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Title:
COOLING AGENT FOR COLD PACKS AND FOOD AND BEVERAGE CONTAINERS
Document Type and Number:
WIPO Patent Application WO/2017/040432
Kind Code:
A1
Abstract:
Safe, stable, non-toxic and recyclable cooling agent compositions comprising solid particulate compounds undergo an endothermic process when mixed with water such that the resulting mixture is useful for cooling surfaces, liquids and solids. The mixtures include ammonium nitrate in an amount of at least 45 wt% of the mixture. Total nitrogen -containing salts exclusive of phosphates are present in an amount less than 68% by weight of the composition. A phosphate salt is also present in an amount as needed to stabilize the composition against detonation. A balance of additional salts is formulated to provide the mixture with a cooling capacity of at least 240 kJ/kg of the mixture.

Inventors:
LEAVITT DAVID (US)
BERGIDA JOHN (US)
Application Number:
PCT/US2016/049331
Publication Date:
March 09, 2017
Filing Date:
August 29, 2016
Export Citation:
Click for automatic bibliography generation   Help
Assignee:
FROSTY COLD LLC (US)
International Classes:
A61F7/10; C09K5/18; F25D5/02
Foreign References:
US20120138848A12012-06-07
US20120138319A12012-06-07
US20050250879A12005-11-10
US8623315B22014-01-07
US6783799B12004-08-31
Attorney, Agent or Firm:
CLEVELAND JR., Dan (Suite 2400Kansas City, Missouri, US)
Download PDF:
Claims:
CLAIMS

1. A cooling agent composition comprising:

a nitrogen-containing salt material present in an amount ranging from 45% to 68% by weight of the composition exclusive of water or other liquid,

the nitrogen-containing salt material including at least in part ammonium nitrate; the nitrogen-containing salt material being exclusive of phosphate salts ;

a phosphate salt including an amount of phosphate sufficient to stabilize the ammonium nitrate from detonation; and

a balance of salts formulated to provide the composition with a cooling capacity of at least 240 kJ/kg of the mixture.

2. The salt mixture of claim 1, wherein the phosphate salt is monobasic ammonium phosphate.

3. The salt mixture of claim 2, wherein the ammonium nitrate is present in an amount greater than 50 wt%.

4. The salt mixture of claim 1, wherein the ammonium nitrate is present in an amount greater than 60 wt%.

5. The salt mixture of claim 1, wherein the nitrogen-containing salt material includes up to 15 wt% potassium nitrate.

6. The salt mixture of claim 1, further comprising less than 1 wt% fumed silica and less than 1 wt% of a coloring additive.

7. The salt mixture of claim 1, wherein the balance of salts includes a chloride salt and provides the mixture with a cooling capacity of at least 245 kJ/kg.

8. The salt mixture of claim 1, wherein the balance of salts provides the mixture with a cooling capacity of at least 250 kJ/kg.

9. The salt mixture of claim 1, wherein the balance of salts provides the mixture with a cooling capacity of at least 255 kJ/kg. 10 In an evaporative cooling system, the improvement comprising:

a salt-based cooling agent composition according to claim 1 in crystalized form on an evaporative support, the salt material having a capacity to provide an endothermic effect to enhance cooling when mixed with water;

means for mixing the cooling agent composition with water to provide the endothermic effect; and

means for recycling the salt material for recrystallization on the evaporative support.

11. The evaporative cooling system of claim 10, constructed and arranged for the cooling of a building area selected from the group consisting of a house, a data center, a computer room, and an industrial facility.

12. The evaporative cooling system of claim 10, constructed and arranged as a cooling tower selected from the group consisting of a counterflow tower and a crossflow tower.

13. The evaporative cooling system of claim 10, constructed and arranged for the cooling of bearings on a solar wind turbine.

14. The evaporative cooling system of claim 10, constructed and arranged for the cooling of a solar panel.

15. The evaporative cooling system of claim 10, wherein the cooling agent composition has a dual use as a fertilizer material according to an industry recognized blend of PK materials.

16. A closed loop cooling system, comprising:

a cooling agent composition according to claim 1;

a mixing chamber operably configured for combining the cooling agent composition with water to provide coolant an endothermic effect;

refrigeration coils configured to receive coolant from the mixing chamber and to discharge spent coolant after the coolant has cooled the refrigeration coils; and a plurality of membrane separation units constructed as a closed-loop system utilizing a plurality of membrane separation technologies for recycle of the spent coolant to produce discrete flow streams as recovered water and salt concentrate; and

recycle pathways for introducing the discrete flow streams to the mixing chamber.

17. The evaporative cooling system of claim 16, wherein the membrane separation technologies include forward osmosis in combination with a second membrane separation technology selected from the group consisting of ultrafiltration, reverse osmosis, nanofiltration, graphene, molecular sieve, and combinations thereof.

18 The evaporative cooling system of claim 17, wherein the second membrane separation technology includes ultrafiltration.

19. A wearable cold pack comprising:

a wearable article of clothing formed with a reservoir for retention of liquid; and a cooling agent composition including a salt according to claim 1 mixed with water in the reservoir.

20. The wearable cold pack of claim 19 constructed and arranged as an article selected from the group consisting of a joint wrap, head wrap, neck wrap, and a shoulder wrap.

21. The wearable cold pack of claim 19 constructed and arranged as of a helmet, neck wrap; personal cooling vest; personal cooling with cold fluid circulation; and a medical bandage.

22. The wearable cold pack of claim 19 constructed and arranged as one of a self- cooling can, self-cooling bottle; multi-pack beverage holder; medical instant cold pack; instant cold cooler with evaporative re-use of the salt; ice cream maker; bottle insert; keg; evaporative cooling unit; fishing tray; just-add-water cold pack; closed-loop refrigerator; instant slushy maker; flexible sports medical insert; cold therapy with compression binding; vaccine / cold chain pack; personal cooling neck wrap; personal cooling vest; personal cooling with cold fluid circulation for race car drivers; personal cooling with cold fluid circulation for hazmat suits and the like; medical emergency cooling for IV administration; body temp, head trauma, or heat exhaustionold cushions or pads for use in pools, sunbathing, wheelchairs, stadiums or other outdoor seating; boxed wine with instant cooling and equipped for evaporative reuse for second pour; trauma cold wraps for knees, leg, vest, blanket; bike helmet with comfort and/or emergency cooling; boot or shoe cooling inserts;

23. In a closed loop refrigeration system, the improvement comprising:

a salt-based cooling agent composition according to claim 1 in concentrated form in a closed loop refrigeration cycle,

the cooling agent composition having a capacity to provide an endothermic effect to enhance cooling when mixed with water; means for mixing the cooling agent composition with water to provide the endothermic effect;

means for recycling the salt material for recrystallization by transfer across a membrane to remove excess water;

means for drawing the excess water from the cooling agent through the membrane; and

means for recovering the excess water for reuse by mixing the water with

concentrated cooling agent.

24. The closed loop refrigeration system of claim 23, constructed and arranged for the cooling of a building area selected from the group consisting of a house, a data center, a computer room, and an industrial facility.

25. The closed loop refrigeration system of claim 23, constructed and arranged as a cooling tower selected from the group consisting of a counterflow tower and a crossflow tower.

26. The closed loop refrigeration system of claim 23, constructed and arranged for the cooling of bearings on a solar wind turbine.

27. The closed loop refrigeration system of claim 23, constructed and arranged for the cooling of a solar panel.

28. The closed loop refrigeration system of claim 23, constructed and arranged for the cooling of food, beverages and drugs medicines.

29. The closed loop refrigeration system of claim 23, wherein the cooling agent composition has a dual use as a fertilizer material according to an industry recognized blend of PK materials.

