CN111684039B - Chemical heat storage material and preparation method thereof - Google Patents
Chemical heat storage material and preparation method thereof Download PDFInfo
- Publication number
- CN111684039B CN111684039B CN201980013119.3A CN201980013119A CN111684039B CN 111684039 B CN111684039 B CN 111684039B CN 201980013119 A CN201980013119 A CN 201980013119A CN 111684039 B CN111684039 B CN 111684039B
- Authority
- CN
- China
- Prior art keywords
- hydroxide
- lithium
- calcium
- magnesium
- chemical heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000000126 substance Substances 0.000 title claims abstract description 87
- 238000005338 heat storage Methods 0.000 title claims abstract description 68
- 239000011232 storage material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 47
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011575 calcium Substances 0.000 claims abstract description 40
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 39
- 239000011777 magnesium Substances 0.000 claims abstract description 39
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 14
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 57
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000002156 mixing Methods 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 23
- 150000002642 lithium compounds Chemical class 0.000 abstract description 12
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 238000011156 evaluation Methods 0.000 description 18
- 239000000920 calcium hydroxide Substances 0.000 description 14
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 14
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 14
- 239000000347 magnesium hydroxide Substances 0.000 description 14
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 14
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000004580 weight loss Effects 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006703 hydration reaction Methods 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 3
- 235000012255 calcium oxide Nutrition 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010908 plant waste Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 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
- 229910021529 ammonia Inorganic materials 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
- 239000002131 composite material Substances 0.000 description 2
- 208000012839 conversion disease Diseases 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
- 230000036571 hydration Effects 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 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
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000001035 drying 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
- 230000020169 heat generation Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising 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
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Sorption Type Refrigeration Machines (AREA)
Abstract
Provided is a chemical heat storage material which stores heat by a dehydration reaction of a hydroxide of calcium and/or magnesium, and which can store heat at a lower temperature while exhibiting a higher reaction rate. The chemical heat-accumulative 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 lithium compound. The total amount of the lithium compound is preferably 0.1 to 50 mol% based on the hydroxide and/or oxide of calcium and/or magnesium.
Description
Technical Field
The invention relates to a chemical heat storage material and a preparation method thereof.
Background
In recent years, reduction in the use of fossil fuels has been demanded due to carbon dioxide emission restrictions, and it is also necessary to utilize exhaust heat in addition to energy saving in each step. As means for utilizing exhaust heat, heat storage with warm water of 100 ℃ or lower of water is known. However, warm water heat storage has problems such as (1) heat storage that cannot be carried out for a long time due to heat release loss, (2) difficulty in compacting a heat storage device because a large amount of water is required because the amount of sensible heat is small, and (3) gradual decrease in output temperature due to an unsteady amount of use. Therefore, in order to promote the domestic use of such exhaust heat, it is necessary to develop a heat storage technique with higher efficiency.
As a heat storage technique with high efficiency, there is a chemical heat storage method, for example. The chemical heat storage method involves chemical changes such as adsorption and hydration of substances, and therefore the amount of heat stored per unit mass is higher than that of a heat storage method based on latent heat or sensible heat of the material itself (water, molten salt, or the like). As the chemical heat storage method, there have been proposed a steam adsorption/desorption method in which water vapor in the atmosphere is adsorbed/desorbed, a reaction in which ammonia is absorbed by a metal salt (ammonia complex formation reaction), and a reaction in which organic substances such as alcohol are adsorbed/desorbed, and the like. The water vapor adsorption-desorption method is most advantageous in consideration of the load on the environment or the simplicity of the apparatus. Calcium hydroxide or magnesium hydroxide is known as a chemical heat storage material used in the steam adsorption/desorption method.
However, calcium hydroxide does not undergo an effective dehydration reaction at a temperature of 100 to 400 ℃ and magnesium hydroxide does not undergo an effective dehydration reaction at a low temperature of 100 to 300 ℃, and thus has a problem that it cannot 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 ℃.
Further, patent document 2 proposes a chemical heat storage material prepared 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, for example, when the plant waste heat is stored, the temperature range of the plant waste heat is 200 to 250 ℃ or lower, and therefore the heat storage operation temperature is not sufficiently low, and it is difficult to efficiently use the plant waste heat, and a further lowering of the operation temperature is required. Improvement of the operating temperature of the chemical heat storage material is still an important issue in terms of improvement of the 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 a hydroxide of calcium and/or magnesium, and that can store heat at a lower temperature while exhibiting a higher reaction rate, and a method for producing the same.
