JPWO2019159791A1 - Chemical heat storage material and its manufacturing method - Google Patents
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- 238000005338 heat storage Methods 0.000 title claims abstract description 106
- 239000000126 substance Substances 0.000 title claims abstract description 95
- 239000011232 storage material Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011575 calcium Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 37
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 36
- 239000011777 magnesium Substances 0.000 claims abstract description 36
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 102
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 69
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 23
- 239000000347 magnesium hydroxide Substances 0.000 claims description 22
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000920 calcium hydroxide Substances 0.000 claims description 19
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 51
- 238000006297 dehydration reaction Methods 0.000 abstract description 22
- 150000002642 lithium compounds Chemical class 0.000 abstract description 12
- 230000000052 comparative effect Effects 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 24
- 235000012254 magnesium hydroxide Nutrition 0.000 description 21
- 238000011156 evaluation Methods 0.000 description 20
- 235000011116 calcium hydroxide Nutrition 0.000 description 15
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 14
- 239000002002 slurry Substances 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 239000002918 waste heat Substances 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000012255 calcium oxide Nutrition 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 235000012245 magnesium oxide Nutrition 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000036571 hydration Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229940087373 calcium oxide Drugs 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- VXJIMUZIBHBWBV-UHFFFAOYSA-M lithium;chloride;hydrate Chemical compound [Li+].O.[Cl-] VXJIMUZIBHBWBV-UHFFFAOYSA-M 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- -1 chloride or bromide Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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- 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
- C09K5/16—Materials undergoing chemical reactions when used
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
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Abstract
カルシウム及び／又はマグネシウムの水酸化物の脱水反応を利用した蓄熱を行なう化学蓄熱材において、より高い反応率を示し、より低温での蓄熱を実現できる化学蓄熱材を提供する。化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、リチウムの化合物としてリチウムの水酸化物及びリチウムの塩化物を共に含む。前記リチウムの化合物の総量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜５０モル％であることが好ましい。Provided is a chemical heat storage material that stores heat by utilizing the dehydration reaction of a hydroxide of calcium and / or magnesium, which exhibits a higher reaction rate and can realize heat storage at a lower temperature. The chemical heat storage material contains both a hydroxide and / or oxide of calcium and / or magnesium, and a hydroxide of lithium and a chloride of lithium as a compound of lithium. The total amount of the lithium compound is preferably 0.1 to 50 mol% with respect to the hydroxide and / or oxide of the calcium and / or magnesium.
Description
本発明は、化学蓄熱材及びその製造方法に関する。 The present invention relates to a chemical heat storage material and a method for producing the same.
近年、二酸化炭素排出規制によって化石燃料の使用削減が求められており、各プロセスの省エネルギー化に加え、排熱の利用を進める必要がある。排熱の利用の手段としては、水を利用した１００℃以下の温水蓄熱が知られている。しかし、温水蓄熱には、（１）放熱損失があるため長時間の蓄熱が不可能である、（２）顕熱量が小さいため大量の水が必要であり、蓄熱設備のコンパクト化が困難である、（３）出力温度が利用量に応じて非定常で、次第に降下する、等の問題がある。したがって、このような排熱の民生利用を進めるためには、より効率の高い蓄熱技術を開発する必要がある。 In recent years, carbon dioxide emission regulations have required reductions in the use of fossil fuels, and in addition to energy conservation in each process, it is necessary to promote the use of waste heat. As a means for utilizing exhaust heat, hot water storage at 100 ° C. or lower using water is known. However, in hot water heat storage, (1) heat storage for a long time is impossible due to heat dissipation loss, and (2) a large amount of water is required because the amount of exposed heat is small, and it is difficult to make the heat storage facility compact. , (3) There are problems such as the output temperature is unsteady depending on the amount of use and gradually drops. Therefore, in order to promote the consumer use of such waste heat, it is necessary to develop a more efficient heat storage technology.
効率の高い蓄熱技術として化学蓄熱法が挙げられる。化学蓄熱法は、物質の吸着、水和等の化学変化を伴うため、材料自体（水、溶融塩等）の潜熱や顕熱による蓄熱法に比べて単位質量当たりの蓄熱量が高くなる。化学蓄熱法としては、大気中の水蒸気の吸脱着による水蒸気吸脱着法、金属塩へのアンモニア吸収（アンミン錯体生成反応）、アルコール等の有機物の吸脱着による反応等が提案されている。環境への負荷や装置の簡便性を考慮すると、水蒸気吸脱着法が最も有利である。水蒸気吸脱着法に用いられる化学蓄熱材として、水酸化カルシウムや水酸化マグネシウムが知られている。 The chemical heat storage method is an example of a highly efficient heat storage technology. Since the chemical heat storage method involves chemical changes such as adsorption and hydration of substances, the amount of heat storage per unit mass is higher than that of the heat storage method using latent heat or sensible heat of the material itself (water, molten salt, etc.). As the chemical heat storage method, a water vapor adsorption / desorption method by adsorption / desorption of water vapor in the atmosphere, ammonia absorption into a metal salt (ammine complex formation reaction), a reaction by adsorption / desorption of an organic substance such as alcohol, and the like have been proposed. Considering the burden on the environment and the convenience of the device, the water vapor absorption / desorption method is the most advantageous. Calcium hydroxide and magnesium hydroxide are known as chemical heat storage materials used in the water vapor adsorption / desorption method.
しかし、水酸化カルシウムは１００〜４００℃、水酸化マグネシウムは１００〜３００℃の低温域では有効な脱水反応を起こさないため、実用的な蓄熱材として機能しないという問題があった。 However, calcium hydroxide does not cause an effective dehydration reaction in a low temperature range of 100 to 400 ° C. and magnesium hydroxide at 100 to 300 ° C., so that there is a problem that it does not function as a practical heat storage material.
この問題を解決するために、特許文献１では、マグネシウムと、ニッケル、コバルト、銅、及びアルミニウムからなる群から選ばれた少なくとも１種の金属成分との複合水酸化物を利用することで、１００〜３００℃程度で蓄熱可能な化学蓄熱材が提案されている。 In order to solve this problem, Patent Document 1 uses a composite hydroxide of magnesium and at least one metal component selected from the group consisting of nickel, cobalt, copper, and aluminum. A chemical heat storage material capable of storing heat at about 300 ° C. has been proposed.
