WO2022176190A1 - Composition de matériau de stockage de chaleur et dispositif de stockage de chaleur - Google Patents

Composition de matériau de stockage de chaleur et dispositif de stockage de chaleur Download PDF

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Publication number
WO2022176190A1
WO2022176190A1 PCT/JP2021/006581 JP2021006581W WO2022176190A1 WO 2022176190 A1 WO2022176190 A1 WO 2022176190A1 JP 2021006581 W JP2021006581 W JP 2021006581W WO 2022176190 A1 WO2022176190 A1 WO 2022176190A1
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WO
WIPO (PCT)
Prior art keywords
heat storage
sugar alcohol
storage material
material composition
compound
Prior art date
Application number
PCT/JP2021/006581
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English (en)
Japanese (ja)
Inventor
知卓 輪島
Original Assignee
三菱電機株式会社
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Filing date
Publication date
Application filed by 三菱電機株式会社 filed Critical 三菱電機株式会社
Priority to JP2021539859A priority Critical patent/JP6949290B1/ja
Priority to PCT/JP2021/006581 priority patent/WO2022176190A1/fr
Publication of WO2022176190A1 publication Critical patent/WO2022176190A1/fr

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Classifications

    • 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
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen
    • C09K15/08—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen containing a phenol or quinone moiety
    • 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
    • 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 a heat storage material composition and a heat storage device including the same.
  • a latent heat storage material is a heat storage material that uses the latent heat that is absorbed or released when a substance undergoes a phase transition. Since the latent heat storage material can absorb or release a large amount of thermal energy at the time of phase transition, it is expected to construct a highly efficient heat storage device using the latent heat storage material.
  • Patent Document 1 describes that a heat storage material composition containing a sugar alcohol, an antioxidant, and a nucleating agent is stable against heat history, and the sugar alcohol has good crystallization properties.
  • Patent Document 2 describes that an antioxidant may be added to a heat storage material composition containing an aqueous solution in which a sugar alcohol and water-soluble salts are dissolved.
  • sugar alcohol liquid deteriorates more quickly at low temperatures than sugar alcohol that is not dissolved or dispersed in water (hereinafter sometimes referred to as "sugar alcohol simple substance").
  • sugar alcohol simple substance a sugar alcohol that is not dissolved or dispersed in water
  • the mechanism by which the sugar alcohol alone deteriorates is different from the mechanism by which the sugar alcohol solution deteriorates, and even if the method is effective for suppressing the deterioration of the sugar alcohol alone (for example, Patent Document 1). , indicates that it is not always an effective method for suppressing the deterioration of the sugar alcohol solution.
  • the antioxidant described in Patent Document 2 is used to suppress oxidation of the sugar alcohol by oxygen present in the environment in which the heat storage material composition is used. Therefore, when the sugar alcohol solution is used in an oxygen-blocked environment, it is considered that the sugar alcohol solution does not deteriorate due to oxidation even if the sugar alcohol solution does not contain an antioxidant.
  • the present inventors have found that if the sugar alcohol solution is heated for a long period of time in an oxygen-blocked environment, the sugar alcohol solution may deteriorate, and that the metal member included in the heat storage device using the sugar alcohol was found to corrode. Deterioration of the sugar-alcohol solution is considered to lead to deterioration in heat storage performance, leading to shortened life of the heat storage device.
  • An object of the present disclosure is to provide a heat storage material composition capable of suppressing deterioration due to long-term heating, and a heat storage device including the same.
  • the heat storage material composition of the present disclosure is a sugar alcohol liquid containing sugar alcohol and water; and a compound having one phenolic hydroxyl group in the molecule.
  • the heat storage material composition of the present disclosure deterioration of the heat storage material composition due to long-term heating can be suppressed, so that the life of the heat storage device can be extended.
  • the heat storage material composition of the present embodiment comprises a sugar alcohol liquid containing sugar alcohol and water, and a compound having one phenolic hydroxyl group in the molecule (hereinafter sometimes referred to as "compound (I)"). ,including.