30. In combination, an article of manufacture that contains the cooling agent composition of claim 1 as the coolant, wherein the article of manufacture is selected from the group consisting of:

a self-cooling can, self-cooling bottle; multi-pack beverage holder; medical instant cold pack; instant cold cooler with evaporative re-use of the salt; ice cream maker; bottle insert; keg; evaporative cooling unit; fishing tray; just-add-water cold pack; closed-loop refrigerator; instant slushy maker; flexible sports medical insert; cold therapy with compression binding; vaccine / cold chain pack; personal cooling neck wrap; personal cooling vest; personal cooling with cold fluid circulation for race car drivers; personal cooling with cold fluid circulation for hazmat suits and the like; medical emergency cooling for IV administration; body temp, head trauma, or heat exhaustion; phase change material; data center with built-in cooling, brewery cooling with evaporative salt recycle; wind turbine or other critical equipment with difficult to reach areas in need of cooling; solar panels cooling; aluminum forms for pouring and curing of concrete; food and beverage serving trays, bowls, mats, and pitchers; koozies for cans or bottles; cold cushions or pads for use in pools, sunbathing, wheelchairs, stadiums or other outdoor seating; boxed wine with instant cooling and equipped for evaporative reuse for second pour; trauma cold wraps for knees, leg, vest, blanket; emergency facility cooling; bike helmet with comfort and/or emergency cooling; boot or shoe cooling inserts; shipping containers; rural or remote community coolers; coolant regeneration-crystallization setup; ice cream or smoothie in a cup; keeping ice cream colder for longer periods of time, building cooling; vaccine storage with evaporative recycle to provide perpetual cooling with no power source; and zero power cooler.

Description:
COOLING AGENT FOR COLD PACKS AND FOOD AND BEVERAGE

CONTAINERS

BACKGROUND OF THE INVENTION

1. Field of the Invention

[0001] This invention relates generally to cooling agents or compositions that can be used to cool surfaces, liquids and solids when activated upon mixing with water and more particularly to cooling agents that are effective, resistant to combustion, insensitive to detonation, non-toxic and recyclable as a balanced NPK fertilizer.

2. Description of the Art

[0002] The present invention relates to compositions which produce an

endothermic reaction when mixed with water, and which are non-toxic, non-explosive and can be recycled as a balanced NPK fertilizer when no longer useful as a cooling agent.

Although not so limited, the invention has particular utility when used as a cooling agent in therapeutic cold packs for the treatment of sprains and injuries; for chilling of beverages and packaged foods; and for other applications where it is desirable to cool surfaces, fluids or objects.

[0003] Compositions producing an endothermic effect and devices or containers that utilize such compositions are known in the prior art. Such compositions typically produce their endothermic effect by either chemical reaction or by heat absorbing processes. Examples of endothermic chemical reactions include: the reaction of barium hydroxide octahydrate crystals with dry ammonium chloride with the subsequent evolution of ammonia; the reaction of thionyl chloride with cobalt(II) sulfate heptahydrate; and the reaction of ethanoic acid with sodium carbonate. Examples of such endothermic processes include: melting ice cubes, melting solid salts, evaporating liquid water, making an anhydrous salt from a hydrate and the dissolution of salts in water.

[0004] As a general rule, compositions that undergo endothermic reactions are useful for cooling but often utilize toxic reactants such as cobalt and barium hydroxide or produce noxious and irritating byproducts such as ammonia, or gasses that are difficult to contain and process such as carbon dioxide. Heat-absorbing processes are thus more commonly used to cool substances compared to chemical reactions. With respect to cold packs and beverage coolers, heat-absorbing processes based upon the dissolution of various salts in water are commonly described. Here the selection of a particular material has primarily been based upon the magnitude of its positive enthalpy of solution (heat of solution) and its solubility in water or another solvent whereby the most effective

compositions have the highest positive heat of solution and highest solubility.

[0005] With respect to the above, US Patent No. 1,894,775 disclosed the use of various sodium, potassium and ammonium salt solutions, including sodium acetate, ammonium nitrate and sodium thiosulfate mixed with water, to provide therapeutic cooling in 1933. Subsequently many other patents have disclosed the use of additional compounds along with various wetting and gelling agents and co-solvents other than water to improve the cooling performance of endothermic compositions when applied to cold packs and beverages. As an example, US Patent 3,957,472 describes a chemical heat transfer unit that uses compounds selected from a group that includes ammonium sulfamate, potassium nitrate, ammonium bisulfate, ammonium bromide, ammonium bicarbonate, ammonium iodide, ammonium magnesium selenate, ammonium maganese sulfate, ammonium phosphate dibasic, ammonium potassium tartrate, ammonium salicylate, ammonium sulfate, ammonium sodium sulfate, ammonium thiocyonate, ammonium persulfate, potassium phosphate, potassium sulfate, potassium sodium tartrate, potassium thiocyanate, potassium iodide, potassium chloride, urea, afenil, sodium acetate, sodium citrate, sodium nitrate, sodium thiocyanate, sodium thiosulfate, citric acid, tartaric acid, ferric ammonium sulfate and thiourea. In another example, US Patent No. 4,081,256 describes an endothermic

composition and cold pack whereby urea, hydrated sodium acetate, potassium chloride, potassium nitrate, ammonium chloride, and guar gum are blended together to extend the cooling life of the cold pack. In still other examples, US Patent No. 4,010,620 utilizes ammonium chloride and ammonium nitrate for maximum cooling effect; US Patent No. 6,233,945 describes an extended life cold pack that uses ammonium nitrate, ammonium sulfamate, ammonium nitrite, ammonium iodide, ammonium bromide, sodium chloride, sodium nitrate, sodium nitrite, sodium carbonate, sodium bicarbonate, potassium nitrate, potassium nitrite, urea, methylurea, and combinations thereof; US Patent No. 5,429,762 discloses a cooling agent consisting of one or more of a group comprised of disodium hydrogen phosphate, sodium dihydrogen phosphate, tri sodium phosphate, sodium

ammonium hydrogen phosphate, diammonium hydrogen phosphate, and hydrates thereof; and US Patent No. 4,010,620 describes a cooling system that utilizes sodium nitrate, ammonium nitrate, ammonium thiocyanate, potassium thiocyanate, and ammonium nitrate individually or in combination.

[0006] A review of the prior art reveals that, although a wide variety of chemical compositions have been disclosed, only a select few are preferred based upon performance as a cooling agent.

[0007] Chemical cooling agents also suffer from the stigma of being a wasteful product that is not easily reused or recycled. Many of the endothermic compounds and compositions shown in Table 1 or disclosed in the prior art are classified as hazardous substances or are harmful to the environment if disposed in an improper or imprudent manner after they no longer have utility as a cooling agent.

[0008] For all of the above reasons, cooling agents and compositions described in the prior art have had limited commercial success with the possible exception of cold pack applications. The most effective commercialized cold pack applications, however, utilize ammonium nitrate or mixtures of ammonium nitrate and urea and are susceptible to increased regulation and subject to restrictions on use, and may not be available for use in consumer products in the future.

SUMMARY

[0009] It is a principal object of this invention to provide safe, non-toxic and recyclable cooling compositions comprising solid particulate compounds that undergo an effective endothermic process when mixed with water such that the resulting mixture is useful for cooling surfaces, liquids and solids. Because ammonium nitrate and urea are already in commercial use for cold pack applications but are in danger of being rendered unmarketable because of concerns about safety and explosivity, it is also an object of the invention to provide safe and non-explosive endothermic compositions that contain these compounds and the other strongly oxidizing cooling agents described herein. It is also an object of this invention to provide endothermic compositions that can be recycled for a beneficial use as balanced NPK fertilizer when they are no longer useful as cooling agents.

[00010] Although not prescribed for various cooling agents, methods for improving the safety of ammonium nitrate for use as a fertilizer are described in the prior art. For example, US Patent No. 3,366,468 disclosed a method for manufacturing desensitized ammonium nitrate having lowered flammability and reduced sensitivity to explosive detonation. Here various ammonium phosphate compounds are incorporated together with ammonium nitrate during process of manufacturing ammonium nitrate fertilizer. The resultant ammonium nitrate fertilizer containing 1% to 5% ammonium phosphate was de- sensitized to explosion and was rendered non-explosive when containing more than 5% ammonium phosphate. US Patent No. 6, 130,139 discloses the use of ammonium phosphate compounds including ammonium polyphosphate as a barrier coating applied to ammonium nitrate prills that reduces the efficacy of the prills as oxidizing agents.

[00011] The present invention combines various ammonium phosphate compounds that are known to suppress flame formation and explosivity and act as fire retardants with the preferred and strongly oxidizing compounds described in Table 1 such that these compounds are rendered non-explosive and resistant to combustion. Unlike the methods disclosed in the prior art, the ammonium phosphate compounds used in this invention do not have to be incorporated with ammonium nitrate or other oxidizing agents during the manufacture of fertilizer or used to coat prills in order to be effective. The selected compounds can simply be blended together to form an intimate mixture when used to prepare a cooling composition. Compositions used in this invention that contain ammonium phosphate compounds along with strongly oxidizing endothermic compounds remain safe and non-explosive even though blended with carbon containing compounds that are known to form explosive mixtures with compounds such as ammonium nitrate. This safety feature is useful for compositions that are used in cold packs, since such cold pack products often contain carbon-based gels and thickening agents such as guar gum, xanthates and carboxymethylcellulose.

