CN110770320B - Chemical heat storage material and method for producing same, and chemical heat pump and method for operating same - Google Patents
Chemical heat storage material and method for producing same, and chemical heat pump and method for operating same Download PDFInfo
- Publication number
- CN110770320B CN110770320B CN201880043821.XA CN201880043821A CN110770320B CN 110770320 B CN110770320 B CN 110770320B CN 201880043821 A CN201880043821 A CN 201880043821A CN 110770320 B CN110770320 B CN 110770320B
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- China
- Prior art keywords
- metal
- chemical heat
- hydroxide
- alkaline earth
- heat storage
- Prior art date
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- 239000000126 substance Substances 0.000 title claims abstract description 183
- 238000005338 heat storage Methods 0.000 title claims abstract description 116
- 239000011232 storage material Substances 0.000 title claims abstract description 84
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- 238000000034 method Methods 0.000 title description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 112
- 239000002184 metal Substances 0.000 claims abstract description 106
- 229910052751 metal Inorganic materials 0.000 claims abstract description 105
- 239000002253 acid Chemical class 0.000 claims abstract description 103
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 62
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 62
- 239000000463 material Substances 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 51
- 150000001339 alkali metal compounds Chemical class 0.000 claims abstract description 27
- 229910052783 alkali metal Inorganic materials 0.000 claims description 24
- 150000001340 alkali metals Chemical class 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000011575 calcium Substances 0.000 claims description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 239000011777 magnesium Substances 0.000 claims description 18
- 229910052749 magnesium Inorganic materials 0.000 claims description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052712 strontium Inorganic materials 0.000 claims description 8
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 88
- 238000006297 dehydration reaction Methods 0.000 abstract description 23
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 32
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 28
- 239000000347 magnesium hydroxide Substances 0.000 description 28
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 28
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 26
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 18
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 17
- 239000000920 calcium hydroxide Substances 0.000 description 17
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 17
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 15
- 229940091250 magnesium supplement Drugs 0.000 description 14
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- -1 aliphatic hydroxy acids Chemical class 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- 230000036571 hydration Effects 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 6
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 6
- 239000011654 magnesium acetate Substances 0.000 description 6
- 229940069446 magnesium acetate Drugs 0.000 description 6
- 235000011285 magnesium acetate Nutrition 0.000 description 6
- 239000000395 magnesium oxide Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 4
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 4
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000010908 plant waste Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000003628 tricarboxylic acids Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- PJJZFXPJNUVBMR-UHFFFAOYSA-L magnesium benzoate Chemical compound [Mg+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 PJJZFXPJNUVBMR-UHFFFAOYSA-L 0.000 description 2
- 239000004337 magnesium citrate Substances 0.000 description 2
- 229960005336 magnesium citrate Drugs 0.000 description 2
- 235000002538 magnesium citrate Nutrition 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- KHPXUQMNIQBQEV-UHFFFAOYSA-N oxaloacetic acid Chemical compound OC(=O)CC(=O)C(O)=O KHPXUQMNIQBQEV-UHFFFAOYSA-N 0.000 description 2
- 150000003009 phosphonic acids Chemical class 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 229940091181 aconitic acid Drugs 0.000 description 1
- 229940114077 acrylic acid Drugs 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 239000004301 calcium benzoate Substances 0.000 description 1
- 235000010237 calcium benzoate Nutrition 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- HZQXCUSDXIKLGS-UHFFFAOYSA-L calcium;dibenzoate;trihydrate Chemical compound O.O.O.[Ca+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 HZQXCUSDXIKLGS-UHFFFAOYSA-L 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
- 239000003795 chemical substances by application Substances 0.000 description 1
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 1
- 235000015165 citric acid Nutrition 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
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000004715 keto acids Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229940071257 lithium acetate Drugs 0.000 description 1
- 229940031993 lithium benzoate Drugs 0.000 description 1
- 229940071264 lithium citrate Drugs 0.000 description 1
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 230000003472 neutralizing effect Effects 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- JXOHGGNKMLTUBP-HSUXUTPPSA-N shikimic acid Chemical compound O[C@@H]1CC(C(O)=O)=C[C@@H](O)[C@H]1O JXOHGGNKMLTUBP-HSUXUTPPSA-N 0.000 description 1
- JXOHGGNKMLTUBP-JKUQZMGJSA-N shikimic acid Natural products O[C@@H]1CC(C(O)=O)=C[C@H](O)[C@@H]1O JXOHGGNKMLTUBP-JKUQZMGJSA-N 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-N squaric acid Chemical compound OC1=C(O)C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
Images
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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
- C09K5/16—Materials undergoing chemical reactions when used
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
- F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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- Organic Chemistry (AREA)
- Sorption Type Refrigeration Machines (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Provided is a chemical heat storage material which exhibits a higher reaction rate and can store heat at a lower temperature in a chemical heat storage material which stores heat by a dehydration reaction of an alkaline earth metal hydroxide. The chemical heat-accumulative material comprises a hydroxide and/or oxide of an alkaline earth metal and an acid salt of a metal. The chemical heat storage material further contains an alkali metal compound, and the amount of the alkali metal compound is preferably 0.1 to 50 mol% relative to the hydroxide and/or oxide of the alkaline earth metal. The amount of the acid salt of the metal is preferably 0.05 to 30 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
Description
Technical Field
The present invention relates to a chemical heat storage material and a method for producing the same, and a chemical heat pump and a method for operating the same.
Background
In recent years, reduction in the use of fossil fuels has been demanded due to carbon dioxide emission restrictions, and it has been necessary to utilize exhaust heat in addition to energy saving in each process. As a means for utilizing the exhaust heat, heat storage in warm water of 100 ℃ or lower is known, which utilizes water. However, the following are present in warm water heat storage: (1) the heat storage device cannot store heat for a long time due to heat release loss, (2) the heat storage device is difficult to be compact because a large amount of water is required because sensible heat is small, and (3) the output temperature is gradually reduced because it is not constant according to the amount of use. Therefore, in order to promote the domestic use of such exhaust heat, it is necessary to develop a more efficient heat storage technique.