さらに、特許文献２では、特許文献１に記載の化学蓄熱材の蓄熱量を改善することを目的に、マグネシウム又はカルシウムの水酸化物に、塩化リチウム等の吸湿性金属塩を添加してなる化学蓄熱材が提案されている。
Further, in
特許文献１及び２に開示された技術によれば、蓄熱動作温度をある程度低温化することができるものの、例えば工場廃熱を蓄熱しようとした時などには、工場廃熱の温度域が２００〜２５０℃又はより低温度域であることから、その蓄熱動作温度は十分に低いものではなく、工場廃熱を効率よく利用することが困難で、動作温度のより一層の低温化を図ることが求められている。蓄熱効率の改良や、蓄熱システムの適用温度域の拡張などの側面からも、化学蓄熱材の動作温度の改良は依然として重要な課題である。
According to the techniques disclosed in
本発明は、上記現状に鑑み、カルシウム及び／又はマグネシウムの水酸化物の脱水反応を利用した蓄熱を行なう化学蓄熱材において、より高い反応率を示し、より低温での蓄熱を実現できる化学蓄熱材及びその製造方法を提供することを目的とする。 In view of the above situation, the present invention is a chemical heat storage material that exhibits a higher reaction rate and can realize heat storage at a lower temperature in a chemical heat storage material that stores heat using a dehydration reaction of a hydroxide of calcium and / or magnesium. And its manufacturing method.
上記の課題を解決するために、本発明者らが種々検討を重ねたところ、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物を含む化学蓄熱材において、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に、リチウムの水酸化物とリチウムの塩化物を共添加してなる組成物が、化学蓄熱材としてより低温での蓄熱を実現できることを見出し、本発明に至った。さらに、本発明者らは鋭意検討を行ったところ、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に添加する、リチウムの水酸化物とリチウムの塩化物の添加比率の範囲を特定することにより、反応温度の低温化により効果が高いことを見出した。 As a result of various studies conducted by the present inventors in order to solve the above problems, hydroxylation of calcium and / or magnesium in a chemical heat storage material containing a hydroxide and / or oxide of calcium and / or magnesium. We have found that a composition obtained by co-adding a hydroxide of lithium and a chloride of lithium to a substance and / or an oxide can realize heat storage at a lower temperature as a chemical heat storage material, and has reached the present invention. Furthermore, as a result of diligent studies, the present inventors specify the range of the addition ratio of lithium hydroxide and lithium chloride to be added to the hydroxide and / or oxide of calcium and / or magnesium. As a result, it was found that the effect is higher by lowering the reaction temperature.
すなわち第一の本発明は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、リチウムの水酸化物、及び、リチウムの塩化物を含む化学蓄熱材に関する。前記化学蓄熱材において、リチウムの水酸化物及びリチウムの塩化物の総量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜５０モル％であることが好ましい。また、リチウムの水酸化物とリチウムの塩化物のモル比率は、０．１〜９の範囲であることが好ましく、０．２５〜４の範囲にあるのがより好ましく、０．５〜２．０の範囲であることがさらに好ましい。
前記化学蓄熱材は、さらに、ニッケル、コバルト、銅、アルミニウム、鉄及び亜鉛からなる群より選択される少なくとも１種の金属の化合物を含んでもよく、前記金属の量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜４０モル％であることが好ましい。
第二の本発明は、化学蓄熱材の製造方法であって、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、リチウムの水酸化物、及び、リチウムの塩化物を混合する工程を含む、製造方法に関する。前記製造方法において、リチウムの水酸化物とリチウムの塩化物の総量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜５０モル％であることが好ましい。また、前記リチウムの水酸化物とリチウムの塩化物のモル比率は、０．１〜９の範囲であることが好ましく、０．２５〜４の範囲にあるのがより好ましく、０．５〜２．０の範囲であることがさらに好ましい。
前記混合工程において、さらに、ニッケル、コバルト、銅、アルミニウム、鉄及び亜鉛からなる群より選択される少なくとも１種の金属の化合物を混合してもよく、前記金属の量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜４０モル％であることが好ましい。That is, the first invention relates to a chemical heat storage material containing a hydroxide and / or oxide of calcium and / or magnesium, a hydroxide of lithium, and a chloride of lithium. In the chemical heat storage material, the total amount of lithium hydroxide and lithium chloride is preferably 0.1 to 50 mol% with respect to the calcium and / or magnesium hydroxide and / or oxide. .. The molar ratio of lithium hydroxide to lithium chloride is preferably in the range of 0.1 to 9, more preferably in the range of 0.25 to 4, and more preferably 0.5 to 2. It is more preferably in the range of 0.
The chemical heat storage material may further contain a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron and zinc, and the amount of the metal is the calcium and / or magnesium. It is preferably 0.1 to 40 mol% with respect to the hydroxide and / or oxide of.
The second invention is a method for producing a chemical heat storage material, which comprises a step of mixing a hydroxide and / or oxide of calcium and / or magnesium with a hydroxide of lithium and a chloride of lithium. Including, regarding the manufacturing method. In the production method, the total amount of lithium hydroxide and lithium chloride is preferably 0.1 to 50 mol% with respect to the calcium and / or magnesium hydroxide and / or oxide. The molar ratio of lithium hydroxide to lithium chloride is preferably in the range of 0.1 to 9, more preferably in the range of 0.25 to 4, and more preferably 0.5 to 2. It is more preferably in the range of 0.0.
In the mixing step, a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron and zinc may be further mixed, and the amount of the metal is the calcium and / or the above. It is preferably 0.1 to 40 mol% with respect to the hydroxide and / or oxide of magnesium.
本発明によると、カルシウム及び／又はマグネシウムの水酸化物の脱水反応を利用した蓄熱を行なう化学蓄熱材において、より高い反応率を示し、より低温での蓄熱を実現できる化学蓄熱材及びその製造方法を提供することができる。 According to the present invention, in a chemical heat storage material that stores heat using the dehydration reaction of a hydroxide of calcium and / or magnesium, a chemical heat storage material that exhibits a higher reaction rate and can realize heat storage at a lower temperature and a method for producing the same. Can be provided.