[00012] When prepared in this manner, the ammonium phosphate compounds, and especially ammonium polyphosphate, also improve the stability and lengthen the shelf-life of mixtures of urea and ammonium nitrate. Mixtures of urea and ammonium nitrate are destabilized by acidic hydrolysis of the urea to form free water which can prematurely solubilize ammonium nitrate during storage. Ammonium polyphosphate is hydroscopic and is thought to act as a scavenger of any free water that might form during the storage of ammonium nitrate/urea mixtures, thus preventing the water from dissolving ammonium nitrate. Urea is also destabilized by other endothermic compounds besides ammonium nitrate when mixed together, and ammonium polyphosphate can also be an effective stabilizer of such mixtures.

[00013] With the current social and political trends favoring sustainability and protection of the environment, chemical products that are non-toxic and can be reused or recycled or disposed of without contributing to pollution and waste are greatly preferred over non-recyclable products. The primary emphasis in the prior art is the disclosure of endothermic compounds that are effective cooling agents with little regard for toxicity of the compounds or their reuse or disposal. The use of a spent cooling agent as fertilizer or plant growth regulator is sometimes mentioned but only as a secondary benefit, primarily with respect to cooling agents that utilize urea, ammonium nitrate, potassium nitrate, ammonium sulfate with attention paid to nitrogen-containing compounds that can be used as nitrogen- containing fertilizers.

[00014] In this present invention, effective endothermic compositions are described that can be reused as a balanced fertilizer containing nitrogen (N), phosphorus (P), and potassium(K) because only balanced fertilizers contain all of the essential primarily nutrients necessary for plant growth. Such compositions have greater residual value compared to solutions that contain only nitrogen or only nitrogen and potassium and are more useful to the end-user and more likely to be reused and recycled instead of being disposed of as a waste material when no longer effective as a coolant.

[00015] Compositions in accordance with this invention thus comprise cooling agents that always include one or more compounds from a group consisting of endothermic compounds shown in Table 1 that contain potassium; one or more compounds from a group of endothermic compounds shown in Table 1 that contain nitrogen; and at least one compound from a group consisting of ammonium phosphate, diammonium phosphate, ammonium polyphosphate, ammonium pyrophosphate and ammonium metaphosphate such that the compound or mixture of compounds in this group is at least 1% by weight of the final composition. The compositions may also include one or more compounds from a group comprising sodium perchlorite (NaC10 3 ), sodium perchlorate (NaC10 4 ), sodium bromate dehydrate (NaBr2H 2 0), sodium acetate trihydrate (NaC 2 H 3 Cv3H 2 0), sodium thiosulfate (Na 2 S 2 0 3 ), sodium thiosulfate pentahydrate (Na 2 S 2 0 3 5H 2 0), trisodium phosphate (Na 3 P0 4 ), and sodium bicarbonate (NaHC0 3 ,) and about 0.5 to 1% thickening agent comprising guar gum, xanthate gum, carboxymethylcellulose, or mixtures thereof. The compositions when mixed with water at around 20°C attain a temperature of around 10°C or less within 60 seconds after mixing and can be recycled for use as a balanced NPK fertilizer when no longer useful as a coolant.

[00016] According to one embodiment, a salt mixture is formulated to contain a maximum of 68% nitrogen-containing salts, such as ammonium nitrate or potassium nitrate, where the 68% cap excludes nitrogen-containing salts that are phosphates. The 68% cap reduces the oxidation performance of the salt mixtures to acceptable levels under Test Series 0.1 : Test for Oxidizing Solids method, as described in the United Nations'

"Recommendations on the Transport of Dangerous Goods Manual of Tests and Criteria, Fifth Revised Edition. The nitrogen-containing salts are preferably nitrates. Ammonium nitrate is particularly preferred.

[00017] Where the nitrogen-containing salts are nitrates, the weight percentage of nitrogen-containing salts is suitably from 45% to 68%, more preferably from 50% to 68%,,, and even more preferably from 55% to 68%.. The 68% cap may be reduced to 60%, 55% or 45% with a corresponding loss of cooling capacity that, practically speaking, does not significantly impair cooling capacity of the salt mixture in the intended environments of use. As used herein, the term "dry salt mixture" includes salts that are combined in dry form, as well as similar salts that have been mixed in water and similar salts that are rearranged in dry form once the water is subsequently evaporated. Preferably, ammonium nitrate comprises at least 45%), 50%, 55% or 60% by weight of the composition exclusive of water or other liquid.

[00018] . In one aspect, a balance of salts is added to formulate the mixture in a manner imparting a cooling capacity of at least 240 kJ/kg of the mixture when the mixture is in dry form. Chloride salts, such as sodium chloride, are preferred for use in the balance of salts.

[00019] In one aspect, the phosphate salt may be monobasic ammonium phosphate. [00020] In one aspect, the ammonium nitrate is present in an amount greater than 60 wt%.

[00021] In one aspect, the balance of salts includes up to 15 wt% potassium nitrate.

[00022] In one aspect, the salt mixture further includes fumed silica in an effective amount to prevent caking but less than 1 wt% Oof the mixture, and/or an effective amount of a coloring additive, such as blue dye, this being also less than 1 wt% of the mixture.

[00023] In one aspect, the mixture described above may be formulated to provide a cooling capacity of at least one of 240 kJ.kg, 245 kJ.kg, 250 kJ/kg or 255 kJ/kg.

[00024] In one aspect, a cooling system, such as an evaporative cooling system, may be improved by the use of these cooling agent compositions. A salt-based cooling agent composition is crystalized onto an evaporative support. The salt material has a capacity to provide an endothermic effect that enhances cooling when mixed with water. A means, such as a mixer, sprayer or nozzle, is provided for mixing the cooling agent composition with water to provide the endothermic effect. A means is also provided for recycling the salt material for recrystallization on the evaporative support. This second means may be a controller that governs operation of the mixer sprayer or nozzle to enhance the crystallization process under the influence of flowing air.

[00025] In one aspect, the cooling agent composition may be primarily ammonium nitrate that has been stabilized against detonation by the addition of an effective amount of phosphate material. There may be added also additional salts to form an industry recognized NPK blend, such that the cooling agent composition at the end of its use may be discarded by use as a fertilizer. Cooling agent compositions of this nature, when in substantially complete crystalized form, may be formulated to provide at least about 120 Btu/lb from the effects of endothermic activity when mixed with water.

[00026] In one aspect, the cooling system may be constructed and arranged for the cooling of a building area selected from the group consisting of a house, a data center, a computer room, and an industrial facility. Alternatively, the evaporative cooling may be constructed and arranged as a cooling tower selected from the group consisting of a counterflow tower and a crossflow tower.

[00027] In one aspect, the cooling system may be constructed and arranged for specialty uses, such as emergency use or permanent use in the cooling of bearings on a solar wind turbine. These bearings and an associated braking system may otherwise overheat, especially in the event of high winds. The cooling system may be constructed and arranged for the cooling of a solar panel, or an industrial cooling tower.

[00028] In other aspects, the cooling agent composition is provided in a wearable cold pack. This may be formed as a wearable article of clothing formed with a reservoir for retention of liquid. The cooling agent composition including salt mixed with water provides cooling activity in the reservoir. The wearable cold pack may be, for example, constructed and arranged as such articles a joint wrap, head wrap, neck wrap, shoulder wrap or helmet.

[00029] In another embodiment, a cooling system, such as a closed loop

refrigeration system, may be improved by the use of these cooling agent compositions. Here a concentrated salt-based cooling agent is utilized within a closed loop endothermic cooling system. The salt material has a capacity to provide an endothermic effect that enhances cooling when mixed with water. When mixed with water the concentrated cooling agent is diluted and is subsequently re-concentrated by a means, such as a forward osmosis membrane, in which water is drawn from the concentrated cooling agent by osmotic pressure generated by a draw material which is then diluted by the water. The diluted draw material is then re-concentrated by a means, such as an ultra-filtration membrane or related membrane technologies (i.e. reverse osmosis, nanofiltration, graphene, molecular seives , etc.), and the extracted water is then recombined with the concentrated cooling agent to provide an endothermic effect that enhances cooling when mixed with water. The draw material solution selected for the forward osmosis system must have a high enough osmolality to generate an osmotic pressure sufficiently greater than the osmotic pressure of the diluted cooling agent.