  • the heat storage material composition may further contain additives such as corrosion inhibitors, supercooling inhibitors, coloring agents, or antioxidants other than compound (I).
  • the heat storage material composition contains the sugar alcohol liquid and the compound (I), even when the heat storage material composition is heated for a long period of time, the heat storage material composition is discolored and the pH of the heat storage material composition is lowered. It is possible to suppress the deterioration of the heat storage material composition. The reason for this is presumed as follows.
  • the heat applied for the heating breaks the molecular chains of the sugar alcohol, and the radicals generated by this breaking further break other molecular chains, causing a chain reaction.
  • the chain reaction decomposes the sugar alcohol and causes the generation of organic acids such as formic acid. Therefore, as the chain reaction progresses, the organic acid accumulates in the sugar alcohol solution. This is thought to cause deterioration of the sugar-alcohol liquid, such as discoloration of the sugar-alcohol liquid and a decrease in pH of the sugar-alcohol liquid.
  • compound (I) converts radicals generated by heat applied for heating. Because it can be captured, chain reactions are less likely to occur. As a result, even if the heat storage material composition is heated for a long period of time, the decomposition of the sugar alcohol and the generation of the organic acid can be suppressed. It is thought that the deterioration of the heat storage material composition such as the deterioration of the heat storage material composition can be suppressed. By suppressing deterioration of the heat storage material composition, it can be expected that stable heat storage performance can be obtained over a long period of time. In addition, by suppressing the decrease in the pH of the heat storage material composition, it is possible to suppress corrosion of metal members included in the heat storage device using the heat storage material composition, so that the life of the heat storage device can be extended. be able to.
  • the heat storage material composition can be prepared by mixing the sugar alcohol liquid and compound (I), and is preferably prepared by adding compound (I) to the sugar alcohol liquid.
  • sugar alcohol liquid contains sugar alcohol and water.
  • the sugar-alcohol liquid may be a state in which part or all of the sugar alcohol is dissolved in water, or part or all of the sugar alcohol is dispersed.
  • the sugar alcohol liquid is preferably an aqueous solution in which all the sugar alcohol is dissolved in water.
  • the sugar alcohol is not particularly limited as long as it is a compound known as a latent heat storage material.
  • sugar alcohols include erythritol, mannitol, xylitol, sorbitol, maltitol, dulcitol, lactitol, palatinit and the like. Among these, erythritol, mannitol, xylitol, and dulcitol are preferred, and erythritol is more preferred, since they have a large amount of heat storage per unit volume when used as a sugar alcohol solution.
  • One or two or more sugar alcohols may be contained in the sugar alcohol liquid.
  • the concentration of the sugar alcohol in the sugar alcohol liquid is not particularly limited, but is usually 30% by weight or more, may be 40% by weight or more, preferably 50% by weight or more, and is 60% by weight or more. is more preferable, and may be 65% by weight or more.
  • the sugar alcohol concentration in the sugar alcohol liquid is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, and may be 75% by weight or less. When two or more sugar alcohols are contained in the sugar alcohol liquid, the sugar alcohol concentration is calculated based on the total weight of all sugar alcohols contained in the sugar alcohol liquid.
  • the concentration of the sugar alcohol in the heat storage material composition may be adjusted so as to obtain the desired heat storage performance. It is preferably 45% by weight or more, more preferably 50% by weight or more, and may be 60% by weight or more.
  • the concentration of the sugar alcohol in the heat storage material composition is usually 90% by weight or less, preferably 85% by weight or less, more preferably 80% by weight or less, and may be 75% by weight or less. .
  • the sugar alcohol concentration is calculated based on the total weight of all sugar alcohols contained in the heat storage material composition.
  • Water used for the sugar alcohol solution includes, for example, pure water, ion-exchanged water, distilled water, reverse osmosis water, and tap water, and one or more of these can be used.
  • the sugar alcohol liquid can be prepared by mixing water and sugar alcohol, and is preferably prepared by adding sugar alcohol to water.