As an efficient heat storage technique, there is a chemical heat storage method. The chemical heat storage method involves chemical changes such as adsorption and hydration of substances, and therefore has a higher heat storage amount per unit mass than a heat storage method using latent heat or sensible heat of a material itself (water, molten salt, or the like). As the chemical heat storage method, there are proposed a water vapor adsorption/desorption method using adsorption and desorption of water vapor in the atmosphere, an ammonia adsorption (ammine complex formation reaction) to a metal salt, a reaction by adsorption and desorption of an organic substance such as ethanol, and the like. The water vapor adsorption and desorption method is most advantageous in view of environmental load and simplicity of the apparatus. Calcium hydroxide and magnesium hydroxide are known as alkaline earth metal hydroxides as chemical heat-accumulative materials for use in the water vapor adsorption and desorption method.
However, these calcium hydroxide and magnesium hydroxide do not undergo an effective dehydration reaction at a low temperature of 100 to 400 ℃, and therefore have a problem that they do not function as a practical heat-storage material.
In order to solve this problem, patent document 1 proposes a chemical heat storage material capable of storing heat at about 100 to 300 ℃.
Patent document 2 proposes a chemical heat storage material obtained by adding a hygroscopic metal salt such as lithium chloride to a hydroxide of magnesium or calcium for the purpose of improving the heat storage amount of the chemical heat storage material described in patent document 1.
Prior art documents:
patent documents:
patent document 1, Japanese patent laid-open No. 2007-309561;
patent document 2, Japanese patent laid-open No. 2009-186119.
Disclosure of Invention
The problems to be solved by the invention are as follows:
according to the techniques disclosed in patent documents 1 and 2, although the heat storage operation temperature can be lowered to some extent, when the plant waste heat is to be stored, for example, the temperature range of the plant waste heat is 200 to 250 ℃ or less, and therefore, the heat storage operation temperature is not sufficiently low, and it is difficult to efficiently use the plant waste heat, and it is desired to further lower the operation temperature. Improvement of the operating temperature of the chemical heat storage material is still an important issue from the viewpoints of improvement of heat storage efficiency, expansion of the applicable temperature range of the heat storage system, and the like.
In view of the above-described situation, an object of the present invention is to provide a chemical heat storage material that stores heat by a dehydration reaction of an alkaline earth metal hydroxide, a chemical heat storage material that exhibits a higher reaction rate and can store heat at a lower temperature, a method for producing the same, a chemical heat pump for storing heat and releasing heat by using the chemical heat storage material, and a method for operating the same.
Means for solving the problems:
in order to solve the above problems, the present inventors have conducted various studies several times and found that a chemical heat storage material comprising a hydroxide and/or an oxide of an alkaline earth metal and an acid salt of a metal can produce a chemical heat storage material which exhibits a higher reaction rate and can store heat at a lower temperature when producing a chemical heat storage material using a dehydration reaction of a hydroxide of an alkaline earth metal, and the present invention has been achieved.
That is, the first invention relates to a chemical heat storage material comprising a hydroxide and/or oxide of an alkaline earth metal and an acid salt of a metal.
The second invention relates to a chemical heat storage material comprising a hydroxide and/or oxide of an alkaline earth metal, a compound of an alkali metal and an acid salt of a metal; the amount of the alkali metal compound is 0.1 to 50 mol% relative to the hydroxide and/or oxide of the alkaline earth metal, and the compound may further contain at least 1 specific metal selected from the group consisting of nickel, cobalt, copper and aluminum; the amount of the specific metal is 0.1 to 40 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
Preferably, the amount of the acid salt of the metal is 0.05 to 30 mol% based on the hydroxide and/or oxide of the alkaline earth metal. Preferably, the alkaline earth metal is at least 1 selected from the group consisting of calcium, magnesium, strontium, and barium, and the alkali metal is at least 1 selected from the group consisting of lithium, potassium, and sodium.
Preferably, the acid salt of a metal is an acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals, and more preferably, the acid salt of a metal is an acid salt of at least 1 metal selected from the group consisting of aluminum, iron, cobalt, nickel, copper and zinc. More preferably, the acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals is an acid salt of at least 1 metal selected from the group consisting of lithium, sodium, potassium, calcium, magnesium, strontium, and barium.
The third invention relates to a manufacturing method, which is a manufacturing method of a chemical heat storage material; comprising a step of mixing a hydroxide and/or an oxide of an alkaline earth metal with an acid salt of the metal.
The fourth invention relates to a method for producing a chemical heat-accumulative material; comprises a step of mixing a hydroxide and/or an oxide of an alkaline earth metal, a compound of an alkali metal and an acid salt of a metal; the amount of the alkali metal compound is 0.1 to 50 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
Relates to the following manufacturing method: in the production method, in the mixing step, a compound of at least 1 specific metal selected from the group consisting of nickel, cobalt, copper, and aluminum may be further mixed; the amount of the metal is 0.1 to 40 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
The fifth invention relates to a chemical heat pump, which utilizes the endothermic dehydration reaction and the hydration exothermic reaction; comprising: a reactor for accommodating a chemical heat storage material containing a hydroxide and/or an oxide of an alkaline earth metal; a heat supply unit thermally connected to the reactor and configured to supply heat from outside to the chemical heat storage material; a heat recovery unit thermally connected to the reactor and configured to take out heat generated from the chemical heat storage material to the outside; a reservoir for storing water; a connection pipe connecting the reactor and the reservoir to allow water to pass therethrough; and a salt supply mechanism for supplying an acid salt of a metal into the chemical heat pump.
A sixth invention relates to a method of operating the chemical heat pump; the method comprises the following steps: supplying an acid salt of a metal to the chemical heat storage material contained in the reactor by the salt supply mechanism; and a step of supplying heat to the chemical heat storage material by the heat supply means, and performing an endothermic dehydration reaction of the chemical heat storage material to store heat. The method may further include a step of moving the water in the reservoir to the reactor to contact the chemical heat storage material, and causing a hydration heat generation reaction of the chemical heat storage material to release heat.
The invention has the following effects:
according to the present invention, a chemical heat storage material which can store heat by a dehydration reaction of an alkaline earth metal hydroxide, exhibits a higher reaction rate, and can store heat at a lower temperature, and a method for producing the same can be provided.
