said beverage, said cooling device further defining a volume not exceeding 30% of said volume of said beverage, said cooling device including at least two separate, substantially non-toxic reactants causing when reacting with one another a non-reversible, entropy increasing reaction producing substantially non-toxic products in a stoichiometric number at least a factor 3, preferably at least a factor 4, and further preferably at least a factor 5 larger than the stoichiometric number of said reactants, said at least two separate substantially non-toxic reactants initially being included in said cooling device separated from one another and being caused to react with one another when opening said container for causing said non-reversible entropy increasing reaction and generating a cooling of said liquids by at least 20° C. within a period of time of no more than 5 min., preferably 3 min., further preferably 2 min. and providing said cooling lasting for at least 10 min. preferably at least 15 min, further preferably at least 20 min.
51. The cooling device according to point 50, further having any of the features of the cooling device according to any of the points 33-47.
52. A container for storing a beverage, said container having a container body and a closure and defining an inner chamber, said inner chamber defining an inner volume and including a specific volume of said beverage,
53. The container according to point 52, wherein any point within said bottom half space defining said maximum distance A to an adjacent point on said outer cooling surface, or, preferably, wherein any point within said inner chamber defining said maximum distance A to an adjacent point on said outer cooling surface.
54. The container according to any of the points 52-53, wherein said inner chamber defines an inner surface, said outer cooling surface defining an area being at least 3 times the area of said inner surface, preferably at least 4 times the area of said inner surface, such as 5 times the area of said inner surface.
55. The container according to any of the points 52-54, wherein said cooling device defining an interior beverage space at least partly enclosed by said outer cooling surface, said interior beverage space defining a transversal dimension between adjacent points of said outer surface, said transversal dimension defining a maximum distance of 2 A.
56. The container according to any of the points 52-55, wherein said outer surface of said cooling device defines a top surface, a bottom surface and a substantially cylindrical surface enclosing said top and bottom surfaces.
57. The container according to any of the points 52-55, wherein said outer surface of said cooling device defines a top surface, a bottom surface and a corrugated surface enclosing said top and bottom surfaces.
58. The container according to any of the points 52-55, wherein said outer surface of said cooling device defines a top surface, a bottom surface and an intermediate surface enclosing said top and bottom surfaces, said intermediate surface having an annular shape, a helical shape, a helicoid shape or a spiral-shape.
59. The container according to any of the points 52-58, wherein said at least two separate substantially non-toxic reactants initially being included in said cooling device are separated from one another by a water soluble membrane and said actuator including a first actuator chamber being filled by water or an aqueous solution equivalent to said beverage.
60. The container according to point 59, wherein said first actuator chamber is flexible, deformable and separated from said water soluble membrane by a pressure activated seal, said cooling device initially being kept at a low pressure and said reaction being initiated when said pressure activated seal being ruptured when the pressure inside said first actuator chamber is increased above a specific high pressure, said low pressure typically being atmospheric pressure or below, said specific high pressure typically being atmospheric pressure or above.
61. The container according to points 59, wherein said first actuator chamber is capable of withstanding pressure variations while said first actuator chamber is closed, said actuator further including a second actuator chamber being filled with a foam generating material, said second actuator chamber being located between said first actuator chamber and said water soluble membrane and separated from said first actuator chamber by a pressure activated seal, said second actuator chamber preferably being separated from said water soluble membrane by one or more pressure activated seals.
62. The container according to point 61, wherein said beverage is a carbonated beverage and said first actuator chamber is filled by gasified water or a gasified aqueous solution equivalent to said beverage, typically constituting carbonated water, said cooling device initially being kept at a high pressure and said reaction being initiated when said pressure activated seal being ruptured when the pressure outside of said first actuator chamber is decreased below a specific low pressure, said high pressure typically being the pressure of_the carbonated beverage such as 2-3 bars whereas said specific low pressure typically being atmospheric pressure.
63. The container according to any of the points 61-62, wherein said first actuator chamber comprises a substantially rigid ampoule being encapsulated within said second actuator chamber.
64. The container according to any of the points 60-63, wherein said pressure activated seal comprises a burst membrane or alternatively a plug, advantageously a plug of liquid metal such as alloys including Gallium and/or Indium.
65. The container according to any of the points 59-64, wherein said water soluble membrane is configured in a layered structure or alternatively in a honeycomb structure or yet alternatively as a coating.
66. The container according to any of the preceding points, wherein said cooling device is manufactured at least partly of plastic foils.
67. A cooling device, preferably a cooling bag, cooling rod or cooling container,
68. The cooling device according to point 67, wherein said at least two separate substantially non-toxic reactants initially being included in said cooling device separated from one another by a water soluble membrane and said actuator including a first actuator chamber being filled by water or an aqueous solution equivalent to said beverage.
69. The cooling device according to any of the points 67-68, wherein said first actuator chamber is flexible, deformable and separated from said water soluble membrane by a pressure activated seal, said cooling device initially being kept at a low pressure and said reaction being initiated when said pressure activated seal being ruptured when the pressure inside of said first actuator chamber is increased above a specific high pressure, said low pressure typically being atmospheric pressure or below, said specific high pressure typically being atmospheric pressure or above.