  • Compound (I) is a compound having one phenolic hydroxyl group in the molecule.
  • a phenolic hydroxyl group refers to a hydroxyl group bonded to a carbon atom constituting a benzene ring.
  • Compound (I) has one phenolic hydroxyl group.
  • a compound having two or more phenolic hydroxyl groups has high reactivity, and when added to a sugar alcohol solution, it reacts with the sugar alcohol and polymerizes, so it hardly contributes to suppression of deterioration of the heat storage material composition.
  • Compound (I) may have one benzene ring to which a phenolic hydroxyl group is bonded in the molecule, and may have a benzene ring in addition to the benzene ring.
  • Compound (I) preferably has one benzene ring in its molecule.
  • the carbon atoms other than the carbon atom to which the phenolic hydroxyl group is bonded are alkyl groups such as methyl group, ethyl group, propyl group, and butyl group, And, an organic group such as an alkoxy group such as a methoxy group and an ethoxy group may be bonded.
  • compound (I) examples include methoxyphenols such as 2-methoxyphenol and 4-methoxyphenol, 2,6-dimethoxyphenol, 2-t-butyl-4-methoxyphenol, cresol, and phenol.
  • the compound (I) contained in the heat storage material composition may be one kind, or two or more kinds.
  • Compound (I) contained in the heat storage material composition is not particularly limited, but is usually 0.003 mol or more, preferably 0.005 mol or more, preferably 0.007 mol, per 1 mol of sugar alcohol. It is more preferably 0.009 mol or more, and is usually 0.025 mol or less, more preferably 0.020 mol or less, and 0.018 mol or less. is more preferable, and may be 0.015 mol or less.
  • the content of compound (I) is calculated based on the total weight of all compounds (I) contained in the heat storage material composition. If the content of compound (I) is within the above range, it is easy to suppress deterioration of the heat storage material composition when heated for a long period of time.
  • the heat storage material composition may contain an additive that is a compound other than the sugar alcohol liquid and compound (I).
  • additives include corrosion inhibitors, supercooling inhibitors, coloring agents, and antioxidants other than compound (I).
  • Corrosion inhibitors include, for example, chromates, phosphates, sodium nitrites, silicates, organic amines, and the like.
  • supercooling inhibitors include metal salts or organic salts of fatty acids such as stearates, palmitates, and behenates.
  • Colorants include known pigments or dyes.
  • Antioxidants other than compound (I) include known sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants.
  • the heat storage device of this embodiment includes a heat storage material composition.
  • the heat storage device includes a container for housing the heat storage material composition, and a heat exchange component for transferring heat from the outside to the heat storage material composition or for transferring the heat of the heat storage material composition to the outside. be able to.
  • the container and heat exchange parts with which the heat storage material composition is in contact are sometimes made of metal members made of metal such as aluminum, aluminum alloy, iron alloy, or copper.
  • metal members made of metal such as aluminum, aluminum alloy, iron alloy, or copper.
  • generation of organic acid and decrease in pH of the heat storage material composition are suppressed even when heated for a long period of time. can be suppressed.
  • Detection of amount of metal Detection of metals in the sugar alcohol solution after heat treatment and detection of metals in the heat storage material composition after heat treatment were performed by plasma emission spectroscopy using "SPS-3100" manufactured by SII Nano Technology Co., Ltd. by analysis.
  • a sugar alcohol solution (a) (concentration of sugar alcohol: 80% by weight) was prepared by mixing 40 g of erythritol as a sugar alcohol and 10 g of water. The heating treatment was carried out under the heating treatment condition (1) in which the temperature was maintained at 5 hours. The color of the sugar alcohol liquid (a) after the heating treatment was visually confirmed, formic acid was detected, and the pH was measured after standing to cool. Table 1 shows the results.