Further, according to the present invention, it is possible to provide a chemical heat pump which exhibits a higher reaction rate and can store heat at a lower temperature in a chemical heat pump which stores heat and releases heat by using a chemical heat storage material which stores heat by a dehydration reaction of an alkaline earth metal hydroxide, and an operating method thereof.
Drawings
Fig. 1 is a conceptual diagram showing a structure of a chemical heat pump according to an embodiment of the present invention;
fig. 2 is a graph showing the change with time of the reaction rate shown in example 1 and comparative examples 1 and 2 (the horizontal axis represents the elapsed time (seconds) from the start of temperature rise, and the vertical axis represents the reaction rate (%);
fig. 3 is a graph showing the change with time of the reaction rate shown in examples 2 to 8 and comparative examples 1 and 2 (the horizontal axis represents the elapsed time (seconds) from the start of temperature rise, and the vertical axis represents the reaction rate (%);
fig. 4 is a graph showing the change with time of the reaction rate shown in examples 9 to 12 and comparative examples 3 and 4 (the horizontal axis represents the elapsed time (seconds) from the start of temperature rise, and the vertical axis represents the reaction rate (%)).
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The chemical heat storage material produced in the present invention utilizes the following reversible reaction by hydroxides and oxides of alkaline earth metals. In the following reaction formulae, calcium or magnesium is used as the alkaline earth metal;
CaO+H 2O⇔Ca(OH) 2delta H = -109.2 kJ/mole
MgO+H 2O⇔Mg(OH) 2Δ H = -81.2 kJ/mole
In the formulae, the reaction in the rightward direction is a hydration exothermic reaction of calcium oxide or magnesium oxide. In contrast, the reaction in the left direction is a dehydration endothermic reaction of calcium hydroxide or magnesium hydroxide. That is, the chemical heat-accumulative material of the present invention can accumulate heat by the dehydration reaction of calcium hydroxide or magnesium hydroxide, and can supply the accumulated thermal energy by the hydration reaction of calcium oxide or magnesium oxide.
The chemical heat-storage material in the present invention may contain either or both of a hydroxide of an alkaline earth metal and an oxide of an alkaline earth metal. Examples of the alkaline earth metal include calcium, magnesium, strontium, and barium. They may be contained in 1 kind alone, or in combination of 2 or more kinds. Among these, calcium and/or magnesium are preferable, and magnesium is more preferable. The alkaline earth metal hydroxide and the alkaline earth metal oxide are preferably: magnesium hydroxide, calcium hydroxide, a composite hydroxide of magnesium and calcium, magnesium oxide, calcium oxide, a composite oxide of magnesium and calcium may be used alone or in combination of 2 or more.
The present invention is characterized in that the chemical heat-accumulative material comprises a hydroxide and/or oxide of the alkaline earth metal and an acid salt of the metal. The acid salt of a metal means a salt formed by reacting a compound of a metal with an acid, and particularly preferably a salt formed by neutralizing a hydroxide of a metal with an acid. Specifically, for example, the following are: magnesium nitrate, magnesium acetate, magnesium benzoate, magnesium citrate, calcium nitrate, calcium acetate, calcium benzoate, calcium citrate, lithium nitrate, lithium acetate, lithium benzoate, lithium citrate, and the like, but are not limited thereto.
Examples of the metal constituting the acid salt of the metal include alkaline earth metals such as calcium, magnesium, strontium, and barium; alkali metals such as lithium, sodium, and potassium; aluminum, iron, cobalt, nickel, copper and zinc. They may be contained in 1 kind alone, or in combination of 2 or more kinds. Among these, calcium, lithium and/or magnesium are preferable, and calcium and/or magnesium are more preferable. The alkaline earth metal constituting the acid salt of the metal may be the same as or different from the alkaline earth metal constituting the hydroxide and/or oxide of the alkaline earth metal, but is preferably the same from the viewpoint of improving the reactivity of the chemical heat storage material. However, when the acid salt of a metal used in the present invention is an acid salt of an alkaline earth metal, it is preferable that a carbonate or chloride of an alkaline earth metal is not used as the acid salt of an alkaline earth metal.
The acid constituting the acid salt of the metal is not particularly limited, and a known acid may be suitably used, and may be an inorganic acid or an organic acid. The acid may be a water-soluble acid, or an acid which is hardly soluble or insoluble in water. Only 1 species may be used, or 2 or more species may be used in combination as appropriate.
Inorganic acids are for example: hydrochloric acid, hydrobromic acid, iodohydric acid, hydrofluoric acid, halogen oxyacids (halogen oxyacids), sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, sulfonic acid, boric acid, hydrocyanic acid, hexafluorophosphoric acid, and the like.
Organic acids are for example: organic sulfonic acids, organic phosphonic acids, aliphatic hydroxy acids (including dihydroxy acids, trihydroxy acids), aromatic hydroxy acids (including dihydroxy acids, trihydroxy acids), aliphatic carboxylic acids (including dicarboxylic acids, tricarboxylic acids), aliphatic unsaturated carboxylic acids (including dicarboxylic acids, tricarboxylic acids), aromatic unsaturated carboxylic acids (including dicarboxylic acids, tricarboxylic acids), other oxo acids, other oxo carboxylic acids, amino acids, and their derivatives.
Organic sulfonic acids are, for example: methanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and the like. Organic phosphonic acids are, for example: dimethyl phosphate, phenylphosphonic acid, and the like. Aliphatic or aromatic hydroxy acids are for example: lactic acid, malic acid, citric acid, tartaric acid, and the like. Aliphatic carboxylic acids or aliphatic unsaturated carboxylic acids are, for example: formic acid, acetic acid, propionic acid, butyric acid, acrylic acid, sorbic acid, pyruvic acid, oxalacetic acid, squaric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, maleic acid, aconitic acid, and the like. Aromatic carboxylic acids or aromatic unsaturated carboxylic acids are: benzoic acid, phthalic acid, salicylic acid, shikimic acid, gallic acid, pyromellitic acid, and the like. Amino acids are for example: aspartic acid, glutamic acid, and the like.