以下、本発明の実施形態を詳細に説明する。
本発明で製造する化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物及び酸化物による以下の反応式で表される可逆反応を利用したものである。
ＣａＯ＋Ｈ２Ｏ⇔Ｃａ（ＯＨ）２ △Ｈ＝−１０９．２ｋＪ／モル
ＭｇＯ＋Ｈ２Ｏ⇔Ｍｇ（ＯＨ）２ △Ｈ＝−８１．２ｋＪ／モルHereinafter, embodiments of the present invention will be described in detail.
The chemical heat storage material produced by the present invention utilizes a reversible reaction represented by the following reaction formula using hydroxides and oxides of calcium and / or magnesium.
CaO + H 2 O⇔Ca (OH) 2 ΔH = −109.2 kJ / mol MgO + H 2 O⇔Mg (OH) 2 ΔH = -81.2 kJ / mol
各式中、右方向への反応は酸化カルシウム又は酸化マグネシウムの水和発熱反応である。反対に、左方向への反応は水酸化カルシウム又は水酸化マグネシウムの脱水吸熱反応である。すなわち本発明の化学蓄熱材は、水酸化カルシウム又は水酸化マグネシウムの脱水反応が進行することによって蓄熱することができ、また、蓄えられた熱エネルギーを、酸化カルシウム又は酸化マグネシウムの水和反応が進行することによって供給することができる。 In each formula, the reaction to the right is a hydration exothermic reaction of calcium oxide or magnesium oxide. On the contrary, the reaction to the left is a dehydration endothermic reaction of calcium hydroxide or magnesium hydroxide. That is, the chemical heat storage material of the present invention can store heat by advancing the dehydration reaction of calcium hydroxide or magnesium hydroxide, and the stored heat energy is used by the hydration reaction of calcium oxide or magnesium oxide. Can be supplied by
本発明における化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物、カルシウム及び／又はマグネシウムの酸化物いずれかを含むものであればよく、双方を含むものであってもよい。また、カルシウムとマグネシウムのいずれか１種を含むものであればよく、双方を含むものであってもよい。 The chemical heat storage material in the present invention may contain any of calcium and / or magnesium hydroxides and calcium and / or magnesium oxides, and may contain both. Further, it may contain any one of calcium and magnesium, and may contain both of them.
本発明の化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に、リチウムの化合物を含むものであって、当該リチウムの化合物として、リチウムの水酸化物及び塩化物を含む化学蓄熱材に関する。リチウムの化合物として、リチウムの水酸化物及び塩化物の両方を配合することで、化学蓄熱材の反応率を高めて、より低温での蓄熱を実現することができる。 The chemical heat storage material of the present invention contains a lithium compound in a hydroxide and / or oxide of calcium and / or magnesium, and the lithium compound contains a hydroxide and a chloride of lithium. Regarding chemical heat storage materials. By blending both lithium hydroxide and chloride as the lithium compound, the reaction rate of the chemical heat storage material can be increased and heat storage at a lower temperature can be realized.
前記リチウムの化合物の使用量に関しては、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物の量を１００モル％としたときに、両化合物の合計量が、０．１〜５０モル％であることが好ましい。この範囲より両化合物の合計量が少なくなると、これら化合物の共添加による反応率向上または蓄熱温度の低温化を達成することが困難になる。また、両化合物の合計量が前記範囲より多くなると、母材となるカルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物への影響が大きく、化学蓄熱材による単位体積又は単位質量あたりの蓄熱量が低下する恐れがある。前記両化合物の合計量は、０．１〜２０モル％が好ましく、０．３〜１５モル％がより好ましく、０．５〜１０モル％がさらに好ましく、０．８〜８モル％がよりさらに好ましく、１〜６モル％が特に好ましい。 Regarding the amount of the lithium compound used, when the amount of the hydroxide and / or oxide of the calcium and / or magnesium is 100 mol%, the total amount of both compounds is 0.1 to 50 mol%. Is preferable. If the total amount of both compounds is smaller than this range, it becomes difficult to improve the reaction rate or lower the heat storage temperature by co-adding these compounds. Further, when the total amount of both compounds is larger than the above range, the influence of calcium and / or magnesium as a base material on the hydroxide and / or oxide is large, and the heat storage per unit volume or mass by the chemical heat storage material is large. The amount may decrease. The total amount of both compounds is preferably 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, further preferably 0.5 to 10 mol%, still more preferably 0.8 to 8 mol%. Preferably, 1-6 mol% is particularly preferred.
さらに、前記リチウムの化合物の含有比率に関しては、モル基準で、前記水酸化リチウムの含有量／前記塩化リチウムの含有量が、０．１〜９の範囲にあることが好ましい。この範囲より前記水酸化リチウムと前記塩化リチウムの含有比率が小さくなったり大きくなったりすると、両化合物の共添加による反応率向上または蓄熱温度の低温化を達成することが困難になる。前記含有比率は、０．２５〜４の範囲にあるのがより好ましく、０．５〜２の範囲にあることがさらに好ましい。 Further, regarding the content ratio of the lithium compound, it is preferable that the content of the lithium hydroxide / the content of the lithium chloride is in the range of 0.1 to 9 on a molar basis. If the content ratio of the lithium hydroxide and the lithium chloride becomes smaller or larger than this range, it becomes difficult to improve the reaction rate or lower the heat storage temperature by co-adding both compounds. The content ratio is more preferably in the range of 0.25 to 4, and even more preferably in the range of 0.5 to 2.
本発明の化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、水酸化リチウム、塩化リチウムに加えて、さらに特定の金属の化合物を含んでも良い。前記特定の金属の化合物をさらに含めることで、化学蓄熱材の反応率をより高めることができる。この時、前記特定の金属の化合物は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と化学的に複合化していることが好ましい。 The chemical heat storage material of the present invention may contain a hydroxide and / or oxide of calcium and / or magnesium, lithium hydroxide, lithium chloride, and a compound of a specific metal. By further including the compound of the specific metal, the reaction rate of the chemical heat storage material can be further increased. At this time, it is preferable that the compound of the specific metal is chemically compounded with a hydroxide and / or oxide of calcium and / or magnesium.
前記特定の金属は、ニッケル、コバルト、銅、アルミニウム、鉄及び亜鉛からなる群より選択され、これらを１種のみ含むものであってもよく、２種以上を組み合わせて含むものであっても良い。このうち、ニッケル、コバルト及びアルミニウムからなる群より選択される少なくとも１種が好ましく、ニッケル及び／又はコバルトがより好ましい。 The specific metal is selected from the group consisting of nickel, cobalt, copper, aluminum, iron and zinc, and may contain only one kind of these, or may contain two or more kinds in combination. .. Of these, at least one selected from the group consisting of nickel, cobalt and aluminum is preferable, and nickel and / or cobalt is more preferable.
