WO2023162972A1 - 蓄冷材 - Google Patents

蓄冷材 Download PDF

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Publication number
WO2023162972A1
WO2023162972A1 PCT/JP2023/006229 JP2023006229W WO2023162972A1 WO 2023162972 A1 WO2023162972 A1 WO 2023162972A1 JP 2023006229 W JP2023006229 W JP 2023006229W WO 2023162972 A1 WO2023162972 A1 WO 2023162972A1
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Prior art keywords
cold storage
storage material
activated carbon
temperature
semi
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PCT/JP2023/006229
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English (en)
French (fr)
Japanese (ja)
Inventor
博宣 町田
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Panasonic Holdings Corp
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Panasonic Holdings Corp
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Priority to CN202380023086.7A priority Critical patent/CN118742621A/zh
Priority to EP23759973.3A priority patent/EP4484518A4/en
Priority to JP2024503166A priority patent/JPWO2023162972A1/ja
Priority to US18/840,362 priority patent/US20250188334A1/en
Publication of WO2023162972A1 publication Critical patent/WO2023162972A1/ja
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/066—Cooling mixtures; De-icing compositions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the present disclosure relates to cold storage materials.
  • Patent Document 1 relates to a supercooling cancellation device such as an ice heat storage device used for the production or processing of food cooled or refrigerated at ice temperatures or air conditioning in buildings.
  • Patent Document 2 relates to a heat storage agent used in air conditioning equipment such as air conditioners or cooling devices such as food, and a method for preparing the heat storage agent.
  • the present disclosure provides a cold storage material that is advantageous from the viewpoint of energy saving and extension of cooling time while containing a predetermined amount of salt.
  • the cold storage material in the present disclosure is at least one salt selected from the group consisting of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate; water and, activated carbon; a silver compound;
  • the salt contains an anionic atomic group having two or more oxygen atoms, The surface of the activated carbon is basic.
  • OH ⁇ ions are attracted to the surface of the activated carbon in the cold storage material and easily adsorbed.
  • tetra-n-butylammonium hydroxide semi-clathrate hydrate or tetra-n-butylphosphonium hydroxide semi-clathrate hydrate is likely to be produced by the catalytic action of the silver compound. Therefore, semi-clathrate hydrate crystals of the above salts, which have crystal structures similar to those of those semi-clathrate hydrates, are likely to form even at a small degree of supercooling.
  • the melting points of tetra-n-butylammonium hydroxide semiclathrate hydrate and tetra-n-butylphosphonium hydroxide semiclathrate hydrate are higher than the melting points of the above salt semiclathrate hydrates.
  • a semi-clathrate hydrate having a high melting point is likely to be efficiently formed even in a small amount. Therefore, most of the semi-clathrate hydrates of the salts tend to decompose at temperatures slightly above the melting point of the semi-clathrate hydrates of the salts having low melting points.
  • the cold storage material can store cold with a small degree of supercooling, and can store a large amount of latent heat as cold heat. Therefore, the above-described cold storage material is advantageous from the viewpoint of energy saving and extension of cooling time.
  • a cold storage material comprising at least one salt selected from the group consisting of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate.
  • the semi-clathrate hydrate of this salt has a low melting point, for example below 20°C.
  • a semi-clathrate hydrate having a high melting point and a mixed semi-clathrate hydrate of a semi-clathrate hydrate having a high melting point and a semi-clathrate hydrate having a low melting point can be formed at the same time.
  • These semi-clathrate hydrates cannot be decomposed at temperatures slightly above the melting point of the low-melting semi-clathrate hydrates.
  • a new problem was found that when the amount of these semi-clathrate hydrates is large, the amount of latent heat available in the cold storage material is reduced.
  • the operating temperature range for that application is, for example, a temperature range assuming cold storage at about 5°C and cooling at about 11°C.
  • the present inventors have found an additive capable of producing semiclathrate hydrate crystals at the desired cooling temperature and decomposing most of the semiclathrate hydrate at the desired cooling temperature. searched for drugs.