The amount of the acid salt of the metal is preferably 0.05 to 30 mol% based on 100 mol% of the hydroxide and/or oxide of the alkaline earth metal. If the amount of the metal acid salt used is less than this, the reaction rate cannot be increased or the heat storage temperature cannot be lowered by the addition of the acid salt. When the amount of the metal acid salt used is more than the above range, the influence on the hydroxide and/or oxide of the alkaline earth metal serving as the base material is large, and the heat storage amount per unit volume or unit mass of the chemical heat storage material may be reduced. The amount of the metal acid salt to be used is preferably 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, still more preferably 0.5 to 10 mol%, still more preferably 0.8 to 8 mol%, and particularly preferably 1 to 6%.
The chemical heat-accumulative material of the present invention may contain an alkali metal compound in addition to the hydroxide and/or oxide of an alkaline earth metal and the acid salt of a metal. By further blending the alkali metal compound, the reaction rate of the chemical heat storage material can be further improved.
The alkali metal constituting the compound of the alkali metal includes lithium, potassium and sodium, and only 1 kind of them may be included, or 2 or more kinds may be combined and included. Among these, lithium and sodium are preferable, and lithium is more preferable. The alkali metal compound is not particularly limited as long as it can exhibit the effects of the present invention, but is preferably a salt having hygroscopicity and capable of adsorbing moisture in the atmosphere or producing a corresponding hydrate. As such salts, for example, there are easily handled: halides such as chloride and bromide, hydroxides, carbonates, acetates, nitrates and sulfates. These may be used alone or in combination of 2 or more.
More specifically, the lithium salt is preferably a lithium halide and/or a lithium hydroxide, and more preferably a lithium chloride, a lithium bromide and/or a lithium hydroxide. The potassium salt is preferably a potassium halide and/or potassium hydroxide, and more preferably potassium chloride, potassium bromide and/or potassium hydroxide. The sodium salt is preferably a sodium halide and/or sodium hydroxide, and more preferably sodium chloride, sodium bromide and/or sodium hydroxide. However, the alkali metal compound and the acid salt of the metal are different compounds, and the case where the alkali metal compound and the acid salt of the metal denote the same compound is not included in the present invention.
The amount of the alkali metal compound used is preferably 0.1 to 50 mol% based on 100 mol% of the hydroxide and/or oxide of the alkaline earth metal. If the amount of the alkali metal compound is less than the above range, it is difficult to increase the reaction rate or lower the heat storage temperature by using the alkali metal compound. If the amount of the alkali metal compound is more than the above range, the heat storage amount per unit volume or unit mass of the chemical heat storage material may decrease. The amount of the alkali metal compound is preferably 0.5 to 30 mol%, more preferably 1.0 to 20 mol%, and still more preferably 2.0 to 10 mol%. The dehydration endothermic temperature of the chemical heat storage material can be controlled by adjusting the amount of the alkali metal compound.
The metal constituting the acid salt of the metal may be an alkali metal. For example, lithium chloride is selected as the acid salt of the metal, and lithium hydroxide is selected as the compound of the alkali metal, and these can be used together. In this embodiment, although the addition amount of these compounds can be adjusted within the range of the present invention, the total molar ratio of the metal acid salt of the alkaline earth metal hydroxide and/or oxide to the alkali metal compound is preferably 0.1% or more and less than 50% by mole, and the molar ratio of the metal acid salt to the alkali metal compound is more preferably in the range of 1: 9 to 9: 1, in the above range.
The chemical heat-accumulative material of the present invention may contain a compound of a specific metal in addition to the hydroxide and/or oxide of an alkaline earth metal, the compound of an alkali metal and the acid salt of a metal. The reaction rate of the chemical heat storage material can be further improved by further including the specific metal compound. In this case, the compound of the specific metal is preferably chemically combined with a hydroxide and/or an oxide of an alkaline earth metal.
The specific metal is selected from the group consisting of nickel, cobalt, copper and aluminum, and may include only 1 kind thereof, or may include 2 or more kinds in combination. Among them, at least 1 selected from the group consisting of nickel, cobalt and aluminum is preferable, and nickel and/or cobalt is more preferable.
The compound of the specific metal is not particularly limited, but is preferably formed by combining with a hydroxide and/or an oxide of an alkaline earth metal, and examples thereof include a halide such as chloride and bromide, a hydroxide, an oxide, a carbonate, an acetate, a nitrate, and a sulfate. These may be used alone or in combination of 2 or more. 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.
The amount of the specific metal compound used is preferably 0.1 to 40 mol% based on 100 mol% of the hydroxide and/or oxide of the alkaline earth metal. If the amount of the specific metal is less than this, it is difficult to increase the reaction rate and lower the heat storage temperature by using the compound of the specific metal. If the amount of the specific metal is more than the above range, the heat storage amount 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%, and still more preferably 10 to 25 mol%. The dehydration endothermic temperature of the chemical heat storage material can be controlled by adjusting the amount of the compound of the specific metal.
The chemical heat-accumulative material of the present invention may be a material in which a hydroxide and/or oxide of an alkaline earth metal, an acid salt of a metal, an optional compound of an alkali metal, and an optional compound of a specific metal are simply physically mixed or dispersed, but is not limited thereto. The material may be one in which a part or all of the components are chemically combined with each other, or one in which a part or all of the components chemically react with each other to generate a third component.
The chemical heat-storage material of the present invention utilizes an endothermic dehydration reaction and a hydration exothermic reaction by an alkaline earth metal hydroxide and an alkaline earth metal oxide. Within this range, the chemical heat-accumulative material of the present invention may contain other components, or may contain other chemical heat-accumulative components or components (e.g., binder) not exhibiting chemical heat-accumulative effect than the above-described constituent components.
The shape of the chemical heat-accumulative material of the present invention is not particularly limited, and may be, for example, a powder, granules, or a molded article. In the production of the chemical heat-accumulative material in the form of powder, granules or molded body, a known method can be applied. For example, in the production of a powdery chemical heat-accumulative material, the steps of sieving, disintegrating and pulverizing may be applied. In addition, in the production of the chemical heat-accumulative material for granules, granulation processes such as extrusion granulation, tumbling granulation, fluidized bed granulation and spray drying can be applied. In the production of the chemical heat-accumulative material for molded articles, the molding steps of pressure molding, injection molding, blow molding, vacuum molding and extrusion molding can be applied. That is, any shape can be selected according to the embodiment of the user as long as the properties of the chemical heat storage material can be implemented without being damaged.