[00030] In one aspect, a salt-based cooling agent composition is crystalized onto an evaporative support. A means, such as a mixer, sprayer or nozzle, is provided for mixing the cooling agent composition with water to provide the endothermic effect. A means is also provided for recycling the salt material for recrystallization on the evaporative support. This second means may be a controller that governs operation of the mixer sprayer or nozzle to enhance the crystallization process under the influence of flowing air.

[00031] In one aspect, the cooling agent composition is provided in a closed loop refrigeration cycle whereby the cooling agent is rendered recyclable and reusable utilizing membrane separation, molecular sieves or other suitable processes to cyclically remove water from the cooling agent and reintroduce water into the concentrated cooling agent to cool the refrigerated fluid flowing through the system.

[00032] In one aspect, These examples show that the dry salt mixtures are rendered stable against detonation if they have at least 10 wt% of a phosphate salt, such as monobasic ammonium phosphate. The dry salt mixtures are formulated against being problematic oxidizers if they contain a maximum of 68 wt% of nitrogen-containing salts, such as ammonium nitrate and/or potassium nitrate. Thus, in combination, the salts preferably have at least 10 wt% of a phosphate salt and 68 wt% or less of a nitrogen-containing salt. . BRIEF DESCRIPTION OF THE DRAWINGS

[00033] Figure 1 shows a cooler that may be used to chill beverages by the endothermic action of a cooling agent composition;

[00034] Fig. 2 is a system schematic drawing of a cooling system utilizing the endothermic action of a cooling agent composition;

[00035] Fig. 3 shows a cooling system utilizing the endothermic action of a cooling agent composition according to one embodiment;

[00036] Fig. 4 shows refrigeration coils that may be used in a cooling system such as that shown in the embodiment of Fig. 3;

[00037] Fig. 5 shows solar panels that may be cooled using refrigeration coils compatible with the embodiment of Fig. 3

[00038] Fig. 6 shows a cooling tower utilizing the endothermic action of a cooling agent composition according to one embodiment;

[00039] Fig. 7 shows a cooling tower utilizing the endothermic action of a cooling agent composition according to one embodiment;

[00040] Fig. 8 shows a distribution basin that may be suitably used in the embodiment of Fig. 7;

[00041] Fig. 9A is a cold pack capable of utilizing the endothermic action of a cooling agent composition according to one embodiment;

[00042] Fig. 9B shows the cooling pack with water and salt constituents mixed to provide endothermic action; [00043] Fig. 10 shows a bicycle helmet with an internal reservoir for receipt of a cooling agent composition according to one embodiment; and

[00044] Fig. 11 shows a closed loop endothermic refrigeration system.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

5 [00045] This is best illustrated by a review of the selected endothermic compounds shown in Table 1.

TABLE 1: SELECTED ENDOTHERMIC COMPOUNDS USEFUL FOR COOLING

SURFACES, SOLIDS AND LIQUIDS

ΚΜη0 4 158.04 1090 43.56 6.3 1.74 4 3 24

K 2 S0 4 174.25 6600 23.8 11.1 1.52 3 2 25

NaF 41.99 52 0.91 4.13 0.09 0 0 25

NaCl 58.44 3000 3.88 359 23.84 12 9 17

NaC10 2 90.44 165 0.33 39 0.14 0 0 25

NaC10 2 -3H 2 0 144.44 165 28.58 39 7.72 13 9 22

NaC10 3 106.44 1200 21.72 101 20.61 25 17 18

NaC10 4 122.44 2100 13.88 201 22.79 18 13 18

NaC10 2 H 2 0 140.44 2100 22.51 201 32.22 26 18 14

NaBr-2H 2 0 138.89 3500 18.64 90.5 12.15 15 11 21

NaBr0 3 150.89 301 26.9 37.4 6.67 12 8 23

NaI-2H 2 0 185.89 4340 16.13 184 15.97 13 9 20

NaI0 3 197.89 180 20.29 9.47 0.97 2 1 25

NaN0 2 68 180 13.89 80.8 16.50 22 15 20

NaN0 3 84.99 3236 20.5 87.6 21.13 27 19 18

NaC 2 H 3 0 2 -3H 2 0 136.08 3530 19.66 85 12.28 16 11 21

Na 2 S 2 0 3 · 5H 2 0 248.17 2300 47.4 79 15.09 20 14 20

NaCN 49 6 1.21 58 1.43 2 2 25

NaCN-2H 2 0 85 6 18.58 82 17.92 24 16 19

NaCNO 65.01 5 19.2 110 32.49 37 26 14

NaCNS 81.05 764 6.83 139 11.71 12 8 21

Na 3 P0 4 163.94 7400 15.9 8.8 0.85 2 1 25

NaHC0 3 83.99 4220 16.7 7.8 1.55 3 2 24

NH 4 C1 53.49 1650 14.78 29.7 8.21 15 11 22

NH 4 C10 4 117.49 100 33.47 20.8 5.93 12 8 23

NH 4 Br 97.94 2700 16.78 78.3 13.42 18 13 21

NH 4 I 144.94 76 13.72 172 16.28 14 10 20

NH 4 I0 3 192.94 500 31.8 182 30.00 25 18 15

NH 4 N0 2 64.04 57 19.25 150 45.09 43 30 10

NH 4 N0 3 80.06 2217 25.69 150 48.13 46 32 9

NH 4 CN 44.06 525 17.57 60 23.93 36 25 17

NH 4 CNS 76.12 954 22.58 144 42.72 42 29 11

(NH 4 ) 3 P0 4 149 3000 14.45 37.7 3.66 6 4 24

CH 3 NH 3 C1 67.52 1600 5.77 30.6 2.61 5 3 24

AgC10 4 207.32 Toxic 7.38 557 19.83 7 5 18

AgN0 2 153.87 Toxic 36.94 4.2 1.01 2 2 25 AgN0 3 169.87 Toxic 22.59 257 34.18 23 16 14

RbC10 4 184.92 3310 56.74 1.3 0.40 1 1 25

RbN0 3 147.47 4625 36.48 44.28 10.95 18 13 21

CsC10 4 232.36 3310 55.44 1.97 0.47 1 1 25

CsN0 3 194.91 1200 40 9.16 1.88 4 3 24

BaCl 2 · 2H 2 0 244.27 118 20.58 31 2.61 5 3 24

MgS04 « 7H20 246.36 2840 16.11 255 16.67 11 8 20

In Table 1, the selected endothermic compounds (solutes) are classified with respect to their toxicity, heat of solution and solubility in water. Toxicity is measured by the oral rat LD 50 value for a compound taken from various toxicological databases or from the Material Safety Data Sheet (MSDS) for the compound or from other indicators of toxicity if LD 50 data isn't available. Compounds with an LD 50 above 1000 are preferred for applications where there is a potential for human and environmental exposure. Heat of solution values are taken from CRC Handbook of Chemistry and Physics, 90th Ed. Solubility values are taken from the Solubility Database shown on the International Union of Pure and Applied Chemistry / National Institute of Standards and Technology website.

[00046] An endothermic process absorbs heat from the environment during the dissolution of the compound in water. The theoretical heat absorbed during the dissolution of compound in 100 gm of water at 25°C in kJ can be calculated from the following equations using the data in the table:

1- [Hs o i] * [moles of solute] = [mass of solution] * C p * [Ti - T 2 ]

where H So i is in kJ/Mol

mass of solution refers to the mass of a saturated solution in 100 gm of water

Cp is assumed to be 4.184 J/g °C

Ti is 20°C

T 2 is the final temperature of the saturated solution

2. Aq = heat absorbed = [mass of solution] * 4.184 * [Ti - T 2 ]

[00047] The theoretical heat absorbed and the final theoretical temperature of the saturated endothermic solutions are shown in the table. [00048] This data was then used to predict the cooling effect of saturated solutions of the various endothermic compounds upon a typical beverage container having a volume of around 12 ounces. For a reference, approximately 60 grams of 200 mesh ammonium nitrate was thoroughly mixed with approximately 50 grams of water in an un-insulated 100 ml sealed container which was then placed in a larger sealed un-insulated container having a volume of around 360 ml that contained around 255 ml of water. The larger sealed container had approximately the same dimensions and surface area as a typical 12 ounce beverage can. After around 30 seconds, the temperature of the saturated solution in the 100 ml container attained -7 °C from an initial temperature of 25°C and after around 3 minutes the temperature of the water in the 360 ml container attained around 9°C from an initial temperature of 25°C. This reference test indicated that the theoretical change in temperature of a saturated solution of ammonium nitrate was approximately 30% more than the measured change in temperature due to heat losses from the 100 ml container while the container was being mixed prior to placing it in the 360 ml container that contained the water. A similar calculation showed that heat losses from the un-insulated 360 ml container was around 50%. The heat loss factors were then used to determine the predicted temperature changes shown in the table for the various saturated salt solutions and for a 360 ml container filled with 255 ml of liquid exposed to the various saturated salt solutions. The predicted results were then used to rate the performance of the selected endothermic compounds in terms of their performance as a cooling agent.