70. The cooling device according to any of the points 67-68, wherein said first actuator chamber is capable of withstanding pressure variations while said first actuator chamber is closed, said actuator further including a second actuator chamber being filled with a foam generating material, said second actuator chamber being located between said first actuator chamber and said water soluble membrane and separated from said first actuator chamber by a pressure activated seal, said second actuator chamber preferably being separated from said water soluble membrane by one or more pressure activated seals
71. The cooling device according to point 70, wherein said first actuator chamber is filled by gasified water, such as carbonated water, said cooling device initially being kept at a high pressure and said reaction being initiated when said pressure activated seal being ruptured when the pressure outside of said first actuator chamber is decreased below a specific low pressure, said high pressure typically being the pressure of the carbonated beverage such as 2-3 bar whereas said specific low pressure typically being atmospheric pressure.
72. The cooling device according to any of the points 69-71, wherein said pressure activated seal comprises a burst membrane.
73. The cooling device according to any of the points 69-71, wherein said pressure activated seal comprises a plug, advantageously a plug of liquid metal such as alloys including Gallium and/or Indium.
74. The cooling device according to any of the points 70-73, wherein said first actuator chamber comprises a substantially rigid ampoule located encapsulated within said second actuator chamber.
75. The cooling device according to any of the points 68-74, wherein said water soluble membrane is configured in layered structure or alternatively in a honeycomb structure or yet alternatively as a coating.
76. The cooling device according to any of the points 68-74, wherein said cooling device is manufactured of plastic foils.
77. The cooling device according to any of the points 67-76, wherein said cooling device constitutes a cooling bag suitable for the treatment of sports injuries, or, a cooling rod for use in drinks, or, a cooling container for prolonging the pot life of two component glue or paint.
78. A method of producing a cooling device according to any of the points 52-78 including the steps of arranging:
79. A cooling device, preferably a cooling bag, cooling rod or cooling container,
80. The cooling device according to point 79, wherein said second membrane is ruptured when the pressure outside said inner chamber is increased above a predetermined value.
81. The cooling device according to point 79, wherein said second membrane is ruptured when the temperature of said second membrane is increased above or decreased below a predetermined value.
82. The cooling device according to any of the points 79-81, wherein said first membrane is ruptured when the pressure outside said outer chamber is decreased below a specific value.
83. The cooling device according to any of the points 79-82, wherein said reactants are separated by a soluble membrane.
84. The cooling device according to any of the points 79-83, wherein said inner chamber and/or outer chamber further including a gelling agent.
85. The cooling device according to any of the points 79-84, wherein said inner chamber and/or outer chamber further including a foaming agent.
85. The cooling device according to any of the points 79-85, wherein said inner chamber and/or outer chamber further including an agent for reducing solubility of said constituent.
86. The cooling device according to any of the points 79-85, wherein said constituent comprise a mixture of citric acid and bicarbonate.
87. The cooling device according to any of the points 79-86, wherein said chemical activator comprise water.
88. The cooling device according to any of the points 79-87, wherein said second membrane is being ruptured by a piercing element.
89. The cooling device according to any of the points 79-87, wherein said first membrane is being ruptured at a predetermined breaking points.
90. The cooling device according to any of the points 79-89, wherein said reactants and said constituent are being provided in the form of granulates.
91. The cooling device according to any of the points 79-90, wherein said cooling device is made of a plastic laminate.
92. A set of cooling devices including a number, such as two or three cooling devices according to any of the points 79-91, said cooling devices being foldably connected for fitting inside a beverage container.
93. A beverage container including a beverage and a cooling device according to any of the point 79-91 or a set of cooling devices according to point 92.
94. The beverage container according to point 93, wherein said second membrane is ruptured in connection with the carbon dioxide flushing of said container, with the filling of said beverage into said beverage container or with the pasteurization of said beverage.
95. The beverage container according to any of the points 93-94, wherein said first membrane is ruptured in connection with opening said beverage container.
96. A method of producing a cooling device, said method comprising the steps of:
97. A method of producing a cooling device, said method comprising the steps of:
98. The method according to point 96, wherein said method further comprising:
99. The method according to any of the points 96-98, wherein said method further comprising any of the features of points 79-91.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10166014.0 | Jun 2010 | EP | regional |
| 10388012.6 | Oct 2010 | EP | regional |
The present application is a Continuation of co-pending International Application No. PCT/EP2011/059902, filed Jun. 15, 2011, the disclosure of which is incorporated herein by reference. This application is also a continuation-in-part of co-pending U.S. patent application Ser. No. 13/133,609, filed Jun. 8, 2011, entitled A SELF COOLING CONTAINER AND A COOLING DEVICE, which is a national phase filing, under 35 U.S.C. §371(c), of International Application No. PCT/EP2009/066703, filed Dec. 9, 2009, the disclosures of which are incorporated herein by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2011/059902 | Jun 2011 | US |
| Child | 13133609 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 13133609 | Jul 2011 | US |
| Child | 13710281 | US |