前記特定の金属の化合物としては特に限定されないが、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と複合化するものであることが好ましく、塩化物、臭化物等のハロゲン化物、水酸化物、酸化物、炭酸塩、酢酸塩、硝酸塩、又は硫酸塩などが挙げられる。これらを単独で使用しても良いし、２種以上を混合して使用しても良い。より具体的には、水酸化ニッケル、水酸化コバルト、ニッケルとコバルトの複合水酸化物、酸化ニッケル、酸化コバルト、及び／又はニッケルとコバルトの複合酸化物が好ましい。 The compound of the specific metal is not particularly limited, but is preferably a compound with a hydroxide and / or oxide of calcium and / or magnesium, and a halide such as chloride or bromide, or a hydroxide. , Oxides, carbonates, acetates, nitrates, sulfates and the like. These may be used alone, or two or more kinds may be mixed and used. More specifically, nickel hydroxide, cobalt hydroxide, a composite hydroxide of nickel and cobalt, nickel oxide, cobalt oxide, and / or a composite oxide of nickel and cobalt are preferable.
前記特定の金属の化合物の使用量としては、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物の量を１００モル％としたときに前記特定の金属の量が０．１〜４０モル％となる量であることが好ましい。これより前記特定の金属の量が少なくなると、前記特定の金属の化合物の使用による反応率向上または蓄熱温度の低温化を達成することが困難となる。また、前記特定の金属の量が前記範囲より多くなると、化学蓄熱材による単位体積又は単位質量あたりの蓄熱量が低下する恐れがある。前記特定の金属の量は、３〜４０モル％が好ましく、５〜３０モル％がより好ましく、１０〜２５モル％がさらに好ましい。当該特定の金属の化合物の使用量を調節することで、化学蓄熱材の脱水吸熱温度を制御することができる。 As for the amount of the compound of the specific metal used, the amount of the specific metal is 0.1 to 40 mol when the amount of the hydroxide and / or oxide of the calcium and / or magnesium is 100 mol%. The amount is preferably%. If the amount of the specific metal is smaller than this, it becomes difficult to improve the reaction rate or lower the heat storage temperature by using the compound of the specific metal. Further, if the amount of the specific metal exceeds the above range, the amount of heat stored per unit volume or unit mass of the chemical heat storage material may decrease. The amount of the specific metal is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%. By adjusting the amount of the compound of the specific metal used, the dehydration endothermic temperature of the chemical heat storage material can be controlled.
本発明における化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、水酸化リチウムと、塩化リチウムと、場合により特定の金属の化合物とが、単に物理的に混合又は分散されているものであってもよいが、これに限定されない。各構成成分の一部又は全部が互いと化学的に複合化したものであってよいし、また、各構成成分の一部又は全部が互いと化学的に反応して第三成分を生じているものであってもよい。 The chemical heat storage material in the present invention is simply a physical mixture or dispersion of a hydroxide and / or oxide of calcium and / or magnesium, lithium hydroxide, lithium chloride, and in some cases a compound of a specific metal. It may be, but is not limited to. Part or all of each component may be chemically complexed with each other, and part or all of each component chemically reacts with each other to form a third component. It may be a thing.
本発明の化学蓄熱材は、カルシウム及び／又はマグネシウムの水酸化物による吸熱脱水反応とカルシウム及び／又はマグネシウムの酸化物の水和発熱反応を利用した化学蓄熱材である。その範囲において、本発明の化学蓄熱材には、他の成分が含まれていても良く、以上で説明した構成成分以外の化学蓄熱成分や、化学蓄熱作用を示さない成分（例えばバインダー）が含まれていても良い。 The chemical heat storage material of the present invention is a chemical heat storage material that utilizes an endothermic dehydration reaction with a hydroxide of calcium and / or magnesium and a hydration exothermic reaction of an oxide of calcium and / or magnesium. Within that range, the chemical heat storage material of the present invention may contain other components, and includes chemical heat storage components other than the constituent components described above and components that do not exhibit a chemical heat storage action (for example, a binder). It may be.
本発明の化学蓄熱材の形状は特に限定されず、化学蓄熱材としての性状を実施可能な程度に損なわない限りにおいては、需要者の実施形態に応じた任意の形状を選択することが可能である。具体的には、本発明の化学蓄熱材は、粉末や、造粒体、成形体などの形状のものであってよい。 The shape of the chemical heat storage material of the present invention is not particularly limited, and any shape can be selected according to the embodiment of the consumer as long as the properties of the chemical heat storage material are not impaired to the extent practicable. is there. Specifically, the chemical heat storage material of the present invention may be in the form of powder, granules, molded articles, or the like.
次に、本発明における化学蓄熱材を製造する方法について説明する。
本発明における化学蓄熱材を製造する方法は特に限定されないが、次に一例を説明する。まず、イオン交換水にカルシウム及び／又はマグネシウムの水酸化物の粉末を加えて攪拌混合する。次いでリチウムの化合物であるリチウムの水酸化物及びリチウムの塩化物を、またはリチウムの化合物と特定の金属の化合物を、同時に又は順次投入してさらに攪拌混合を行う。得られたスラリーを乾燥させ、乾燥粉末として化学蓄熱材を製造することができる。攪拌混合の方法は特に限定されず、溶媒であるイオン交換水とカルシウム及び／又はマグネシウムの水酸化物の粉末等が十分に混合されればよい。Next, the method for producing the chemical heat storage material in the present invention will be described.
The method for producing the chemical heat storage material in the present invention is not particularly limited, but an example will be described below. First, calcium and / or magnesium hydroxide powder is added to ion-exchanged water and mixed by stirring. Next, a lithium hydroxide and a lithium chloride, which are lithium compounds, or a lithium compound and a specific metal compound are added simultaneously or sequentially, and further stirring and mixing is performed. The obtained slurry can be dried to produce a chemical heat storage material as a dry powder. The method of stirring and mixing is not particularly limited, and it is sufficient that ion-exchanged water as a solvent and powder of a hydroxide of calcium and / or magnesium are sufficiently mixed.