[00049] The compounds predicted in the table to be most useful as cooling agents should show at least a 10°C reduction in temperature when dissolved in water and include urea (CO( H 2 ) 2 ), potassium fluoride dihydrate (KF 2(H 2 0), potassium chloride (KC1), potassium bromide (KBr), potassium iodide (KI), potassium nitrite (KN0 2 ), potassium nitrate (KN0 3 ), potassium thiosulfate pentahydrate (K 2 S 2 0 3 5H 2 0), potassium cyanide (KCN), potassium cyanate (KCNO), potassium thiocyanide (KCNS), sodium perchlorite (NaC10 3 ), sodium perchl orate (NaC10 3 ), sodium perchlorite dihydrate (NaC10 2 H 2 0), sodium bromide dihydrate (NaBr2H 2 0), sodium nitrite (NaN0 2 ), sodium nitrate (NaN0 3 ), sodium acetate trihydrate (NaC 2 H3C 3H 2 0), sodium thiosulfate pentahydrate

(Na 2 S 2 0 3 5H 2 0), sodium cyanide dihydrate (NaCN 2H 2 0), sodium cyanate (NaCNO), ammonium chloride ( H,C1), ammonium bromide ( H 4 Br), ammonium iodide ( H 4 I), ammonium iodate ( H 4 IO 3 ), ammonium nitrite ( H 4 NO 2 ), ammonium nitrate ( H 4 NO 3 ), ammonium cyanide ( H 4 CN), ammonium thiocyanide ( H 4 CNS), silver nitrate (AgN0 3 ) and rubidium nitrate (RbN0 3 ).

[00050] Of this group, potassium fluoride dehydrate, potassium nitrite, potassium thiosulfate pentahydrate, potassium cyanide, potassium cyanate, potassium thiocyanide, sodium nitrite, sodium cyanide dihydrate, sodium cyanate, ammonium iodide, ammonium iodate, ammonium nitrite, ammonium cyanide, ammonium thiocyanide, and silver nitrate have LD 50 values below 1000 or are toxic and are less than desirable for use in a consumer- oriented product such as a cold pack or beverage coolant. Potassium nitrite, potassium nitrate, sodium perchlorite, sodium perchlorate, sodium perchlorite dihydrate, sodium nitrite, sodium nitrate, ammonium nitrite and ammonium nitrate are all strong oxidizing agents and thus are reactive and have a tendency to promote combustion or are unstable during storage. Urea is also described as being unstable when mixed or blended with a wide variety of other endothermic compounds including ammonium nitrate, and blends of urea and other compounds that are described in the prior art as having synergistic coolant properties are rendered ineffective by a reduced shelf-life. Potassium nitrite, potassium nitrate, sodium nitrate, ammonium nitrite and ammonium nitrate are also capable of detonation and explosion, with ammonium nitrate having a particularly bad reputation as the explosive of choice for weapons of terror even though it is one of the most effective cooling agents disclosed in Table 1 and in the prior art. Mixtures of ammonium nitrate and urea are also commonly formulated together to make powerful commercial explosives.

[00051] A preferred composition within the broad ranges set forth above, which exhibits an optimum combination of properties, consists essentially of compounds or blends of compounds: (1) such that the mixture contains nitrogen, phosphorus and potassium ( PK); (2) such that the mixture shows at least a 14°C drop in temperature when mixed with water; and (3) that are non-toxic or have an LD 50 greater than 1000. In one aspect, the preferred composition is thus selected from a group consisting of urea, potassium nitrate, potassium thiosulfate pentahydrate, sodium nitrate, ammonium nitrate, ammonium phosphate ammonium polyphosphate, and combinations thereof. . In parts by weight, the preferred composition contains about 50 to 95 parts ammonium nitrate; about 0 to 50 parts urea; about 0 to 50 parts sodium nitrate; about 4 to 30 parts potassium nitrate or potassium thiosulfate pentahydrate; and between 1 and 10 parts ammonium phosphate or ammonium polyphosphate. Preferably about 90 parts by weight water are added to this composition to initiate the endothermic reaction.

[00052] Although the particle size of the various components of the composition can vary depending upon the application, the components must be blended together to create an intimate mixture whereby the particles of ammonium phosphate or polyphosphate are in very close contact or proximity to the particles of urea, potassium nitrate, sodium nitrate and ammonium nitrate. To that end, the components of the composition are typically co-milled together to create an intimate mix having an average particle size of at least 100 mesh and preferably greater than 200 mesh.

[00053] For example, a cooling agent composition that is useful for cold packs contains 50 parts ammonium nitrate, 40 parts urea, 4 parts potassium nitrate, 5 parts ammonium polyphosphate and around 1 part guar gum or xanthate powder added as a thickening agent. The mixture of components is co-milled to form a 100 mesh powder that when mixed with around 90 parts water is effective to reduce the temperature of the mixture by around 20°C within 120 seconds after dissolution of the components and can maintain cooling of a surface for at least 15 minutes. The dry-milled cooling agent composition is stable, non-toxic, non-explosive and safe to use as a consumer product. The saturated solution containing the cooling agent composition forms a balanced NPK liquid fertilizer having an NPK ratio of 42-1.4-1.6.

[00054] As another example, a cooling agent composition that is useful for chilling canned or bottled beverages contains 90 parts ammonium nitrate, 5 parts potassium nitrate and 5 parts ammonium phosphate. The mixture of components is co-milled to form a 200 plus mesh powder that when mixed with around 90 parts water is effective to reduce the temperature of the mixture by around 30°C within 60 seconds after dissolution of the components and can be used to rapidly cool a beverage where rapidity of cooling is more important than maintaining a cooling effect. The dry -milled cooling agent composition is non-toxic, non-explosive and safe to use as a consumer product. The saturated solution containing the cooling agent composition forms a balanced NPK liquid fertilizer having an NPK ratio of 32-1.4-2. [00055] The cooling agent composition described above may be used in a variety of applications. In one aspect, Fig. 1 shows a cooler 100 with a plurality of open cylinders 102, 104, 106 for receipt of a beverage, such as beverage 108. Wall 110 is shown with a breakaway section for purposes of illustration to reveal an interior chamber 112 enclosed by shell 114. The shell 114 is preferably made of a waterproof insulating material, such as Styrofoam or plastic encased styrofoam. As shown in Fig. 1, water 116 is being poured through opening 118 for mixing with the cooling agent composition. The mixture is rising to level 120 and will eventually cover the exterior surface of cylinder sleeve 122. The cylinder sleeve 122 may be made, for example, out of plastic that is more conductive to heat than is the shell 114, because it is desirable to enhance heat transfer for purposes of cooling beverages.

[00056] It will be appreciated that cooler 100 is shown as a beverage cooler, but the cylinders 102, 104, 106 may be made with changed dimensions complementary to any number of other items that may require cooling in circumstances, for example, where there may be a lack of refrigeration. The cooler as shown may therefore, be adapted to cool blood, blood plasma, dialysis materials, vaccines, organs for transplant, or food products such as milk or ice cream. The cooler 100 may even be formed as a coolant reservoir for an ice cream maker, or as a slushie or daiquiri maker.

[00057] Fig. 2 shows a cooling system 200 that may be used in applications including food service, commercial refrigeration, chillers for use in machinery or plants, dialysis and medical equipment, dehumidifiers, computers, data centers, or air conditioning units. Valves 202, 204 may be used for selective isolation of corresponding salt water reservoirs 206, 208 on lines 210, 212. Flow through line 214 communicates salt water to membrane filter 216. The membrane filter 216 may be, for example, a Perforene™ filter as produced by Lockheed Martin. This type of filter is capable of separating salts from water in the above-described cooling agent composition for remixing that is later to occur. The membrane filter 216 may include, for example, a perforated graphene sheet supported by a backing sheet 220. In the arrangement shown, deionized water 222 passes through the membrane filter 216 and into line 224. Salt concentrates exit through line 226 under control of valve 228. The salt concentrates may be optionally subjected to a drying unit 230 for more complete drying. This drying unit may be, for example, solar powered, an open air system or one that undergoes the application of heat energy from hydrocarbon fuels. The finished salt concentrates 232 may be conveyed to cooler 234, which is used for purposes described above, then with recycle through line 236 for resupply of salt water 206 in a closed process loop. Alternatively, the recycle may be supplied as salt water 208.