  • a desired cooling temperature is, for example, a temperature lower than the melting point of the semiclathrate hydrate by 5°C or higher.
  • the desired cooling temperature is at least 1° C. above the melting point.
  • the inventor of the present invention searched for the additive through a great deal of trial and error. As a result, the present inventors found that the combination of a specific activated carbon and a silver compound produced semiclathrate hydrate crystals at the desired cooling temperature and most of the semiclathrate hydrate at the desired cooling temperature. It was found that decomposition is possible. Based on this new discovery, the inventors have come to form the subject matter of this disclosure.
  • the present disclosure provides at least one salt selected from the group consisting of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate, from the viewpoint of energy saving and extension of cooling time. To provide an advantageous cold storage material.
  • Embodiment 1 Embodiment 1 will be described below with reference to FIG.
  • the cold storage material in Embodiment 1 contains at least one salt selected from the group consisting of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate, water, activated carbon, and a silver compound.
  • Salts contain anionic groups with two or more oxygen atoms.
  • the surface of activated carbon is basic.
  • a semi-clathrate hydrate is formed in the crystallization of the cold storage material.
  • the clathrate hydrate means a crystal formed by forming a cage-shaped crystal by hydrogen bonding of water molecules, which are host molecules, and enclosing a guest substance, which is a substance other than water, in it.
  • semiclathrate hydrates are crystals formed by the participation of guest substances in hydrogen bonding networks of water molecules.
  • the concentration at which water molecules and guest substances just form a hydrate is called the harmonic concentration.
  • the concentration of the guest substance in the cold storage material can be adjusted at or near the harmonic concentration.
  • the cold storage material has a predetermined melting point.
  • the melting point of the cold storage material can be measured using a differential scanning calorimeter (DSC), as is well known in the cold storage material technical field.
  • DSC differential scanning calorimeter
  • Fig. 1 is a graph showing the characteristics of pre-crystallized cold storage material during cooling.
  • the horizontal and vertical axes represent time t and temperature T, respectively.
  • the temperature of the cold storage material is maintained at a temperature equal to or lower than the crystallization temperature.
  • a cool storage material is arranged inside the cool storage tank, and the refrigerant is stored around the cool storage material inside the cool storage tank. The temperature of the refrigerant stored around the cold storage material is adjusted to a temperature below the crystallization temperature so that the temperature of the cold storage material is maintained below the crystallization temperature.
  • a coolant is, for example, water.
  • high-temperature refrigerant is supplied to the inside of the cold storage tank, and the cold storage material is gradually warmed. See interval F in FIG.
  • high-temperature refrigerant is supplied to the inside of the cold storage tank at the end of section E, that is, at the beginning of section F, the temperature around the cold storage material gradually increases.
  • the temperature of the cold storage material When the temperature of the cold storage material reaches the melting point Tm of the cold storage material, the temperature of the cold storage material is kept near the melting point Tm of the cold storage material. See interval G in FIG. If there is no cold storage material inside the cold storage tank, the temperature of the refrigerant stored inside the cold storage tank rises continuously as shown in section Z in FIG. On the other hand, if the cold storage material is present inside the cold storage tank, the temperature of the refrigerant stored inside the cold storage tank is kept near the melting point Tm of the cold storage material in section G. In this way, the cold storage material exhibits a cold storage effect. At the end of section G, the crystals in the cold storage material melt and disappear. As a result, the cold storage material is liquefied. It is understood that the longer the duration of the section G in which the temperature of the cold storage material is maintained near the melting point Tm, the higher the cooling performance of the cold storage material.
  • the cold storage material can be cooled and reused.
  • the cold storage material satisfies, for example, the following conditions (I) and conditions (II). If the cold storage material satisfies these conditions, the cold storage material can be advantageously used in food production or food processing processes or air conditioning for cooling.