Next, a method for producing the chemical heat-accumulative material of the present invention will be described.
The method for producing the chemical heat-accumulative material of the present invention is not particularly limited, and for example, an acid salt of a metal is first dissolved in deionized water to prepare an acid salt aqueous solution, and a powder of a hydroxide of an alkaline earth metal is added thereto and mixed with stirring. Here, the alkali metal compound, or the alkali metal compound and the specific metal compound may be added at the same time. The obtained slurry may be dried to produce the chemical heat-accumulative material as a dry powder. The stirring and mixing method is not particularly limited, and deionized water as a solvent may be sufficiently mixed with the powder of the hydroxide of the alkaline earth metal.
The order of addition of the components may be changed. In this case, for example, the chemical heat storage material may be produced by dissolving an alkali metal compound or an alkali metal compound and a specific metal compound in deionized water, adding a powder of a hydroxide of an alkaline earth metal thereto to produce a slurry, adding an acid salt of the metal, and drying the slurry.
Alternatively, the chemical heat-accumulative material may be produced by adding a metal and an acid to the mixture under ordinary conditions and reacting the mixture to form an acid salt of the metal, without using the acid salt of the metal itself.
The chemical heat storage material of the present invention can store heat by absorbing heat from a heat source of about 100 to 400 ℃, for example, unused heat from factory exhaust heat, and dehydrating the heat. The dehydrated chemical heat storage material can be easily maintained in a heat storage state by being kept in a dry state, and can be transported to a desired place while maintaining the heat storage state. In the case of heat release, the heat of hydration reaction (in some cases, the heat of adsorption of water vapor) can be extracted as thermal energy by contact with water, preferably water vapor. Further, cooling energy may be generated by adsorbing water vapor in one of the hermetically sealed spaces and evaporating water in the other.
The chemical heat storage material of the present invention is also suitable for use when the heat of exhaust gas discharged from an engine, a fuel cell, or the like is effectively used. For example, the heat of the exhaust gas can be utilized for shortening the warm-up operation of the automobile, improving the comfort of the passengers, improving the fuel consumption, reducing the harm of the exhaust gas due to the activity of the exhaust catalyst, and the like. In particular, in the engine, the load due to the operation is not constant, and the exhaust output is not stable, so that direct use of exhaust heat from the engine is not necessarily efficient, which is accompanied by inconvenience. When the chemical heat storage material of the present invention is used, exhaust heat from an engine is temporarily chemically stored and heat output is performed as needed, so that more ideal exhaust heat utilization is possible.
The chemical heat-accumulative material of the present invention can prevent or restore the deterioration of heat-accumulative capacity by appropriately supplementing an acid salt of a metal after repeating heat accumulation and heat release for a plurality of times, respectively. The metal acid salt may be supplemented to the heat-accumulative material, and the specific form thereof is not particularly limited. The acid salt of the metal may be replenished after the chemical heat storage material is taken out from the chemical heat pump or the target system (for example, a vehicle), or a mechanism for replenishing the acid salt of the metal to the chemical heat storage material at an arbitrary timing may be provided in the system of the chemical heat pump or the target system, so that the acid salt of the metal is replenished while the chemical heat pump or the target system is continuously operated without taking out the chemical heat storage material.
Next, an embodiment of a chemical heat pump using the chemical heat storage material of the present invention will be described.
Fig. 1 is a conceptual diagram illustrating a structure of a chemical heat pump according to an embodiment of the present invention. The chemical heat pump 10 has a reactor 11 containing a chemical heat storage material. The chemical heat storage material 21 contained in the reactor 11 is not particularly limited as long as it contains a hydroxide and/or an oxide of an alkaline earth metal. The chemical heat-accumulative material of the present invention may contain an acid salt of a metal in addition to the hydroxide and/or oxide of an alkaline earth metal, or may not contain an acid salt of a metal. The metal compound may or may not further contain an alkali metal compound, a specific metal compound, or the like. The chemical heat storage material 21 is preferably the chemical heat storage material of the present invention.
A heat supply unit 12 for supplying heat from the outside, such as plant waste heat, to the chemical heat storage material in the reactor 11 is thermally connected to the reactor 11. Thereby, the dehydration reaction of the chemical heat storage material is performed by supplying heat to the chemical heat storage material. That is, the hydroxide of an alkaline earth metal as a chemical heat storage material discharges water and converts it into an oxide, thereby enabling heat storage by the chemical heat pump.
Then, water is supplied to the alkaline earth metal oxide produced by the endothermic dehydration reaction, thereby causing the hydration heat generation reaction of the chemical heat storage material. That is, the oxide reacts with water to generate hydroxide, and heat is generated. In this manner, the heat recovery unit 13 for taking out heat generated from the chemical heat storage material to the outside is thermally connected to the reactor 11. The heat recovered from the chemical heat pump by the heat recovery unit 13 can be effectively used in any use thereafter. The heat recovery unit 13 may be integrally configured with the heat supply unit 12.
The water discharged from the chemical heat storage material in the reactor 11 by the endothermic dehydration reaction or the water supplied to the chemical heat storage material for the hydration heat generation reaction is stored in the storage tank 14. The water 22 in the reservoir may be liquid water or may be water vapor. Although not shown, the reservoir 14 may be provided with a second heat supply means for heating water in the reservoir and a second heat recovery means for taking out evaporation heat or condensation heat of the water to the outside.
The reactor 11 and the reservoir 14 are connected by a connecting pipe 15 for passing the water. The water discharged from the chemical heat-accumulative material in the reactor 11 during the dehydration reaction is transferred to the reservoir 14 through the connection pipe 15, and the water stored in the reservoir 14 is transferred to the reactor 11 through the connection pipe 15, thereby performing the hydration heat-generating reaction. The water may be moved by converting the water into steam by heating or reducing the pressure, or by arranging the reactor 11 and the storage tank 14 vertically and dropping the water. The connection pipe 15 may be provided with an on-off valve 16 for appropriately shutting off the water movement.