[00058] Fig. 3 shows a forced air cooling system 300, which is formed of a refrigeration unit 302, an evaporative cooling unit 304, and an optional dehumidifier unit 306. A mixer 308 blends a crystalized form of the cooling agent composition 310 with water provided from the dehumidifier unit 306, as described in more detail below. The mixture provides endothermic action where, for example, the crystalized cooling agent composition may provide cooling to the effect of 130 Btu/lb when mixed with water, or another level of cooling depending upon the selected salts. Mixer 308 provides the liquid coolant n mixture to coolant basin 314. A circulating pump 316 circulates the cold liquid mixture from coolant basin 314 through refrigeration coils 318 and then into the evaporative cooling unit 304 through return line 320. A fan 322 circulates air from chamber 324 through coils 318 for provision of cool air 326 to the refrigeration unit 302.

[00059] The return line 320 discharges 328 onto an evaporative support, such as an evaporative cooling pad 330. Fan 332 pulls air 334 across the evaporative cooling pad 330. The evaporative cooling pad 330 is sized to crystallize salts in the water (or other solvent) from discharge 328. The crystallization may be partial or substantially complete. Where, for example, the dried salt composition applied to mixer 308 provides an endothermic effect of 130 Btu/lb, the crystallization on evaporative pad 330 now provides the opposite effect in the amount of 130/lb. This is compensated by the evaporative cooling effect of water volatilizing on the evaporative cooling pad 330. The enthalpy of vaporization of water provides about 970 Btu/lb of water, which overwhelms the heating effect as the salt crystalizes.

[00060] Salts crystallizing on the evaporative cooling pad 330 will eventually clog the pad to impede the flow of air 334 into chamber 324. Periodically then, at time intervals as needed to avoid such clogging, deionized water from a second discharge 335 may be used to clean the evaporative cooling pad 330. A mechanical actuator, such as a roller (not depicted), may be used to enhance solvolysis and/or dislodgement of crystalline salts from the evaporative cooling pad 330. Alternatively, a sonication device (not depicted), may be used to enhance solvolysis and/or dislodgement of crystalline salts from the evaporative cooling pad 330.

[00061] The materials released from the evaporative cooling pad and associated water fall as salt material 310 into coolant basin 314 of the refrigeration unit 302.

[00062] The air 314 in chamber 324 is accordingly cooled and the water content of air 314 is increased by the evaporation process. This cool moist air enters dehumidifier 306. As is known in the art, dehumidifiers may operate on a variety of principles. By way of example, these include mechanical or refrigerative dehumidifiers that drawn air over a refrigerated coil, Peltier heat pumps, adsorption desiccants, and ionic membranes. A preferred form of dehumidifier 306, according to one embodiment, is a membrane compressed air dryer, such as may be purchased on commercial order and the HMD™ or HMM Sweepsaver™ products from SPX/Hankinson International of Ocala Florida. In this type of system, as is known in the art, compressed air may be filtered through a coalescing filter to remove piqued water droplets. The air then passes internally through a system of hollow fibers in one or more membrane bundles. Simultaneously, a portion of dried air is directed over the exterior surfaces of the fibers. To sweep water vapor that has penetrated the fiber membrane. The sweep air absorbs water from the membrane and may be discharged from the system. Alternatively, as depicted in Fig. 3, water drips from the external surfaces and is collected for discharge through recycle line 336. Cool dry air blows through vent 340 and may be used, for example, to cool a house, a data center, a computer room, an operating room, vending machine, or a manufacturing facility. The dehumidifier unit 306 is optional because it will not be necessary or desirable in all instances to dehumidify the air exiting chamber 324.

[00063] The parts of forced air cooling system 300 may be constructed for application-specific uses. By way of example, the refrigeration coils 318 may be specially constructed for niche applications, for example, as shown in Fig. 4. Coils 400 are specially constructed to fit around the bearings of a wind turbine generator . The coils may also have a flattened configuration for use in cooling solar panels 500. In the solar panel application, the excess solar heat advantageously assists in drying salts of the cooling agent composition.

[00064] Fig. 6 is a midsectional view of a counterflow cooling system 600 that may be used as an industrial cooling tower. Dry air 602 enters the system as pulled by fan 604. The dry air 602 passes through a fill material 606 that is wet by the action of spray nozzles 608, 610. This converts the dry air 602 into warm moist air 612. Excess liquid from spray nozzles 608, 610 collects in basin 614 after passing through the fill material 606, having been chilled by the action of water evaporating in the fill material. This liquid is applied to a cooling use 616, such as the cooling of a building, a nuclear reactor, or an electrical generation plant.

[00065] The cooling effect is enhanced by use of the cooling agent composition as described above. The cooling agent is contained in the water emanating from nozzles 608, 610. The spray pattern onto fill material 606 is divided into zones, such as zones A, B, C, D and E. Each zone is allocated a corresponding water source, such as nozzle 610 is allocated to zone A. The nozzles for each zone are selectively activated, for example, under the direction of controller 618, by providing periodic spray bursts or continuous low volume spray, to facilitate drying of the cooling agent composition with resultant salt crystallization on the fill material 606. Then the nozzles may be activated to flush one or more zones to achieve endothermic action by solvolysis of the crystallized salt material. This reduces the temperature of water or other liquid that is collected in the collection basin 614 and applied to cooling use 616. The manner of operation directed by controller 618 may be determined, for example, according to a multivariate correlation relating temperature, air moisture content, salt content, type of salt, time of application, and air flow rate to a desired level of crystallization as determined by empirical data in the intended environment of use. Not all of these variables will be necessary for this correlation, but a plurality of these variables is preferred. Other models relating these variables, such as a neural network or adaptive filter may also be used.

[00066] Fig. 7 is a midsectional view of a crossflow cooling system 700. In this system, hot water 702 enters a distribution basin 704 that controls distribution of water to fil material 706. Fan 708 pulls dry air external across the fill material 706, which is wet with water from the distribution basin 704. This provides evaporative cooling of the water, which passes through fill material 710 under the influence of gravity into collection basin and is delivered to cooling use 714.

[00067] The cooling effect is enhanced by use of the cooling agent composition as described above. The cooling agent is contained in the water emanating from distribution basin 704. As shown in Fig. 8, the distribution basin 704 includes a reservoir 800 for collecting hot water. The reservoir 800 is drained by selective activation of valves 802, 804, 086, 808, which are electronically opened and closed as determined by controller 810. As above, each valve is allocated to a corresponding zone (not depicted) located in the filler material 706 beneath the distribution basin 704. The manner of delivery facilitates drying of cooling agent composition in the water with resultant salt crystallization on the fill material 704. Then respective valves of the distribution basin may be activated to flush one or more zones to achieve endothermic action by solvolysis of the crystallized salt material. This reduces the temperature of water or other liquid that is collected in the collection basin 712 and applied to cooling use 714.

[00068] The manner of operation directed by controller 810 may be determined, for example, according to a multivariate correlation relating temperature, air moisture content, salt content, type of salt, time of application, and air flow rate to a desired level of crystallization as determined by empirical data in the intended environment of use. Not all of these variables will be necessary for this correlation, but a plurality of these variables is preferred. Other models relating these variables, such as a neural network or adaptive filter may also be used.

[00069] Fig. 9A shows a cold pack 900 formed of thermosealed plastic 902 that defines a water pouch 904 and a salt pouch 906. The salt material within salt pouch 906 is a cooling agent composition as described above. A divider 908 separates the water pouch 904 from the salt pouch 906. The divider 908 forms a comparatively weak seal as compared to a perioral seal, such as by being thinner and so also weaker. Either water pouch 904 or salt pouch 906 may be manually squeezed to rupture the divider 908 for mixing of water and salt. Fig. 9B shows the cold pack 900 after activation in this manner, with mixture 910 providing an endothermic reaction for cooling purposes. This cold pack may be used for medical applications, or in the cooling of food and beverage products.