  • condition (I) for example, in the process of food production or food processing, or in air conditioning for cooling, the refrigerant cooled by the refrigerator using late-night power is supplied to the cold storage tank to crystallize the cold storage material. is about 5°C. If the set temperature of the refrigerator is less than 5°C, the refrigerant may freeze due to variations in operating conditions of the refrigerator. It is desirable from the viewpoint of preventing freezing of the refrigerant that condition (I) is satisfied.
  • condition (II) in the food production/processing process and air conditioning for cooling, it is necessary to cool down to about 11°C.
  • a refrigerant that has stored cold energy using late-night power returns to the cold storage tank at a temperature of about 11° C. or higher through the circulation path between the cold storage tank and the object to be cooled.
  • the cold storage material needs to cool such a cold storage material, and it is important that cooling is possible at about 11° C. using latent heat.
  • the melting point of n-pentadecane is 9.9° C.
  • the latent heat associated with melting of n-pentadecane is 164 kJ/kg. Therefore, when the condition (II) is satisfied, the cold storage material tends to be superior to the cold storage material containing n-pentadecane in terms of cold storage performance.
  • the difference between the cold storage temperature and the cold discharge temperature can be adjusted to about 6°C.
  • the melting point of the cold storage material can be set to a temperature 1° C. lower than the cold release temperature according to the usage conditions.
  • the cold storage temperature is at least 5° C. lower than the melting point of the cold storage material. If the cold storage temperature needs to be adjusted to be lower than the melting point of the cold storage material by more than 5°C, the power consumption of the refrigerator will increase, which is not advantageous from the viewpoint of energy saving.
  • the heat of fusion is also called the latent heat.
  • the anionic atomic group is not limited to a specific atomic group as long as it has two or more oxygen atoms.
  • Anionic groups are, for example, carboxylic acids with up to 6 carbon atoms (carboxylate ions).
  • the anionic atomic group may contain at least one selected from the group consisting of 2-ethylbutanoate, acetate, and pentanoate. In this case, the cold storage material easily satisfies the above conditions (I) and (II).
  • the anionic atomic group may be SO 4 2- , CO 3 2- , PO 4 3- , or NO 3 - . There may be.
  • the ratio of the salt content to the water content is not limited to a specific value.
  • the ratio is, for example, 2% or more and 4% or less on a molar basis.
  • the melting point and latent heat of the cold storage material increase. can be maximum.
  • the salt concentration at which this water and salt form a semi-clathrate hydrate in just the right amount is also called the harmonic concentration.
  • the ratio of the salt content to the water content is 2% or more and 4% or less on a molar basis, the salt concentration in the cold storage material is easily adjusted to the harmonic concentration or the vicinity of the harmonic concentration.
  • the activated carbon is not limited to a specific activated carbon as long as its surface is basic. For example, when the activated carbon taken out from the cold storage material is washed and then dispersed in pure water, and the pH of the dispersion shows basicity, it can be determined that the surface of the activated carbon is basic.
  • the activated carbon may dissolve, for example, at least one selected from the group consisting of Na and K into the water of the cold storage material. Activated carbon may elute at least one selected from the group consisting of Na and K into pure water when dispersed in pure water, for example.
  • the concentration of Na dissolved in the water of the cold storage material is not limited to a specific value. Its concentration is, for example, 3 mg/L or more. At least part of Na eluted into the water of the cold storage material is derived from activated carbon.
  • the concentration of K dissolved in the water of the cold storage material is not limited to a specific value. Its concentration is, for example, 20 mg/L or more. At least part of the K eluted into the water of the cold storage material is derived from activated carbon.
  • the content of activated carbon in the cold storage material is not limited to a specific value.
  • the content is, for example, 2% by mass or less. In this case, condition (II) is more likely to be satisfied.
  • the size of activated carbon is not limited to a specific value.
  • Activated carbon may comprise particles having a maximum diameter of, for example, 1 mm or more.
  • Activated carbon may comprise particles having a maximum diameter of less than 1 mm.