各成分を加える順序は変更してもよい。この場合、例えば、最初にリチウムの化合物、または、リチウムの化合物と特定の金属の化合物をイオン交換水に溶解して、これにカルシウム及び／又はマグネシウムの水酸化物の粉末を加えてスラリーを作製し、必要に応じて金属の酸塩を添加した後に、乾燥させて化学蓄熱材を製造することができる。 The order in which each component is added may be changed. In this case, for example, a lithium compound or a lithium compound and a specific metal compound are first dissolved in ion-exchanged water, and a hydroxide powder of calcium and / or magnesium is added thereto to prepare a slurry. Then, if necessary, a metal acid salt can be added and then dried to produce a chemical heat storage material.
形状が粉末、造粒体、又は成形体の化学蓄熱材を製造するにあたっては、既知の手法を適用することが可能である。例えば、粉末の化学蓄熱材を製造する際には篩別、解砕、粉砕工程を適用することが可能である。また、造粒体の化学蓄熱材を製造する際には押出造粒、転動造粒、流動層造粒、スプレードライ等の造粒工程を適用することができる。成形体の化学蓄熱材を製造する際には、プレス成形、射出成形、ブロー成形、真空成形、押出成形による成形工程を適用することができる。 Known techniques can be applied in the production of chemical heat storage materials of powder, granules, or moldings in shape. For example, when producing a powdered chemical heat storage material, it is possible to apply sieving, crushing, and crushing steps. Further, when producing a chemical heat storage material for a granulated material, a granulation step such as extrusion granulation, rolling granulation, fluidized bed granulation, or spray drying can be applied. When producing a chemical heat storage material for a molded product, a molding process by press molding, injection molding, blow molding, vacuum molding, or extrusion molding can be applied.
本発明の化学蓄熱材は、１００〜３００℃程度の熱源、例えば工場排熱等からの未利用熱を吸熱して脱水することにより蓄熱することができる。脱水された化学蓄熱材は、乾燥状態に保つことにより容易に蓄熱状態を維持することができ、またその蓄熱状態を維持しながら所望の場所へ持ち運ぶことができる。放熱する場合には、水、好ましくは水蒸気と接触させることにより水和反応熱（場合により、水蒸気収着熱）を熱エネルギーとして取り出すことができる。また、気密封鎖空間内の一方で水蒸気収着を行わせると共に、他方では水を蒸発させることにより冷熱を発生させることもできる。 The chemical heat storage material of the present invention can store heat by absorbing and dehydrating unused heat from a heat source of about 100 to 300 ° C., for example, exhaust heat from a factory. The dehydrated chemical heat storage material can be easily maintained in a heat storage state by keeping it in a dry state, and can be carried to a desired place while maintaining the heat storage state. When radiating heat, the heat of hydration reaction (in some cases, the heat of sorption of water vapor) can be extracted as heat energy by contacting with water, preferably water vapor. Further, it is also possible to generate cold heat by accumulating water vapor on one side of the airtight chain space and evaporating water on the other side.
また、本発明の化学蓄熱材は、エンジンや燃料電池等から排出される排気ガスの熱を有効利用するのにも適している。例えば、排気ガスの熱は、自動車の暖機運転の短縮、搭乗者のアメニティーの向上、燃費の改善、排気ガス触媒の活性向上による排気ガスの低害化等に活用することができる。特に、エンジンでは運転による負荷が一定でなく排気出力も不安定であることから、エンジンからの排気熱の直接利用は必然的に非効率であり、不便を伴う。本発明の化学蓄熱材を利用すると、エンジンからの排気熱を一旦化学的に蓄熱し、熱需要に応じて熱出力することで、より理想的な排気熱利用が可能となる。 Further, the chemical heat storage material of the present invention is also suitable for effectively utilizing the heat of exhaust gas discharged from an engine, a fuel cell, or the like. For example, the heat of the exhaust gas can be utilized for shortening the warm-up operation of the automobile, improving the amenities of the passengers, improving the fuel efficiency, and reducing the harm of the exhaust gas by improving the activity of the exhaust gas catalyst. In particular, in an engine, the load due to operation is not constant and the exhaust output is unstable, so that the direct use of exhaust heat from the engine is inevitably inefficient and inconvenient. By using the chemical heat storage material of the present invention, the exhaust heat from the engine is once chemically stored and heat is output according to the heat demand, so that more ideal exhaust heat utilization becomes possible.
以下に実施例を掲げて本発明をさらに詳細に説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.
（評価方法）
各実施例及び比較例で得られた化学蓄熱材について、熱重量／示差熱分析測定装置（アドバンス理工製、ＴGＤ９６００）を用いて熱評価を行った。具体的には、試料である化学蓄熱材を電子天秤で計量し、熱天秤内の白金製セルに２０ｍｇ載せた。次いで、反応器内の試料に対して不活性なパージガス（アルゴン）を１００ｍＬ／分で流しながら、１２０℃で試料の物理吸着水を乾燥除去した。その後、マグネシウム系化学蓄熱材の試料は昇温速度２０℃／分で２７０℃まで加熱し、１時間維持し、脱水反応を行った。カルシウム系化学蓄熱材の試料は昇温速度２０℃／分で３５０℃まで加熱し、６時間維持し、脱水反応を行った。(Evaluation methods)
The chemical heat storage materials obtained in each Example and Comparative Example were subjected to thermal evaluation using a thermogravimetric / differential thermal analysis measuring device (manufactured by Advance Riko, TGD9600). Specifically, the chemical heat storage material as a sample was weighed with an electronic balance, and 20 mg was placed on a platinum cell in the heat balance. Next, the physically adsorbed water of the sample was dried and removed at 120 ° C. while flowing an inert purge gas (argon) to the sample in the reactor at 100 mL / min. Then, the sample of the magnesium-based chemical heat storage material was heated to 270 ° C. at a heating rate of 20 ° C./min and maintained for 1 hour to carry out a dehydration reaction. The sample of the calcium-based chemical heat storage material was heated to 350 ° C. at a heating rate of 20 ° C./min, maintained for 6 hours, and subjected to a dehydration reaction.