Means for solving the problems:
the present inventors have made various studies to solve the above-described problems, and found that a chemical heat storage material containing a hydroxide and/or oxide of calcium and/or magnesium, in which a hydroxide of lithium and a chloride of lithium are added together to a hydroxide and/or oxide of calcium and/or magnesium, can store heat at a lower temperature, and the present invention has been obtained. Further, the present inventors have conducted extensive studies and found that the range of the ratio of lithium hydroxide and lithium chloride added to the calcium and/or magnesium hydroxide and/or oxide is specified, and that the temperature of the reaction temperature can be lowered more efficiently.
That is, the first invention relates to a chemical heat storage material comprising 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 the hydroxide of lithium and the chloride of lithium is preferably 0.1 to 50 mol% based on the hydroxide and/or oxide of calcium and/or magnesium. The molar ratio of the lithium hydroxide to the lithium chloride is preferably in the range of 0.1 to 9, more preferably in the range of 0.25 to 4, and still more preferably in the range of 0.5 to 2.0;
the chemical heat storage material may further include at least one metal compound selected from the group consisting of nickel, cobalt, copper, aluminum, iron, and zinc, and the amount of the metal is preferably 0.1 to 40 mol% based on the hydroxide and/or oxide of calcium and/or magnesium;
the second invention relates to 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, a hydroxide of lithium, and a chloride of lithium. In the preparation method, the total amount of the hydroxide of lithium and the chloride of lithium is preferably 0.1 to 50 mol% relative to the hydroxide and/or oxide of calcium and/or magnesium. The molar ratio of the lithium hydroxide to the lithium chloride is preferably in the range of 0.1 to 9, more preferably in the range of 0.25 to 4, and still more preferably in the range of 0.5 to 2.0;
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 preferably 0.1 to 40 mol% based on the hydroxide and/or oxide of calcium and/or magnesium.
The invention has the following effects:
according to the present invention, it is possible to provide a chemical heat storage material which can store heat at a lower temperature by showing a higher reaction rate in a chemical heat storage material which stores heat by a dehydration reaction of a hydroxide of calcium and/or magnesium, and a method for producing the same.
Drawings
Fig. 1 is a graph showing the change with time of the reaction rate shown in examples 1 to 4 and comparative examples 1 to 3 (the horizontal axis is the elapsed time (seconds) from the time when the temperature rises to 200 ℃, and the vertical axis is the reaction rate (%);
fig. 2 is a graph showing the change with time of the reaction rate shown in example 5 and comparative examples 4 to 6 (the horizontal axis represents the elapsed time (seconds) from the time when the temperature rises to 200 ℃, and the vertical axis represents the reaction rate (%)).
Detailed Description
The following describes in detail embodiments of the present invention
The chemical heat storage material prepared in the present invention utilizes a reversible reaction represented by the following reaction formula based on hydroxides and oxides of calcium and/or magnesium:
CaO＋H 2O⇔Ca(OH) 2 △H＝－109．2kJ/mol
MgO＋H 2O⇔Mg(OH) 2 △H＝－81．2kJ/mol。
in the formulae, the reaction in the rightward direction is an exothermic reaction of hydration of calcium oxide or magnesium oxide. Conversely, the reaction in the leftward 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 performing a dehydration reaction of calcium hydroxide or magnesium hydroxide, and can supply the accumulated heat energy by performing a hydration reaction of calcium oxide or magnesium oxide.
The chemical heat-accumulative material of the present invention may include any one or both of a hydroxide of calcium and/or magnesium and an oxide of calcium and/or magnesium. The metal may include any one of calcium and magnesium, or both of them.
The chemical heat storage material of the invention relates to the following chemical heat storage materials: the compound comprises hydroxide and/or oxide of calcium and/or magnesium and lithium, and the lithium compound comprises hydroxide and chloride of lithium. Both of a hydroxide and a chloride of lithium are blended as a lithium compound, so that the reaction rate of the chemical heat storage material is increased, and heat storage at a lower temperature can be realized.
The amount of the lithium compound used is preferably 0.1 to 50 mol% in total, based on 100 mol% of the hydroxide and/or oxide of calcium and/or magnesium. If the total amount of the two compounds is less than this range, it becomes difficult to increase the reaction rate or lower the heat storage temperature by the co-addition of these compounds. If the total amount of the two compounds is more than the above range, the effect on the hydroxide and/or oxide of calcium and/or magnesium 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 total amount of the two compounds is preferably 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, further preferably 0.5 to 10 mol%, further preferably 0.8 to 8 mol%, and particularly preferably 1 to 6 mol%.
Further, the content ratio of the lithium compound is preferably in the range of 0.1 to 9 in terms of the content of lithium hydroxide/the content of lithium chloride on a molar basis. If the content ratio of the lithium hydroxide and the lithium chloride is less than or greater than this range, it is difficult to achieve an increase in the reaction rate or a reduction in the heat storage temperature by the co-addition of the two compounds. The content ratio is more preferably in the range of 0.25 to 4, and still more preferably in the range of 0.5 to 2.