  • Activated carbon for example, is submerged in the liquid cold storage material. A part of the activated carbon may be suspended in the liquid cold storage material.
  • the silver compound is not limited to a specific compound.
  • Silver compounds include, for example, Ag2O , AgO, Ag2CO3 , Ag3PO4 , AgF, Ag2SO4 , Ag2CrO4 , Ag2WO4 , and carboxylic acids having up to 5 carbon atoms . At least one selected from the group consisting of silver is included.
  • the content of the silver compound in the cold storage material is not limited to a specific value.
  • the ratio of the silver compound content to the salt content is, for example, 0.05% or more and 0.10% or less on a molar basis.
  • the cold storage material may further contain additives that are components other than the salt, water, activated carbon, and silver compound described above.
  • additives are supercooling inhibitors, thickeners, and preservatives.
  • the cold storage material does not have to contain additives.
  • the cold storage material may consist only of the salt, water, activated carbon, and silver compound described above.
  • the cold storage material can be produced by mixing the above salt, water, activated carbon, and silver compound.
  • the surface of activated carbon is basic. Therefore, in cold storage, OH ⁇ ions can be attracted and adsorbed on the surface of the activated carbon of the cold storage material.
  • tetra-n-butylammonium hydroxide semi-clathrate hydrate or tetra-n-butylphosphonium hydroxide semi-clathrate hydrate can be produced by the catalytic action of silver compounds. Thereby, in cold storage, semi-clathrate hydrate crystals of the above salts with a crystal structure similar to that of those semi-clathrate hydrates can be produced with a small degree of supercooling.
  • Tetra-n-butylammonium hydroxide semi-clathrate hydrate or tetra-n-butylphosphonium hydroxide semi-clathrate hydrate can be efficiently formed in small amounts by the above activated carbon and silver compounds. Therefore, in standing to cool, most of the semi-clathrate hydrate of the salt tends to decompose at a temperature slightly above the melting point of the semi-clathrate hydrate of the salt having a low melting point. For example, 85% or more of the semi-clathrate hydrate of the above salt can decompose at a temperature of 1° C. above the melting point of the semi-clathrate hydrate of the above salt.
  • the cold storage material includes at least one salt selected from the group consisting of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate, water, and activated carbon. and a silver compound. Salts contain anionic groups with two or more oxygen atoms. The surface of activated carbon is basic.
  • crystals of the semi-clathrate hydrate of the above salt are likely to be generated at a small degree of supercooling.
  • crystals of semi-clathrate hydrate of the above salt are likely to form at a temperature 5° C. lower than the melting point of the cold storage material. Therefore, it is easy to reduce the energy required for cold storage of the cold storage material.
  • most of the semi-clathrate hydrates of the salts tend to decompose at temperatures slightly above the melting point of the semi-clathrate hydrates of the salts having low melting points. For this reason, the time during which the cooling can be performed tends to become long. In this way, the cold storage material is advantageous from the viewpoint of energy saving and extension of cooling time.
  • the activated carbon may dissolve, for example, at least one selected from the group consisting of Na and K into the water of the cold storage material.
  • semi-clathrate hydrate crystals of the above salts are more likely to form at small degrees of supercooling.
  • 3 mg/L or more of Na may be dissolved in the water of the cold storage material.
  • semi-clathrate hydrate crystals of the above salts are more likely to form at small degrees of supercooling.
  • 20 mg/L or more of K may be dissolved in the water of the cold storage material.
  • semi-clathrate hydrate crystals of the above salts are more likely to form at small degrees of supercooling.
  • the anionic atomic group may be a carboxylic acid (carboxylate ion) having 6 or less carbon atoms.
  • carboxylic acid carboxylate ion
  • semi-clathrate hydrate crystals of the above salts are more likely to form at small degrees of supercooling.
  • the anionic atomic group may be 2-ethylbutanoate.
  • the decomposition temperature of the semi-clathrate hydrate of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate is about 9.9° C. and about 8.3° C., respectively.