化学蓄熱材の反応率の算出は、揮発成分等の影響を除外するため、２００℃に昇温した時点での化学蓄熱材の重量を開始重量として反応率０％に設定し、マグネシウム又はカルシウムの水酸化物が全て酸化物に変化したと仮定した場合の重量減少値を反応率１００％と定めて行った。 In the calculation of the reaction rate of the chemical heat storage material, in order to exclude the influence of volatile components, etc., the reaction rate is set to 0% with the weight of the chemical heat storage material at the time of heating to 200 ° C as the starting weight, and magnesium or calcium. The weight loss value when it was assumed that all the hydroxides were changed to oxides was set as the reaction rate of 100%.
マグネシウム系化学蓄熱材の性能評価は、特に、２００℃到達時点から１,２００秒が経過した時点での重量減少値から算出された反応率に基づいて行なった。すなわち、本評価方法は、水酸化マグネシウムの熱分解が実質的に進行しない温度である２７０℃で化学蓄熱材を所定時間保持した時点での反応率を比較するものである。当該反応率が高いほど、吸熱脱水反応が早く進行しており、蓄熱量が大きく、かつ、より低温の熱によって蓄熱できることを示している。なお、表中の相対反応率の数字は、絶対値ではなく、比較例１における反応率を基準の１とした時の相対値を示すものである。 The performance evaluation of the magnesium-based chemical heat storage material was carried out based on the reaction rate calculated from the weight reduction value at the time when 1,200 seconds had passed from the time when the temperature reached 200 ° C. That is, this evaluation method compares the reaction rate at the time when the chemical heat storage material is held for a predetermined time at 270 ° C., which is a temperature at which the thermal decomposition of magnesium hydroxide does not substantially proceed. The higher the reaction rate, the faster the endothermic dehydration reaction proceeds, indicating that the amount of heat stored is large and that heat can be stored by heat at a lower temperature. The numbers of the relative reaction rates in the table are not absolute values, but indicate relative values when the reaction rate in Comparative Example 1 is set to 1 as a reference.
カルシウム系化学蓄熱材の性能評価は、特に、２００℃到達時点から３,６００秒が経過した時点での重量減少値から算出された反応率に基づいて行なった。すなわち、本評価方法は、水酸化カルシウムの熱分解が実質的に進行しない温度である３５０℃で化学蓄熱材を所定時間保持した時点での反応率を比較するものである。当該反応率が高いほど、吸熱脱水反応が早く進行しており、蓄熱量が大きく、かつ、より低温の熱によって蓄熱できることを示している。なお、表中の相対反応率の数字は、絶対値ではなく、比較例４における反応率を基準の１とした時の相対値を示すものである。 The performance evaluation of the calcium-based chemical heat storage material was carried out based on the reaction rate calculated from the weight loss value at the time when 3,600 seconds had passed from the time when the temperature reached 200 ° C. That is, this evaluation method compares the reaction rate when the chemical heat storage material is held for a predetermined time at 350 ° C., which is a temperature at which the thermal decomposition of calcium hydroxide does not substantially proceed. The higher the reaction rate, the faster the endothermic dehydration reaction proceeds, indicating that the amount of heat stored is large and that heat can be stored by heat at a lower temperature. The numbers of the relative reaction rates in the table are not absolute values, but indicate relative values when the reaction rate in Comparative Example 4 is set to 1 as a reference.
（実施例１）
水酸化マグネシウム（和光純薬工業製、純度９９．９%）を２ｇ秤量した。つづいて塩化リチウム一水和物(和光純薬工業製、純度９９．９％)を０．２０７ｇ秤量し、さらに水酸化リチウム一水和物（和光純薬工業製、純度９９．９％）を０．１４４ｇ秤量した。この時の試料組成（モル比）は、水酸化マグネシウム：塩化リチウム：水酸化リチウム＝１００：１０：１０である。イオン交換水５０ｍＬに、上記で秤量した塩化リチウム及び水酸化リチウムを投入し、水溶液を調製した。次いで、この水溶液に水酸化マグネシウムを投入し、ロータリーエバポレーターを用いて攪拌してスラリーを作製した。該スラリーをさらに加熱し水分を蒸発させた後、乾燥機（アドバンテック東洋 ＤＲＡ３３０ＤＡ）にて空気中１２０℃で１２時間以上乾燥させて水分を除去することで、化学蓄熱材を製造した。得られた化学蓄熱材について、上記評価方法で脱水反応挙動を確認し、反応率を算出した。(Example 1)
2 g of magnesium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%) was weighed. Next, weigh 0.207 g of lithium chloride monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%), and further add lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%). Weighed 0.144 g. The sample composition (molar ratio) at this time is magnesium hydroxide: lithium chloride: lithium hydroxide = 100: 10:10. Lithium chloride and lithium hydroxide weighed above were added to 50 mL of ion-exchanged water to prepare an aqueous solution. Next, magnesium hydroxide was added to this aqueous solution and stirred using a rotary evaporator to prepare a slurry. After further heating the slurry to evaporate the water content, the slurry was dried in air at 120 ° C. for 12 hours or more in a dryer (Advantech Toyo DRA330DA) to remove the water content, thereby producing a chemical heat storage material. The dehydration reaction behavior of the obtained chemical heat storage material was confirmed by the above evaluation method, and the reaction rate was calculated.
（実施例２）
水酸化マグネシウム、塩化リチウム、水酸化リチウムのモル比を１００：２０：２０になるように試薬を秤量し、実施例１と同様の操作で試料調製と評価を行った。(Example 2)
The reagents were weighed so that the molar ratios of magnesium hydroxide, lithium chloride, and lithium hydroxide were 100:20:20, and sample preparation and evaluation were performed in the same manner as in Example 1.
（実施例３）
水酸化マグネシウム、塩化リチウム、水酸化リチウムのモル比を１００：５：５になるように試薬を秤量し、実施例１と同様の操作で試料調製と評価を行った。(Example 3)
The reagents were weighed so that the molar ratios of magnesium hydroxide, lithium chloride, and lithium hydroxide were 100: 5: 5, and sample preparation and evaluation were performed in the same manner as in Example 1.
（実施例４）
水酸化マグネシウム、塩化リチウム、水酸化リチウムのモル比を１００：６：１２になるように試薬を秤量し、実施例１と同様の操作で試料調製と評価を行った。(Example 4)
The reagents were weighed so that the molar ratios of magnesium hydroxide, lithium chloride, and lithium hydroxide were 100: 6: 12, and sample preparation and evaluation were performed in the same manner as in Example 1.