[00070] It will be appreciated that cooling is a function of variables including time. Thus, if salts of the cooling agent composition dissolve too slowly over time, the net cooling effect upon a target object may not be as great as it could be if the salts were to dissolve all at once. It has been discovered that the salt materials dissolve more quickly if a minor amount of water is present with the crystalized salt material. Thus for example, for 1% to 5% by weight of water may be premixed with the salt material to speed solvolysis upon the further addition of water. The amount of water is preferably from 2% to 3% by weight. Thus, the salt material in pouch 906 may have the consistency of a wet sand material. The premix with water does reduce somewhat the endothermic capacity of the salt material, but in many applications results in greater effective cooling by increasing the speed of solvolysis.

[00071] The cold pack 900 is not limited to the shape shown in Figs. 9A and 9B. This structure may be fashioned into a joint wrap, such as a knee or ankle wrap, a head wrap, neck wrap, or shoulder wrap. These devices may be constructed of hollow materials to provide an integral reservoir for retention of the cooling agent composition when mixed as a liquid or, alternatively, the cold pack 900 may be placed into a pouch within these articles of clothing. By way of example, Fig. 10 shows a bicycle helmet 1000 with a pouch 1002 for receipt of cold pack 900. The cold pack 900 does not require divider 908 and may be made to accept the cooling agent composition in crystallized form to which water may be added and sealed for retention by use of a threaded cap or other closure. The location of pouch 1002 is a the back of the neck, but other locations may be used, such as any contact point that may protect the skull in the manner of a water helmet. Bicycle helmets of the prior art are usually filled with styrofoam materials, as is well known, but accordant to the present instrumentalities the styrofoam is replaced with a bladder for retention of a cooling agent composition that is selectively mixed with water to cool the head while cycling.

[00072] Again, as to any of the foregoing embodiments, the cooling agent composition may be provided as a fertilizer blend with NPK content for an intended purpose. Thus, if the salt of the cooling agent composition needs renewal, it is a simple matter to dispose of the old salts by using them as a fertilizer, such as a spray fertilizer. A particularly preferred form of the cooling agent composition for many such uses is ammonium nitrate that has been stabilized against detonation by the addition of phosphate material, such as from 3% to 8% by weight phosphate. To this may be added additional salts to provide a desired NPK blend, such as a 14-7-7 or 12-12-12 blend. However, it is desirable to keep the ammonium nitrate content high, for example, as more than 50% or more than 80% of the composition by weight due to the excellent endothermic capacity of ammonium nitrate, together with the relatively low toxicity of this material. [00073] As shown by the instrumentalities discussed above, various products may be made incorporating a reservoir that contains salt material for cooling action by the addition of water. These products may include, for example, self-cooling cans or bottles; multi-pack beverage holders; medical instant cold packs; instant cold coolers with

evaporative re-use of the salt; ice cream makers; bottle inserts; kegs; evaporative cooling units; fishing trays; just-add-water cold packs; closed-loop refrigeration; instant slushy makers; flexible sports medical inserts; cold therapy with compression binding; vaccine / cold chain packs; personal cooling neck wrap; personal cooling vest; personal cooling with cold fluid circulation for race car drivers or hazmat suits and the like; medical emergency cooling for - IV, body temp, head trauma, heat exhaustion and the like; phase change material such as material that changes phase at -17°F, 0°F, or 28°F; data centers, brewery cooling with evaporative salt recycle; wind turbines or other critical equipment with difficult to reach areas in need of cooling; solar panels cooling; aluminum forms for pouring and curing of concrete; food and beverage serving trays, bowls, mats, pitchers and the like;

koozies for cans or bottles; cold cushions or pads for use in pools, sunbathing, wheelchairs, stadiums or other outdoor seating; boxed wine with instant cooling and equipped for evaporative reuse for second pour; trauma cold wraps for knees, leg, vest, blanket;

emergency facility cooling; bike helmet with comfort and/or emergency cooling; boot or shoe cooling inserts; shipping containers; rural or remote community coolers; coolant regeneration-crystallization setup; ice cream or smoothie in a cup; keeping ice cream colder for longer periods of time, building cooling; vaccine storage with evaporative recycle to provide perpetual cooling with no power source; and zero power cooler.

[00074] Fig. 11 shows a closed loop endothermic cooling system 1100 based upon the use of an endothermic cooling agentl 102, which may be a dry salt or salt concentrate salt solution as described above. The endothermic cooling agent 1102 is mixed with recycled water 1104 in mixing chamber 1106 and immediately supplied heat exchanger 1108, which may be for example refrigeration coils such as the coils of a refrigerator or other cooler, or the coils of an air conditioning unit. This mixing with water 1104 activates the cooling agent 1102 to enhance the cooling effect of refrigeration coils 1108 due to endothermic action of the cooling agent when mixed with water. The spent cooling agent 1110 exits refrigeration coils 1108 and passes to a forward osmosis (FO) membrane 1112, which provides two outputs, namely: (1) the dry salt or salt concentrate 1102, and (2) a more dilute liquid stream including brinel 114 to ultrafiltration (UF) membrane 1116. The UF membrane may alternatively utilize, for example, a related membrane technology such as reverse osmosis, nanofiltration, graphene, or molecular sieve where feasible. These technologies suitably operate where osmolality of the draw solution selected for FO processing is sufficiently high so as to generate an osmotic pressure sufficiently greater than the osmotic pressure of the coolant. The UF membrane 1116 provides two outputs, namely: (1) recovered/recycle water 1104 for use in the mixing chamber 1106 and, and (2) a dendrimer or draw solution 1118 for submission to the FO membranel 112.

[00075] The system 1100 may be provided for any cooling purpose described above including, without limitation, use in cooling a house, a data center, a computer room, an industrial facility, a counterflow tower, a crossflow tower, bearings of a wind turbine, a solar panel, vaccines, beverages, and medicines.

[00076] Use of the system 1100 provides significant energy savings over comparable cooling units known to the prior art. By way of example, a refrigeration peak pull down capacity 600W and operating capacity of 500W determined as cooling capacity in a system 1100 as shown is approximately equivalent to a 2,050 Btu/hr refrigeration unit, based upon a ton of refrigerant being equivalent to the energy required to melt 2,000 lbs of ice in 24 hours. Moreover, the mixing and activation coolant period or cycle of system 1100 based upon 1.1 lb of dry salt mixture and 2.1 lb coolant when mixed with recycle water is around 40 seconds to maintain an average cooler temperature of 3.5°C (37.4°F). This assumes that the respective components of system 1100 are sized to provide ninety mixing and activation cycles per hour to maintain the desired coolant temperature. WORKING EXAMPLES

[00077] The following discussion teaches by way of example, and not by limitation. These examples show that the dry salt mixtures are rendered stable against detonation if they have at least 10 wt% of a phosphate salt, such as monobasic ammonium phosphate. The dry salt mixtures are formulated against being problematic oxidizers if they contain a maximum of 68 wt% of nitrogen-containing salts, such as ammonium nitrate and/or potassium nitrate. Thus, in combination, the salts preferably have at least 10 wt% of a phosphate salt and 68 wt% or less of a nitrogen-containing salt.

[00078] Inclusion of 10 wt% phosphate materials, while being useful for purposes of stabilizing the salt mixtures at issue against ANFO-type detonation, are not a panacea for other issues. Even with the phosphate materials being included, the dry salt mixtures may still be classified as strong oxidizers and, in particular, oxidizer s that are sufficiently strong to invoke unfavorable regulatory compliance issues. By way of example, a particularly preferred salt mixture was prepared by combining the following ingredients, which are expressed as weight percentages of the total dry salt mixture. :

51.00% by weight ammonium nitrate;

33.70% ammonium phosphate, monobasic;

15.00%) potassium nitrate;

0.15%) silicon dioxide as fumed silica

0.15%) food color, blue powder

[00079] The dry salt mixture was subjected to oxidation tests according to the standard set forth in Test Series O. l : Test for Oxidizing Solids method, as described in the United Nations' "Recommendations on the Transport of Dangerous Goods Manual of Tests and Criteria, Fifth Revised Edition." As specified in the test method, the powder was sieved, with only the minus 500 micron (-35 mesh sieve fraction) material being used in the testing. The powder was mixed with dried fibrous cellulose (with the particle size specification spelled-out in the test method) in 30 gram samples at mass ratios of 1 : 1 and 4: 1 powder to cellulose. As specified in the test method, the 30 gram batches of cellulose/powder were loaded into a 60° glass funnel, sealed at the narrow end, with an internal diameter of 70 mm. A cardboard lid was placed on top of the funnel, to allow it to be inverted without spilling any of its contents. The inverted funnel was placed on top of a properly shaped resistance wire (as specified in the test method), which was lying flat on a low heat conducting ceramic plate. The cardboard was slid out from under the sample, thereby forming a truncated conical pile of material. With the test set-up positioned in a suitable fume cupboard, power was applied to the resistance wire (15 volts DC, producing 10 amps of current for a power output of 150 watts). A lab timer was used to measure the time required for the sample to ignite and burn to completion, with power being applied throughout the test. If the sample did not ignite, the heating was continued for 3 minutes, and then the test was concluded. As specified in the test method, a sample of dried/sieved reagent grade potassium bromate was used as the solid oxidizer standard. It was mixed with the dried cellulose at a 3 :7 ratio (mass ratio of potassium bromate to cellulose), and tested for its burning time using the same test procedure as described above. The average burning times of the various powder/cellulose mixtures were then compared to the average burning time of the 3 :7 potassium

bromate/cellulose mixture.