  • the latent heat values of semi-clathrate hydrates of tetra-n-butylammonium carboxylate and tetra-n-butylphosphonium carboxylate are about 200 kJ/kg and about 195 kJ/kg, respectively.
  • the silver compounds include Ag2O , AgO, Ag2CO3 , Ag3PO4 , AgF, Ag2SO4 , Ag2CrO4 , Ag2WO4 , and up to 5 It may contain at least one selected from the group consisting of silver carboxylates having carbon atoms.
  • semi-clathrate hydrate crystals of the above salts are more likely to form at small degrees of supercooling. Therefore, the cold storage material is more advantageous from the viewpoint of energy saving and lengthening of cooling time.
  • FIG. 2 shows a cold storage system 1a according to the second embodiment.
  • the cold storage system 1 a includes a cold storage tank 10 , a refrigerator 20 , an object to be cooled 30 , a first circulation path 22 and a second circulation path 32 .
  • a refrigerant 11 is stored inside the cold storage tank 10 .
  • the coolant 11 is water, for example.
  • the cold storage tank 10 can be placed, for example, in the basement of a food factory or building.
  • a plurality of cool storage modules 12 are arranged inside the cool storage tank 10 .
  • a plurality of cold storage modules 12 are immersed in the refrigerant 11 .
  • the cold storage module 12 includes, for example, a resin container having a rectangular parallelepiped outer shape and the above-described cold storage material housed inside the container.
  • the thickness of the plate material forming the container is, for example, 3 mm or less.
  • the cool storage material housed inside the container of the cool storage module 12 has a thickness of 20 mm or less in a solid state, for example.
  • a plurality of cases 14 are arranged inside the cold storage tank 10 .
  • a plurality of cold storage modules 12 are arranged at predetermined intervals.
  • the first circulation path 22 is formed between the refrigerator 20 and the cold storage tank 10 .
  • a pump (not shown) is arranged in the first circulation path 22 .
  • the operation of this pump causes the refrigerant 11 to circulate between the refrigerator 20 and the cold storage tank 10 through the first circulation path 22 as indicated by the solid line arrow in FIG. .
  • the refrigerator 20 is operated using late-night power, for example.
  • the second circulation path 32 is formed between the object to be cooled 30 and the cold storage tank 10 .
  • a pump (not shown) is arranged in the second circulation path 32 .
  • the operation of this pump causes the refrigerant 11 to circulate between the object to be cooled 30 and the cold storage tank 10 through the second circulation path 32 as indicated by the dashed arrow in FIG. do.
  • Due to heat exchange between the refrigerant 11 warmed in the object to be cooled 30 and the cold storage module 12 cold heat stored as latent heat in the cold storage material inside the cold storage module 12 is released to the refrigerant 11, and cooling is performed. .
  • Cooling operation of the cold storage system 1a can be performed, for example, during the day when the temperature tends to rise.
  • the cooling object 30 is placed, for example, on a manufacturing floor inside a food factory or in a building room.
  • the cold storage system 1a not only the sensible heat of the refrigerant 11 but also the latent heat of the cold storage material can be used, so the amount of cold heat that can be stored in the cold storage tank 10 tends to increase.
  • the number of cool storage modules 12 arranged inside the cool storage tank 10 is not limited to a specific value.
  • the shape of the cool storage module 12 is not limited to a rectangular parallelepiped shape, and may be other shapes.
  • the size of the cool storage module 12 is not limited to a specific size.
  • the size and shape of the case 14 in the cold storage system 1a are not limited to a specific aspect. In the cold storage system 1 a , the case 14 may be omitted and the plurality of cold storage modules 12 may be directly arranged inside the cold storage tank 10 .
  • the volume of the cold storage material present inside the cold storage tank 10 In order to increase the amount of cold heat that can be stored in the cold storage tank 10, it is advantageous for the volume of the cold storage material present inside the cold storage tank 10 to be large.