The chemical heat pump of the present invention is provided with a salt supply mechanism for supplying an acid salt of a metal into the chemical heat pump. The salt supply mechanism includes an openable and closable salt supply port 17 provided on a wall surface of the connection pipe 15 or the like at least for supplying an acid salt of a metal to the system of the chemical heat pump. The salt supply mechanism may further include a salt storage unit (not shown) for storing an acid salt of the metal. The salt storage part is connected to the salt supply port 17.
As the acid salt of the metal supplied from the salt supply port 17, the acid salt of the metal can be used. The acid salt of the metal may be supplied alone, or may be mixed with an appropriate medium, and may be supplied in the form of, for example, an aqueous solution. The metal acid salt may be supplied as a liquid or a powder. Can also be supplied by spraying.
The position of the salt supply port 17 is not particularly limited, and may be a position where the metal acid salt is supplied into the chemical heat pump and the metal acid salt and the chemical heat storage material can be brought into contact with each other. When the salt supply port 17 is provided in the connection pipe 15 as shown in fig. 1, for example, when a metal acid salt is supplied from the salt supply port 17 into the chemical heat pump when water is transferred from the accumulator 14 to the reactor 11, the metal acid salt can be introduced into the reactor 11 together with water and brought into contact with the chemical heat storage material in the reactor 11. The salt supply port 17 may be provided in the reactor 11 or in the reservoir 14.
By supplying an acid salt of a metal into the chemical heat pump by the salt supply means, the chemical heat storage material mainly composed of a hydroxide and/or an oxide of an alkaline earth metal comes into contact with the acid salt of a metal, and as described in the first invention, a higher reaction rate can be achieved and heat storage at a lower temperature can be achieved. According to the chemical heat pump of the present invention, the chemical heat storage material stored in the chemical heat pump can be supplemented with an acid salt of a metal. Thus, the deterioration of the heat storage performance of the chemical heat storage material can be prevented or repaired after repeating heat storage and heat release for a plurality of times.
Since the chemical heat storage material in the chemical heat pump can be supplemented with an acid salt of a metal, the chemical heat storage material contained in the chemical heat pump may contain a hydroxide and/or an oxide of an alkaline earth metal, and the acid salt of a metal may not be prepared in advance. However, the chemical heat storage material to be stored in the chemical heat pump is preferably prepared in advance as a metal acid salt.
The addition of the acid salt of the metal to the chemical heat pump may be performed only once or may be performed a plurality of times. In the present invention, particularly when heat storage and heat release of the chemical heat pump are repeated and as a result, the reaction rate exhibited by the chemical heat storage material decreases, improvement of the reaction rate during heat storage of the chemical heat pump can be expected by adding the acid salt of the metal.
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to these examples.
(evaluation method)
The chemical heat-accumulative materials obtained in examples and comparative examples were evaluated thermally using a thermogravimetry/differential thermal analysis measuring apparatus (TG/DTA 6300, manufactured by Seiko instruments). Specifically, the samples of the magnesium-based chemical heat storage material were heated to 300 ℃ and the samples of the calcium-based chemical heat storage material were heated to 400 ℃ under atmospheric conditions, at a temperature increase rate of 10 ℃/min, and then the weight loss and differential heat were measured over time while keeping the temperature constant. Based on the obtained weight loss values, the reaction rate was calculated as the ratio of magnesium hydroxide to magnesium oxide or the ratio of calcium hydroxide to calcium oxide in each chemical heat-storage material.
The reaction rate was calculated by setting the weight of the chemical heat-accumulative material at the time point of raising the temperature to 200 ℃ as the starting weight to 0% in order to exclude the influence of volatile components and the like, and setting the weight loss value assuming that all of the magnesium hydroxide was changed to magnesium oxide or all of the calcium hydroxide was changed to calcium oxide as the reaction rate of 100%.
The evaluation of the performance of the magnesium-based chemical heat storage material was carried out based on the reaction rate calculated from the weight loss value at the time point 4,000 seconds after the start time point of temperature rise. That is, the present evaluation method compares the reaction rates at the time points after the chemical heat-accumulative material is held at 300 ℃ that is a temperature at which thermal decomposition of magnesium hydroxide does not substantially proceed. The higher the reaction rate, the faster the endothermic dehydration reaction proceeds, indicating that the heat storage amount is large and heat can be stored by heat at a lower temperature. The numbers of the relative reaction rates in the table do not represent absolute values, but represent relative values when the reaction rates of the respective comparative examples are 100.
The evaluation of the performance of the calcium-based chemical heat storage material was performed based on the reaction rate calculated from the weight loss value at the time point after 3000 seconds had elapsed from the time point of the start of temperature rise. That is, the present evaluation method compares the reaction rate at a time point after the chemical heat-accumulative material is held at 400 ℃ which is a temperature at which thermal decomposition of calcium hydroxide progresses slowly, for a predetermined time. The higher the reaction rate, the faster the endothermic dehydration reaction proceeds, indicating that the heat storage amount is large and heat can be stored by heat at a lower temperature. The numbers of the relative reaction rates in the table do not represent absolute values, but represent relative values when the reaction rates of the comparative examples are 100.
The magnesium hydroxide used in the examples and comparative examples was the magnesium hydroxide produced by the inventors of the present invention. The purity of magnesium hydroxide was calculated by subtracting the main impurities, Ca, Si, P, S, Fe, B, and Na, from 100% by oxide conversion in a multielement simultaneous fluorescence X-ray analyzer (product of simulx 12 co., ltd.). The BET specific surface area was measured by a gas adsorption method (BET method) using nitrogen gas using a specific surface area measuring apparatus (Macsorb, manufactured by mount tech co. The volume average particle diameter was measured by a laser diffraction scattering particle size distribution measuring apparatus (MT 3300 manufactured by japan ltd.).
As calcium hydroxide used in the examples and comparative examples, a commercially available reagent (reagent Special grade, purity 95%, manufactured by Kanto chemical industries, Ltd.) was used.