[00080] The material studied would have been classified as a Class 5.1 Oxidizer for transportation purposes if the powder exhibited a slower burning time when mixed at a 1 : 1 ratio with cellulose than did a comparative standard made of a 3 :7 potassium

bromate/cellulose mixture. In this test, the powder exhibited a slower burning time when mixed at a 1 : 1 ratio with cellulose than did a comparative standard made of a 3 :7 potassium bromate/cellulose mixture. Therefore, according to the UN test criteria, the powder was not considered to be a strong oxidizer of the type classified in Division 5.1, and so the material "Passed" the oxidation tests..

[00081] The dry salt mixture was also subjected to detonation testing. These tests was conducted to evaluate the comparative sensitivity of the salt as an explosive mixture. As a control, in order to oxygen balance a pure ground ammonium nitrate (AN) baseline powder, it was necessary to add approximately 5.8% diesel fuel oil to the AN powder, thereby producing the explosive commonly called ANFO. This material was loaded at respective loading densities of 0.81 g/cc, 0.82 g/cc and 0.84 g/cc into a 1 inch diameter steel pipe to form a charge primed with a 0.5 lb cast booster. The charges were evaluated for detonability using the confined critical diameter test. Point-to-point Velocity of Detonation (VOD) probes were attached to the last 6 inch sections of each pipe charge to serve as a detonation witness, similar detonation test data. The foregoing salt mixture was subjected to similar detonation tests, and it was determined that the material did not detonate. Therefore the material "Passed" the detonation testing. Test data for other salt mixtures are

summarized in the following Tables A through H. TABLE A

Cooling

NPK Content Ability

Nitrogen Potassium

(wt % Phosphorus (wt %

% of blend Total (wt % Total Total

(by weight) Ingredient Blend) Blend) Blend) kJ/kg

89.00% Ammonium Nitrate 29.4 0 0.0 286

0.70% Potassium Nitrate 0.1 0 0.3 2

Ammonium

Phosphate,

10.00% Monobasic 1.1 4.8 0.0 10

Silicon Dioxide,

0.15% Fumed Silica 0.0 0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0 0.0 0

100.00% 30.6 4.8 0.3 298

Btu/lb 128

Total

Test Series Cooling

0.1: Not tested Percent 100%

Total

Cooling

Detonate? Not tested. Drop (ΔΤ) 56.30

TABLE B

Cooling

NPK Content Ability

Nitrogen Potassium

(wt % Phosphorus (wt %

% of blend Total (wt % Total Total

(by weight) Ingredient Blend) Blend) Blend) kJ/kg

72.00% Ammonium Nitrate 23.8 0.0 0.0 231

7.00% Potassium Nitrate 0.9 0.0 3.1 24

Ammonium

Phosphate,

20.70% Monobasic 2.3 9.9 0.0 20

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0 Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 26.9 9.9 3.1 275

118

Btu/lb

Total

Test Series Cooling 92% O.l: Not tested Percent

Total

Cooling 52.06

Detonate? No Drop (ΔΤ)

TABLE C

Cooling

NPK Content Ability

Nitrogen Potassium

(wt % Phosphorus (wt %

% of blend Total (wt % Total Total

(by weight) Ingredient Blend) Blend) Blend) kJ/kg

72.00% Ammonium Nitrate 23.8 0.0 0.0 231

9.00% Potassium Nitrate 1.2 0.0 4.0 31

Ammonium

Phosphate,

18.70% Monobasic 2.1 9.0 0.0 18

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 27.0 9.0 4.0 280

120

Btu/lb

Total

Test Series Cooling 94% O.l: Fail Percent

Total

Cooling 53.00

Detonate? No Drop (ΔΤ) TABLE D

Cooling

NPK Content Ability

Nitrogen Potassium

(wt % Phosphorus (wt %

% of blend Total (wt % Total Total

(by weight) Ingredient Blend) Blend) Blend) kJ/kg

53.50% Ammonium Nitrate 17.7 0.0 0.0 172

15.00% Potassium Nitrate 2.0 0.0 6.6 52

Ammonium

Phosphate,

31.20% Monobasic 3.4 15.0 0.0 30

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 23.0 15.0 6.6 254

109

Btu/lb

Total

Test Series Cooling 85% 0.1: Fail Percent

Total

Cooling 47.99

Detonate? No Drop (A°F)

TABLE E

Cooling

NPK Content Ability

Nitrogen Potassium

% of blend (wt % Phosphorus (wt %

(by Total (wt % Total Total

weight) Ingredient Blend) Blend) Blend) kJ/kg

52.00% Ammonium Nitrate 17.2 0.0 0.0 167

12.70% Potassium Nitrate 1.7 0.0 5.6 44 Ammonium

Phosphate,

35.00% Monobasic 3.9 16.8 0.0 34

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 22.7 16.8 5.6 245

105

Btu/lb

Total

Test Series Cooling 82% 0.1: Not tested Percent

Total

Cooling 46.27

Detonate? No Drop (ΔΤ)

TABLE F

Cooling

NPK Content Ability

Nitrogen Potassium

% of blend (wt % Phosphorus (wt %

(by Total (wt % Total Total weight) Ingredient Blend) Blend) Blend) kJ/kg

52.00% Ammonium Nitrate 17.2 0.0 0.0 167

15.00% Potassium Nitrate 1.7 0.0 6.6 52

Ammonium

Phosphate,

32.70% Monobasic 3.9 15.7 0.0 32

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 22.7 15.7 6.6 250

108

Btu/lb Total 84%

Test Series Cooling

0.1: Not tested Percent

Total 47.35

Cooling

Detonate? No Drop (A°F)

TABLE G

Cooling

NPK Content Ability

Nitrogen Potassium

% of blend (wt % Phosphorus (wt %

(by Total (wt % Total Total weight) Ingredient Blend) Blend) Blend) kJ/kg

51.00% Ammonium Nitrate 16.8 0.0 0.0 164

15.00% Potassium Nitrate 2.0 0.0 6.6 52

Ammonium

Phosphate,

33.70% Monobasic 3.7 16.2 0.0 33

Silicon Dioxide,

0.15% Fumed Silica 0.0 0.0 0.0 0

Food Color, Blue

0.15% Powder 0.0 0.0 0.0 0

100.00% 22.5 16.2 6.6 248

107

Btu/lb

Total

Test Series Cooling 83%

0.1: Pass Percent

Total

Cooling 46.93

Detonate? No Drop (A°F)

TABLE H

Cooling

NPK Content Ability

Nitrogen Potassium

% of blend (wt % Phosphorus (wt %

(by Total (wt % Total Total weight) Ingredient Blend) Blend) Blend) kJ/kg 66.00% Ammonium Nitrate 21.8 0.0 0.0 212

23.70% Potassium Chloride 3.1 0.0 10.4 82

Ammonium 10 Phosphate,

10.00% Monobasic 1.1 4.8 0.0

Silicon Dioxide,

0.225% Fumed Silica 0.0 0.0 0.0

Food Color, Blue

0.075% Powder 0.0 0.0 0.0

100.00% 26.0 4.8 10.4 303

130

Btu/lb

Total

Test Series Cooling 102%

O.l: Pass Percent

Pass

(Borderline explosive

with weak effect Total

when mixed with Cooling 57.36

Detonate? fuel oil) Drop (ΔΤ)

[00082] It is thus apparent that the compositions of the present invention accomplish the principal objectives set forth above. Various modifications may be made without departing from the spirit and scope of the invention.