  • the volume of the cold storage material present inside the cold storage tank 10 can be determined in consideration of the balance between the amount of cold energy and the manufacturing cost.
  • the cold storage module 12 when the cold storage tank 10 is placed in the basement of a food factory or building, heat is rapidly exchanged between the refrigerant and the cold storage material from the viewpoint of rapid cold storage during the night and rapid release of cold during the day. It is very important to. For this reason, it is advantageous for the cold storage module 12 to have a large surface area. For example, it is desirable that the cold storage module 12 is thin with small dimensions in a specific direction and configured in a shape with a large surface area. Therefore, it is advantageous for the cold storage material housed inside the container of the cold storage module 12 to have a small thickness in the solid state. In addition, it is advantageous that the thickness of the plate material forming the container of the cool storage module 12 is small.
  • TBA-Acetate tetra-n-butylammonium-acetate
  • TBA-Acetate was purchased from Sigma-Aldrich Japan G.K.
  • Tetra-n-butylammonium-pentanoate is abbreviated as "TBA-Pentanoate”.
  • TBA-Pentanoate was synthesized from the reaction of silver pentanoate with tetra-n-butylammonium iodide.
  • Silver pentanoate was synthesized from the reaction of pentanoic acid and silver nitrate.
  • Tetra-n-butylammonium iodide and pentanoic acid were purchased from Tokyo Kasei Kogyo.
  • TBP-Acetate Tetra-n-butylphosphonium-acetate
  • TBP-Acetate was synthesized from the reaction of silver acetate with tetra-n-butylphosphonium iodide.
  • Silver acetate and tetra-n-butylphosphonium iodide were purchased from Fujifilm Wako Pure Chemical Industries.
  • Tetra-n-butylammonium-2-ethylbutanoate is abbreviated as "TBA-2-EB”.
  • TBA-2-EB was synthesized from the reaction of silver 2-ethylbutyrate and tetra-n-butylammonium iodide.
  • Silver 2-ethylbutyrate was synthesized from the reaction of 2-ethylbutyric acid and silver nitrate. Tetra-n-butylammonium iodide and 2-ethylbutyric acid were purchased from Tokyo Kasei Kogyo. Silver nitrate was purchased from Fujifilm Wako Pure Chemical.
  • Activated carbon A is activated carbon whose surface exhibits basicity, and was purchased from Kuraray Co., Ltd. and was Kuraray Coal activated carbon for removing harmful gases or malodorous gases.
  • Activated carbon B is an activated carbon whose surface exhibits acidity and was BGX purchased from Kuraray.
  • Ag 2 O was purchased from Fujifilm Wako Pure Chemical. AgO was purchased from Fujifilm Wako Pure Chemical. Ag acetate was purchased from Fujifilm Wako Pure Chemical. AgF was purchased from Sigma-Aldrich Japan LLC. Ag 2 CO 3 was purchased from Fujifilm Wako Pure Chemical.
  • Example 1 As shown in Table 1, TBA-Acetate, pure water, Ag 2 O, and activated carbon A were added to a screw tube with a capacity of 9 ml to obtain a mixture. The mixture was sufficiently stirred inside the screw tube to obtain a cold storage material according to Example 1. Screw tubes were glass tubes with screwed caps. When the cold storage material according to Example 1 was in a liquid state, the activated carbon A sank to the bottom of the glass tube. Activated Carbon A contained particles with a maximum diameter greater than or equal to 1 mm.
  • Example 2 A cold storage material according to Example 2 was obtained in the same manner as in Example 1, except that TBA-Pentanoate, pure water, Ag 2 O, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 2 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 3 A cold storage material according to Example 3 was obtained in the same manner as in Example 1, except that TBP-Acetate, pure water, Ag 2 O, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 3 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 4 A cold storage material according to Example 4 was obtained in the same manner as in Example 1, except that TBA-2-EB, pure water, Ag 2 O, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 4 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 5 A cold storage material according to Example 5 was obtained in the same manner as in Example 1, except that TBA-Acetate, pure water, AgO, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 5 was in a liquid state, the activated carbon A sunk to the bottom of the glass tube.