(example 1)
5g of magnesium hydroxide (purity 99% or more, BET specific surface area 8.4 m) were weighed2Volume average particle diameter of 3.5 μm)/g), and further, magnesium acetate (kanto chemical, extra grade) was weighed in an amount of 2.4 mol% relative to the magnesium hydroxide. The weighed magnesium acetate was dissolved in 50mLIonized water to obtain magnesium acetate solution. The weighed magnesium hydroxide was put into the magnesium acetate aqueous solution, and stirred with an electromagnetic stirrer at a rotation speed of 60 (rpm) for 300 seconds to prepare a slurry. This slurry was dried in a dryer (DRA 430DA, manufactured by Advantec corporation) at 110 ℃ for 12 hours or more to remove water, thereby producing a chemical heat-accumulative material. The thermal behavior of the obtained chemical heat-accumulative material was confirmed by the above evaluation method, and the reaction rate was calculated.
Comparative example 1
For magnesium hydroxide (purity more than 99%, BET specific surface area 8.4 m)2Volume average particle diameter of 3.5 μm/g) itself, and the reaction rate was calculated in the same manner as described above.
Table 1 shows the numbers obtained by converting the reaction rates obtained in example 1 into relative reaction rates, based on 100 of the reaction rates of the magnesium hydroxide monomer obtained in comparative example 1.
Fig. 2 is a graph showing the change with time of the reaction rate shown in example 1 and comparative example 1, and comparative example 2 described later. The relative reaction rates shown in table 1 are relative values calculated based on the reaction rates at the 4000 second time point in the graph in fig. 2.
[ Table 1]
The magnesium hydroxide monomer of comparative example 1 to which the acid salt of the metal was not added had an extremely low reaction rate under the evaluation conditions used herein, and the endothermic dehydration reaction hardly proceeded. As can be seen from table 1 and fig. 2, the chemical heat-accumulative material of example 1, which was prepared by adding an acid salt of a metal to magnesium hydroxide, had a significantly improved reaction rate and a rapidly proceeding endothermic dehydration reaction as compared with comparative example 1 under the same evaluation conditions as comparative example 1. From this fact, it is understood that the chemical heat-accumulative material of example 1 has a larger accumulative amount of heat than the magnesium hydroxide alone of comparative example 1, and can accumulate heat even with heat of a lower temperature.
As is clear from fig. 2, the reaction rate of example 1 is much higher than that of comparative example 2, which will be described later, in which only lithium hydroxide is added to magnesium hydroxide. The reaction rate at the time of 4000 seconds in example 1 was converted into a relative reaction rate, which was calculated as 292, with the reaction rate at the time of 4000 seconds in comparative example 2 being 100.
(example 2)
5g of magnesium hydroxide was weighed, and an amount of magnesium nitrate (and Wako pure chemical industries, Ltd.) was weighed in an amount of 2.4 mol% relative to the magnesium hydroxide, and an amount of lithium hydroxide monohydrate (Kanto chemical industries, Ltd., purity 98.0%) was weighed in an amount of 20 mol% relative to the magnesium hydroxide. The weighed magnesium nitrate was dissolved in 50mL of deionized water to obtain an aqueous magnesium nitrate solution. The weighed magnesium hydroxide and lithium hydroxide monohydrate were put into the magnesium nitrate aqueous solution, and stirred with an electromagnetic stirrer at a rotation speed of 60 (rpm) for 300 seconds to produce a slurry. This slurry was dried in a dryer (DRA 430DA, manufactured by Advantec corporation) at 110 ℃ for 12 hours or more to remove water, thereby producing a chemical heat-accumulative material. The thermal behavior of the obtained chemical heat-accumulative material was confirmed by the above evaluation method, and the reaction rate was calculated.
(example 3)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that magnesium acetate (kanto chemical reagent, special grade) was used instead of magnesium nitrate, and the reaction rate was calculated in the same manner.
(example 4)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that magnesium chloride (kanto chemical reagent, special grade) was used instead of magnesium nitrate, and the reaction rate was calculated in the same manner.
(example 5)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that magnesium benzoate (and optical pure chemical reagent, purity: 95.0%) was used instead of magnesium nitrate, and the reaction rate was calculated in the same manner.
(example 6)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that magnesium citrate (and a chemical reagent for a photochemical agent) was used in place of magnesium nitrate in an amount of 0.8 mol% based on magnesium hydroxide, and the reaction rate was calculated in the same manner.
(example 7)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that lithium chloride (special grade, purity 99.0%) was used in place of magnesium nitrate in an amount of 10 mol% based on magnesium hydroxide, and the reaction rate was calculated in the same manner.
(example 8)
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that lithium iodide (Wako pure chemical industries, 1 st grade) was used instead of magnesium nitrate, and the reaction rate was calculated in the same manner.
Comparative example 2
A chemical heat-accumulative material was prepared in the same manner as in example 2 except that magnesium nitrate was not used and 50mL of deionized water was charged with magnesium hydroxide instead of the magnesium nitrate aqueous solution, and the reaction rate was calculated in the same manner.
In table 2, the numbers obtained by converting the reaction rates obtained in examples 2 to 8 into relative reaction rates are shown based on 100 of the reaction rate obtained in comparative example 2 in which the chemical heat-accumulative material was produced without adding an acid salt of a metal.
FIG. 3 is a graph showing the change with time of the reaction rate shown in examples 2 to 8 and comparative example 2. The relative reaction rates shown in table 2 are relative values calculated based on the reaction rates at the 4000 second time point in the graph in fig. 3.
[ Table 2]
As can be seen from table 2 and fig. 3, the chemical heat-storage materials of examples 2 to 8, which were produced by adding lithium hydroxide as an alkali metal compound to magnesium hydroxide and adding an acid salt of a metal, had a significantly improved reaction rate and rapidly progressed the endothermic dehydration reaction, compared to the chemical heat-storage material of comparative example 2, which was produced without adding an acid salt of a metal. It is understood from this that the chemical heat-accumulative materials of examples 2 to 8 can accumulate heat even with heat at a lower temperature than the chemical heat-accumulative material of comparative example 2.
(example 9)
5g of calcium hydroxide (Kanto chemical reagent, special grade, purity 95% or more) was weighed, and calcium nitrate tetrahydrate (Kanto chemical reagent, grade 1) was weighed in an amount of 2.4 mol% relative to the calcium hydroxide, and lithium hydroxide monohydrate (Kanto chemical reagent, special grade, purity 98.0%) was weighed in an amount of 20 mol% relative to the calcium hydroxide. The weighed calcium nitrate was dissolved in 50mL of deionized water to obtain an aqueous calcium nitrate solution. The weighed calcium hydroxide and lithium hydroxide monohydrate were put into this calcium nitrate aqueous solution, and stirred with an electromagnetic stirrer at a rotation speed of 60 (rpm) for 300 seconds to produce a slurry. This slurry was dried in a dryer (DRA 430DA, manufactured by Advantec corporation) at 110 ℃ for 12 hours or more to remove water, thereby producing a chemical heat-accumulative material. The thermal behavior of the obtained chemical heat-accumulative material was confirmed by the above evaluation method, and the reaction rate was calculated.