（比較例１）
実施例１で用いた水酸化マグネシウムに対してリチウム化合物を添加していないものを試料とし、評価を行った。(Comparative Example 1)
A sample in which a lithium compound was not added to the magnesium hydroxide used in Example 1 was used as a sample and evaluated.
（比較例２）
水酸化マグネシウム、塩化リチウム、水酸化リチウムのモル比を１００：２０：０になるように試薬を秤量し、実施例１と同様の操作で試料調製と評価を行った。(Comparative Example 2)
The reagents were weighed so that the molar ratios of magnesium hydroxide, lithium chloride, and lithium hydroxide were 100: 20: 0, and sample preparation and evaluation were performed in the same manner as in Example 1.
（比較例３）
水酸化マグネシウム、塩化リチウム、水酸化リチウムのモル比を１００：０：２０になるように試薬を秤量し、実施例１と同様の操作で試料調製と評価を行った。(Comparative Example 3)
The reagents were weighed so that the molar ratios of magnesium hydroxide, lithium chloride, and lithium hydroxide were 100: 0: 20, and sample preparation and evaluation were performed in the same manner as in Example 1.
（実施例５）
水酸化カルシウム（和光純薬工業製、純度９９．９%）を２ｇ秤量した。つづいて塩化リチウム一水和物(和光純薬工業製、純度９９．９％)を０．０８２ｇ秤量し、さらに水酸化リチウム一水和物（和光純薬工業製、純度９９．９％）を０．０５７ｇ秤量した。この時の試料組成（モル比）は、水酸化カルシウム：塩化リチウム：水酸化リチウム＝１００：５：５である。イオン交換水５０ｍＬに、上記で秤量した塩化リチウム及び水酸化リチウムを投入し、水溶液を調製した。次いで、この水溶液に水酸化カルシウムを投入し、ロータリーエバポレーターを用いて攪拌してスラリーを作製した。該スラリーをさらに加熱し水分を蒸発させた後、乾燥機（アドバンテック東洋 ＤＲＡ３３０ＤＡ）にて空気中１２０℃で１２時間以上乾燥させて水分を除去することで、化学蓄熱材を製造した。得られた化学蓄熱材について、上記評価方法で脱水反応挙動を確認し、反応率を算出した。(Example 5)
2 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%) was weighed. Next, weigh 0.082 g of lithium chloride monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%), and further add lithium hydroxide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.9%). Weighed 0.057 g. The sample composition (molar ratio) at this time is calcium hydroxide: lithium chloride: lithium hydroxide = 100: 5: 5. Lithium chloride and lithium hydroxide weighed above were added to 50 mL of ion-exchanged water to prepare an aqueous solution. Next, calcium hydroxide was added to this aqueous solution and stirred using a rotary evaporator to prepare a slurry. After further heating the slurry to evaporate the water content, the slurry was dried in air at 120 ° C. for 12 hours or more in a dryer (Advantech Toyo DRA330DA) to remove the water content, thereby producing a chemical heat storage material. The dehydration reaction behavior of the obtained chemical heat storage material was confirmed by the above evaluation method, and the reaction rate was calculated.
（比較例４）
実施例５で用いた水酸化カルシウムに対してリチウム化合物を添加していないものを試料とし、評価を行った。(Comparative Example 4)
Evaluation was performed using a sample in which a lithium compound was not added to the calcium hydroxide used in Example 5.
（比較例５）
水酸化カルシウム、塩化リチウム、水酸化リチウムのモル比を１００：１０：０になるように試薬を秤量し、実施例５と同様の操作で試料調製と評価を行った。(Comparative Example 5)
The reagents were weighed so that the molar ratios of calcium hydroxide, lithium chloride, and lithium hydroxide were 100: 10: 0, and sample preparation and evaluation were performed in the same manner as in Example 5.
（比較例６）
水酸化カルシウム、塩化リチウム、水酸化リチウムのモル比を１００：０：１０になるように試薬を秤量し、実施例５と同様の操作で試料調製と評価を行った。(Comparative Example 6)
The reagents were weighed so that the molar ratios of calcium hydroxide, lithium chloride, and lithium hydroxide were 100: 0: 10, and sample preparation and evaluation were performed in the same manner as in Example 5.
表１では、比較例１で得られた水酸化マグネシウム単体の反応率（脱水反応転化率）を基準とし、実施例１〜４、比較例２〜３で得られた反応率を相対反応率に換算して得られた数字を示した。 In Table 1, the reaction rate (dehydration reaction conversion rate) of magnesium hydroxide alone obtained in Comparative Example 1 is used as a reference, and the reaction rates obtained in Examples 1 to 4 and Comparative Examples 2 to 3 are used as relative reaction rates. The numbers obtained by conversion are shown.
図１は、実施例１〜４、比較例１〜３で示された反応率の経時変化を示すグラフである。なお、表１で示した相対反応率は、図１におけるグラフの１,２００秒時点での反応率に基づいて算出した相対値である。 FIG. 1 is a graph showing changes over time in the reaction rates shown in Examples 1 to 4 and Comparative Examples 1 to 3. The relative reaction rate shown in Table 1 is a relative value calculated based on the reaction rate at 1,200 seconds in the graph in FIG. 1.
比較例１の水酸化マグネシウム単体は、ここで用いている評価条件下では脱水反応転化率が低く、吸熱脱水反応がほとんど進行しなかった。表１及び図１より、水酸化リチウムと塩化リチウムを所定の比率で共添加して製造した実施例１から４の化学蓄熱材は、比較例１と同じ評価条件下において、比較例１と比較して反応率が大幅に高く、吸熱脱水反応が迅速に進行していることが確認できる。これより、実施例１から４の化学蓄熱材は、比較例１の水酸化マグネシウム単体と比較して、蓄熱量が大きく、また、より低温の熱でも蓄熱できることが分かる。 The magnesium hydroxide simple substance of Comparative Example 1 had a low dehydration reaction conversion rate under the evaluation conditions used here, and the endothermic dehydration reaction hardly proceeded. From Table 1 and FIG. 1, the chemical endothermic materials of Examples 1 to 4 produced by co-adding lithium hydroxide and lithium chloride in a predetermined ratio were compared with Comparative Example 1 under the same evaluation conditions as Comparative Example 1. It can be confirmed that the reaction rate is significantly high and the endothermic dehydration reaction is proceeding rapidly. From this, it can be seen that the chemical heat storage materials of Examples 1 to 4 have a large amount of heat storage as compared with the magnesium hydroxide simple substance of Comparative Example 1, and can store heat even at a lower temperature.