  • a heat storage material composition (E1) was prepared by adding 0.38 g of 4-methoxyphenol as the compound (I) to the sugar alcohol liquid (a) prepared in the same manner as in Reference Example 1, and then placed in a pressurized sealed container. A heating treatment was performed under the heating treatment condition (2) in which the mixture was placed in a thermostat set at a temperature of 90° C. and held for 30 days. The color of the heat storage material composition (E1) after the heating treatment was visually confirmed, formic acid was detected, and the pH was measured after standing to cool. Table 1 shows the results.
  • a heat storage material composition (E2) was prepared in the same manner as the heat storage material composition (E1) of Example 1, except that 2-methoxyphenol was used as compound (I) instead of 4-methoxyphenol. prepared and heat treated. After the heat treatment, the heat storage material composition (E2) was visually checked for color, detected formic acid, and measured for pH. Table 1 shows the results.
  • a heat storage material composition (C1) was prepared by adding 0.27 g of hydroquinone to the sugar alcohol liquid (a) prepared by the same procedure as in Reference Example 1, and placed in a pressure-sealed container at a set temperature of 90°C. The heating treatment was performed under the heating treatment condition (2) of holding for 30 days in a constant temperature bath. The color of the heat storage material composition (C1) after the heating treatment was visually confirmed, formic acid was detected, and the pH was measured after standing to cool. Table 1 shows the results.
  • a heat storage material composition (C2) was prepared by adding 0.42 g of methoxyhydroquinone to the sugar alcohol liquid (a) prepared by the same procedure as in Reference Example 1, and placed in a pressure-sealed container, and the temperature was set to 90°C. The heating treatment was performed under the heating treatment condition (2) of holding for 30 days in a constant temperature bath. The color of the heat storage material composition (C2) after the heating treatment was visually confirmed, formic acid was detected, and the pH was measured after standing to cool. Table 1 shows the results.
  • the heat storage material composition containing the sugar alcohol liquid and compound (I) was colorless and transparent even when heated for a long period of time, and the decrease in pH was suppressed (Example 1 and 2).
  • the sugar alcohol solution containing no compound (I) was heated for a short period of time, deterioration was suppressed (Reference Example 1).
  • the color turned brown and the pH decreased (Comparative Examples 1 and 2). Since the heat storage material composition containing the compound (I) can suppress deterioration of the heat storage material composition due to long-term heating, the heat storage material composition containing the compound (I) stabilizes the heat storage performance over a long period of time. It is thought that it can be made into
  • the heat storage material composition turned black and the pH decreased (Comparative Examples 3 and 4). From the color change of the heat storage material composition, it is considered that the compound having multiple phenolic hydroxyl groups forms a reaction product generated by the reaction with the sugar alcohol, so it contributes to suppressing the deterioration of the heat storage material composition. is considered difficult.
  • a sugar alcohol solution (b) (concentration of sugar alcohol: 60% by weight) was prepared by mixing 30 g of erythritol as a sugar alcohol and 20 g of water. The heating treatment was carried out under the heating treatment condition (4) of holding for 14 days at . The color of the sugar alcohol liquid (b) after the heat treatment was visually confirmed, and the pH was measured after standing to cool. Table 2 shows the results.
  • a heat storage material composition (E3) was prepared by adding 0.38 g of 4-methoxyphenol as the compound (I) to the sugar alcohol liquid (a) prepared in the same manner as in Reference Example 1, and placed in a pressure sealed container. A heating treatment was performed under the heating treatment condition (4) in which the temperature was set to 90° C. and held for 14 days in a constant temperature bath. The color of the heat storage material composition (E3) after the heating treatment was visually confirmed, and the pH was measured after standing to cool. Table 2 shows the results.
  • a heat storage material composition (E4) was prepared by adding 0.38 g of 4-methoxyphenol as the compound (I) to the sugar alcohol liquid (b) prepared in the same manner as in Comparative Example 6, and placed in a pressure-sealed container. A heating treatment was performed under the heating treatment condition (4) in which the temperature was set to 90° C. and held for 14 days in a constant temperature bath. The color of the heat storage material composition (E4) after the heating treatment was visually confirmed, and the pH was measured after standing to cool. Table 2 shows the results.