(example 10)
A chemical heat-accumulative material was prepared in the same manner as in example 9 except that calcium chloride (special grade, kanto chemical reagent) was used instead of calcium nitrate, and the reaction rate was calculated in the same manner.
(example 11)
A chemical heat-accumulative material was prepared in the same manner as in example 9 except that lithium nitrate (and ultrapure chemical industrial reagent, specialty grade) was used in place of calcium nitrate, and the reaction rate was calculated in the same manner.
(example 12)
A chemical heat-accumulative material was prepared in the same manner as in example 9 except that lithium chloride (special grade, kanto chemical reagent) was used instead of calcium nitrate, and the reaction rate was calculated in the same manner.
Comparative example 3
A chemical heat-accumulative material was prepared in the same manner as in example 9 except that calcium nitrate was not used and 50mL of deionized water was charged with calcium hydroxide instead of the calcium nitrate aqueous solution, and the reaction rate was calculated in the same manner.
Comparative example 4
The reaction rate was calculated similarly for calcium hydroxide (special grade, purity 95% or more) itself.
[ Table 3]
Table 3 shows numbers obtained by converting the reaction rates obtained in examples 9 to 12 and comparative example 4 into relative reaction rates, based on 100 of the reaction rate obtained in comparative example 3 in which the chemical heat-accumulative material was produced without adding an acid.
Fig. 4 is a graph showing the change with time of the reaction rate shown in examples 9 to 12 and comparative examples 3 and 4. The relative reaction rates shown in table 3 are relative values calculated based on the reaction rates at the time point of 3000 seconds in the graph in fig. 4.
As can be seen from table 3 and fig. 4, the chemical heat-accumulative materials of examples 9 to 12, which were prepared by adding an acid salt of a metal, had a significantly improved reaction rate and the endothermic dehydration reaction proceeded rapidly, compared to the chemical heat-accumulative material of comparative example 3 and the calcium hydroxide monomer of comparative example 4, which were prepared without adding an acid salt of a metal. It is understood from the above that the chemical heat-accumulative materials of examples 9 to 12 can accumulate heat even with heat at a lower temperature than the chemical heat-accumulative material of comparative example 3 and the calcium hydroxide monomer of comparative example 4, which were manufactured without adding an acid salt of a metal.
Description of the symbols:
10 a chemical heat pump;
11 a reactor;
12 a heat supply unit;
13 a heat recovery unit;
14 a reservoir;
15 connecting pipes;
16 an opening and closing valve;
17 a salt supply port;
21 a chemical heat storage material;
22 water.
Claims (8)
1. A chemical heat storage material is characterized in that,
comprising a hydroxide and/or oxide of an alkaline earth metal, a compound of an alkali metal and an acid salt of a metal;
the amount of the alkali metal compound is 0.5 to 30 mol% based on the hydroxide and/or oxide of the alkaline earth metal,
the compound of the alkali metal is hydroxide of the alkali metal,
the acid salt of a metal is an acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals,
the amount of the acid salt of the metal is 0.1 to 20 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
2. The chemical heat storage material according to claim 1,
the alkaline earth metal in the hydroxide and/or oxide of an alkaline earth metal is at least 1 selected from the group consisting of calcium, magnesium, strontium, and barium.
3. The chemical heat storage material according to claim 1,
the alkali metal in the alkali metal compound is at least 1 selected from the group consisting of lithium, potassium and sodium.
4. The chemical heat storage material according to claim 1,
the acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals is an acid salt of at least 1 metal selected from the group consisting of lithium, sodium, potassium, calcium, magnesium, strontium, and barium.
5. A method for producing a chemical heat-accumulative material,
comprises a step of mixing a hydroxide and/or an oxide of an alkaline earth metal, a compound of an alkali metal and an acid salt of a metal;
the amount of the alkali metal compound is 0.5 to 30 mol% based on the hydroxide and/or oxide of the alkaline earth metal,
the compound of the alkali metal is hydroxide of the alkali metal,
the acid salt of a metal is an acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals,
the amount of the acid salt of the metal is 0.1 to 20 mol% based on the hydroxide and/or oxide of the alkaline earth metal.
6. The manufacturing method according to claim 5,
the alkaline earth metal in the hydroxide and/or oxide of an alkaline earth metal is at least 1 selected from the group consisting of calcium, magnesium, strontium, and barium.
7. The manufacturing method according to claim 5,
the alkali metal in the alkali metal compound is at least 1 selected from the group consisting of lithium, potassium and sodium.
8. The manufacturing method according to claim 5,
the acid salt of at least 1 metal selected from the group consisting of alkali metals and alkaline earth metals is an acid salt of at least 1 metal selected from the group consisting of lithium, sodium, potassium, calcium, magnesium, strontium, and barium.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017129554 | 2017-06-30 | ||
| JP2017-129554 | 2017-06-30 | ||
| JP2018025570 | 2018-02-16 | ||
| JP2018-025570 | 2018-02-16 | ||
| PCT/JP2018/024454 WO2019004314A1 (en) | 2017-06-30 | 2018-06-27 | Chemical heat storage material, method for producing same, chemical heat pump, and method for operating chemical heat pump |
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| JP6582356B2 (en) * | 2015-06-12 | 2019-10-02 | 国立大学法人東京工業大学 | Chemical heat storage material |
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| CN110770320A (en) | 2020-02-07 |
| SA520410933B1 (en) | 2022-11-01 |
| KR20200024792A (en) | 2020-03-09 |
| WO2019004314A1 (en) | 2019-01-03 |
| KR102599491B1 (en) | 2023-11-07 |
| JP2019137826A (en) | 2019-08-22 |
| JP6471947B1 (en) | 2019-02-20 |
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