さらに、実施例１から４の水酸化リチウムと塩化リチウムを所定の比率で共添加した化学蓄熱材は、比較例２及び３の水酸化リチウム又は塩化リチウムを単体で添加した化学蓄熱材と比較しても、蓄熱量が大きく、また、より低温の熱でも蓄熱できることが分かる。 Further, the chemical heat storage material in which lithium hydroxide and lithium chloride in Examples 1 to 4 were co-added at a predetermined ratio was compared with the chemical heat storage material in which lithium hydroxide or lithium chloride was added alone in Comparative Examples 2 and 3. However, it can be seen that the amount of heat stored is large and that even lower temperature heat can be stored.
表２では、比較例４で得られた水酸化カルシウム単体の反応率（脱水反応転化率）を基準とし、実施例５、比較例５及び６で得られた反応率を相対反応率に変換して得られた数字を示した。 In Table 2, the reaction rate (dehydration reaction conversion rate) of calcium hydroxide alone obtained in Comparative Example 4 is used as a reference, and the reaction rates obtained in Examples 5, 5 and 6 are converted into relative reaction rates. The numbers obtained from the above are shown.
図２は、実施例５、比較例４〜６で示された反応率の経時変化を示すグラフである。なお、表２で示した相対反応率は、図２におけるグラフの３,６００秒時点での反応率に基づいて算出した相対値である。 FIG. 2 is a graph showing the time course of the reaction rate shown in Example 5 and Comparative Examples 4 to 6. The relative reaction rate shown in Table 2 is a relative value calculated based on the reaction rate at 3,600 seconds in the graph in FIG.
比較例４の水酸化カルシウム単体は、ここで用いている評価条件下では脱水反応転化率が低く、吸熱脱水反応がほとんど進行しなかった。表２及び図２より、水酸化リチウムと塩化リチウムを所定の比率で共添加して製造した実施例５の化学蓄熱材は、比較例４と同じ評価条件下において、比較例４と比較して反応率が大幅に高く、吸熱脱水反応が迅速に進行していることが確認できる。これより、実施例５の化学蓄熱材は、比較例４の水酸化カルシウム単体と比較して、蓄熱量が大きく、また、より低温の熱でも蓄熱できることが分かる。 The calcium hydroxide simple substance of Comparative Example 4 had a low dehydration reaction conversion rate under the evaluation conditions used here, and the endothermic dehydration reaction hardly proceeded. From Table 2 and FIG. 2, the chemical endothermic material of Example 5 produced by co-adding lithium hydroxide and lithium chloride in a predetermined ratio was compared with Comparative Example 4 under the same evaluation conditions as Comparative Example 4. It can be confirmed that the reaction rate is significantly high and the endothermic dehydration reaction is proceeding rapidly. From this, it can be seen that the chemical heat storage material of Example 5 has a large amount of heat storage as compared with the simple substance of calcium hydroxide of Comparative Example 4, and can store heat even at a lower temperature.
さらに、実施例５の水酸化リチウムと塩化リチウムを所定の比率で共添加した化学蓄熱材は、比較例５及び６の水酸化リチウム又は塩化リチウムを単体で添加した化学蓄熱材と比較しても、蓄熱量が大きく、また、より低温の熱でも蓄熱できることが分かる。
Further, the chemical heat storage material to which lithium hydroxide and lithium chloride are co-added in a predetermined ratio of Example 5 can be compared with the chemical heat storage material to which lithium hydroxide or lithium chloride is added alone in Comparative Examples 5 and 6. It can be seen that the amount of heat stored is large and that even lower temperature heat can be stored.
Claims (10)
前記金属の量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜４０モル％である、請求項１〜４のいずれかに記載の化学蓄熱材。Further, it contains a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron and zinc.
The chemical heat storage material according to any one of claims 1 to 4, wherein the amount of the metal is 0.1 to 40 mol% with respect to the hydroxide and / or oxide of the calcium and / or magnesium.
カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物と、リチウムの水酸化物、及び、リチウムの塩化物を混合する工程を含む、製造方法。A method for manufacturing chemical heat storage materials
A production method comprising the steps of mixing a hydroxide and / or oxide of calcium and / or magnesium with a hydroxide of lithium and a chloride of lithium.
前記金属の量は、前記カルシウム及び／又はマグネシウムの水酸化物及び／又は酸化物に対して０．１〜４０モル％である、請求項６〜９のいずれかに記載の製造方法。
In the mixing step, a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron and zinc is further mixed.
The production method according to any one of claims 6 to 9, wherein the amount of the metal is 0.1 to 40 mol% with respect to the hydroxide and / or oxide of the calcium and / or magnesium.
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| US20140358206A1 (en) * | 2013-05-31 | 2014-12-04 | Laurie HIROKANE | Therapeutic heating and cooling packs comprising decorative elements |
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2019
- 2019-02-06 WO PCT/JP2019/004259 patent/WO2019159791A1/en active Application Filing
- 2019-02-06 CN CN201980013119.3A patent/CN111684039B/en active Active
- 2019-02-06 JP JP2020500433A patent/JP7248989B2/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007309561A (en) * | 2006-05-17 | 2007-11-29 | Tokyo Institute Of Technology | Chemical heat pump |
| JP2009186119A (en) * | 2008-02-07 | 2009-08-20 | Tokyo Institute Of Technology | Chemical heat pump |
| JP2013216763A (en) * | 2012-04-06 | 2013-10-24 | Toyota Central R&D Labs Inc | Chemical heat storage material, and reaction device, heat storage device, and vehicle |
| JP2017002220A (en) * | 2015-06-12 | 2017-01-05 | 国立大学法人東京工業大学 | Chemical heat storage material |
| JP2017218492A (en) * | 2016-06-06 | 2017-12-14 | 古河電気工業株式会社 | Chemical thermal storage material and heat storage container using chemical thermal storage material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111684039B (en) | 2021-12-28 |
| KR20200121305A (en) | 2020-10-23 |
| CN111684039A (en) | 2020-09-18 |
| JP7248989B2 (en) | 2023-03-30 |
| WO2019159791A1 (en) | 2019-08-22 |
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