  • a sugar alcohol liquid (c) (concentration of sugar alcohol: 40% by weight) was prepared by mixing 20 g of erythritol as a sugar alcohol and 30 g of water.
  • a heat storage material composition (E5) was prepared by adding 0.38 g of 4-methoxyphenol as compound (I) to this sugar alcohol liquid (c), placed in a pressurized sealed container, and set to a temperature of 90°C. The heating treatment was performed under the heating treatment condition (4) of holding for 14 days in a constant temperature bath. The color of the heat storage material composition (E5) after the heating treatment was visually confirmed, and the pH was measured after standing to cool. Table 2 shows the results.
  • the heat storage material composition containing a sugar alcohol solution with a sugar alcohol concentration of 40% to 80% by weight and compound (I) suppresses a decrease in pH even when heated for a long period of time. did it.
  • the heat storage material composition containing sugar alcohol solutions with sugar alcohol concentrations of 60% by weight and 80% by weight and compound (I) is excellent in suppressing discoloration and pH drop even when heated for a long period of time. rice field.
  • Example 6 A test piece of aluminum (Al), a test piece of iron (Fe), and a copper (Cu) test were applied to the heat storage material composition (E1) prepared in the same procedure as in Example 1 and placed in a pressure-sealed container. After performing a heating treatment under the heating treatment condition (2) in which the immersed piece was held for 30 days in a constant temperature bath with a set temperature of 90° C., the test piece was taken out. After the heating treatment, the heat storage material composition (E1) was visually checked for color, formic acid and metal were detected, and after cooling, the pH was measured. Table 3 shows the results.
  • the heat storage material composition containing the sugar alcohol solution and the compound (I) suppresses discoloration, accumulation of formic acid, and dissolution of the metal even when in contact with the metal for a long period of time under heating conditions. I was able to Therefore, in the heat storage device using the heat storage material composition containing the sugar alcohol liquid and the compound (I), it is possible to suppress the corrosion of the metal member included in the heat storage device, so that it is possible to extend the life of the heat storage device. can. In Comparative Example 7, it is considered that the pH did not decrease because hydroxide ions were generated as the test piece corroded.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette composition de matériau de stockage de chaleur comprend : une solution d'alcool de sucre comprenant un alcool de sucre et de l'eau ; et un composé ayant un groupe hydroxyle phénolique dans la molécule.
PCT/JP2021/006581 2021-02-22 2021-02-22 Composition de matériau de stockage de chaleur et dispositif de stockage de chaleur WO2022176190A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
JP2021539859A JP6949290B1 (ja) 2021-02-22 2021-02-22 蓄熱材組成物及び蓄熱デバイス
PCT/JP2021/006581 WO2022176190A1 (fr) 2021-02-22 2021-02-22 Composition de matériau de stockage de chaleur et dispositif de stockage de chaleur

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60163989A (ja) * 1984-02-03 1985-08-26 Agency Of Ind Science & Technol 相転移熱蓄熱体
JPS61218683A (ja) * 1985-03-25 1986-09-29 Agency Of Ind Science & Technol 相転移熱蓄熱材料
JP2014019718A (ja) * 2012-07-12 2014-02-03 Hakugen:Kk 保冷剤
JP6818942B1 (ja) * 2019-10-18 2021-01-27 三菱電機株式会社 蓄熱式給湯器

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10183111A (ja) * 1996-10-29 1998-07-14 Mitsubishi Chem Corp 蓄熱・放熱方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60163989A (ja) * 1984-02-03 1985-08-26 Agency Of Ind Science & Technol 相転移熱蓄熱体
JPS61218683A (ja) * 1985-03-25 1986-09-29 Agency Of Ind Science & Technol 相転移熱蓄熱材料
JP2014019718A (ja) * 2012-07-12 2014-02-03 Hakugen:Kk 保冷剤
JP6818942B1 (ja) * 2019-10-18 2021-01-27 三菱電機株式会社 蓄熱式給湯器

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JPWO2022176190A1 (fr) 2022-08-25

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