  • Example 6 A cold storage material according to Example 6 was obtained in the same manner as in Example 1, except that TBA-Acetate, pure water, Ag acetate, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 6 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 7 A cold storage material according to Example 7 was obtained in the same manner as in Example 1, except that TBA-2-EB, pure water, AgO, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 7 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 8 A cold storage material according to Example 8 was obtained in the same manner as in Example 1, except that TBA-2-EB, pure water, AgF, and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 8 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 9 A cold storage material according to Example 9 was obtained in the same manner as in Example 1 except that TBA-2-EB, pure water, Ag 2 CO 3 and activated carbon A were added in the amounts shown in Table 1. When the cold storage material according to Example 9 was in a liquid state, the activated carbon A sank to the bottom of the glass tube.
  • Example 1 A cold storage material according to Comparative Example 1 was obtained in the same manner as in Example 1, except that TBA-Acetate, pure water, and Ag 2 O were added in the amounts shown in Table 1. The cold storage material according to Comparative Example 1 did not contain activated carbon.
  • Comparative example 2 A cold storage material according to Comparative Example 2 was obtained in the same manner as in Example 1, except that TBA-Acetate, pure water, Ag 2 O, and activated carbon B were added in the amounts shown in Table 1.
  • Comparative Example 3 A cold storage material according to Comparative Example 3 was obtained in the same manner as in Example 1, except that TBA-Acetate, pure water, and activated carbon A were added in the amounts shown in Table 1. The cold storage material according to Comparative Example 3 did not contain Ag2O .
  • the temperature of the reference material reached minus 20 degrees Celsius
  • the temperature of the reference material was maintained at minus 20 degrees Celsius for 10 minutes.
  • the temperature of the reference material was then increased from minus 20 degrees Celsius to 30 degrees Celsius at a rate of 1 degree Celsius/minute.
  • the crystallized cold storage material started to melt, only the latent heat was absorbed, so the temperature rise stagnated.
  • the melting ended it converged to the temperature rise line of the original program again.
  • the endothermic peak temperature at this time was determined as the melting point of the cold storage material, and the heat absorption amount was determined as the latent heat amount of the cold storage material.
  • the DSC-8500 was used to measure the melting points and latent heat amounts of the cold storage materials according to each example and each comparative example. Table 2 shows the results.
  • Table 2 shows the evaluation results of the crystallization characteristics and melting characteristics of the cold storage materials according to each example and each comparative example.
  • An aqueous solution of ammonium carboxylate was obtained in the same manner as in Example 4, except that activated carbon A and silver compound were not added.
  • the aqueous solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a liquid sample.
  • a small amount of nitric acid was added to this liquid sample and further diluted 100 times with pure water to obtain an analytical sample ⁇ .
  • aqueous solution of ammonium carboxylate to which activated carbon A was added was obtained in the same manner as in Example 4, except that no silver compound was added.
  • the aqueous solution was filtered through a syringe filter with a pore size of 0.45 ⁇ m to obtain a liquid sample.
  • a small amount of nitric acid was added to this liquid sample and further diluted 100 times with pure water to obtain an analytical sample ⁇ .
  • ICP-MS inductive plasma mass spectrometry
  • the cold storage material according to each example could store cold with a small degree of supercooling and store a large amount of latent heat as cold heat.
  • cold storage at a small degree of supercooling cannot be expected, and it was shown that the amount of latent heat that can be stored as cold heat is difficult to increase.
  • the cold storage material according to each example can store cold with a smaller degree of supercooling than the cold storage material according to each comparative example, and can store a large amount of latent heat as cold heat. For this reason, the cold storage material according to each example is advantageous from the viewpoint of energy saving and extension of cooling time.
  • the cold storage material of the present disclosure can be used in applications requiring cooling or cold insulation, such as food factories and buildings.

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