The chemical heat-accumulative material of the present invention may contain a compound of a specific metal in addition to a hydroxide and/or oxide of calcium and/or magnesium, lithium hydroxide, lithium chloride. By further including the specific metal compound, the reaction rate of the chemical heat storage material can be further improved. In this case, the compound of the specific metal is preferably chemically combined with a hydroxide and/or oxide of calcium and/or magnesium.
The specific metal is selected from the group consisting of nickel, cobalt, copper, aluminum, iron, and zinc, and may include only one of these metals or a combination of two or more of these metals. Among them, at least one 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 a compound of a hydroxide and/or an oxide of calcium and/or magnesium, for example, a halide such as chloride or bromide, a hydroxide, an oxide, a carbonate, an acetate, a nitrate, or a sulfate. These may be used alone or in combination of two 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 is preferably 0.1 to 40 mol% based on 100 mol% of the hydroxide and/or oxide of calcium and/or magnesium. If the amount of the specific metal is less than this, it is difficult to achieve an increase in the reaction rate or a reduction in the heat storage temperature due to the use of 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 be reduced. The amount of the specific metal is preferably 3 to 40 mol%, more preferably 5 to 30 mol%, and further preferably 10 to 25 mol%. By adjusting the amount of the specific metal compound, the dehydration endothermic temperature of the chemical heat storage material can be controlled.
The hydroxide and/or oxide of calcium and/or magnesium, lithium hydroxide, lithium chloride, and optionally a compound of a specific metal of the chemical heat-accumulative material of the present invention may be simply physically mixed or dispersed, but is not limited thereto. Some or all of the components may be chemically combined with each other, or some or all of the components may be chemically reacted with each other to produce a third component.
The chemical heat-accumulative material of the present invention is a chemical heat-accumulative material utilizing an endothermic dehydration reaction of a hydroxide of calcium and/or magnesium and an exothermic hydration reaction of an oxide of calcium and/or magnesium. 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 not exhibiting chemical heat-accumulative action (e.g., binder) other than the above-described components.
The shape of the chemical heat-accumulative material of the present invention is not particularly limited, and any shape may be selected according to the required embodiment as long as the shape of the chemical heat-accumulative material is not impaired. Specifically, the chemical heat-accumulative material of the present invention may be in the form of powder, granules, molded articles, etc.
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 an example thereof will be described below. First, a powder of a hydroxide of calcium and/or magnesium is added to deionized water and stirred to mix. Next, a hydroxide of lithium and a chloride of lithium, which are lithium compounds, or a lithium compound and a compound of a specific metal are simultaneously or sequentially charged and further stirred and mixed. The obtained slurry (slurry) was dried to prepare a chemical heat-accumulative material as a dry powder. The method of stirring and mixing is not particularly limited, and deionized water as a solvent may be sufficiently mixed with powders of calcium and/or magnesium hydroxide, and the like.
The order of addition of the ingredients may also be altered. In this case, for example, a lithium compound or a lithium compound and a specific metal compound are dissolved in deionized water, and a powder of a hydroxide of calcium and/or magnesium is added thereto to prepare a slurry, and a metal acid salt is added as necessary, followed by drying to prepare a chemical heat storage material.
In the case of producing a chemical heat-accumulative material in the form of a powder, granules or molded article, conventional methods can be applied. For example, in the case of preparing a powdered chemical heat-accumulative material, the steps of sieving, disintegrating and pulverizing may be applied. In addition, when preparing the chemical heat storage material of granules, granulation steps such as extrusion granulation, rolling granulation, fluidized bed granulation, and spray drying (spray dry) can be applied. In the production of the chemical heat-accumulative material of molded article, the molding step of pressure (press), injection molding, blow molding, vacuum molding or extrusion molding can be applied.
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 ℃, for example, factory exhaust 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 generation, the heat of hydration reaction (in some cases, the heat of adsorption of water vapor) can be extracted as thermal energy by contacting with water, preferably water vapor. Further, one of the airtight sealed spaces can adsorb water vapor and the other can generate cooling energy by evaporating water.
The chemical heat storage material of the present invention is 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 of the automobile warm-up, improvement of comfort for the occupant, improvement of fuel efficiency, reduction of harm of the exhaust gas due to improvement of activity of the exhaust gas catalyst, and the like. In particular, the load of the engine during running is not constant and the exhaust output is unstable, so that direct use of the exhaust heat from the engine is inevitably inefficient and inconvenient. If the chemical heat storage material of the present invention is used, exhaust heat from the engine is temporarily chemically stored, and heat output is performed as needed, thereby making it possible to more optimally utilize the exhaust heat.
Examples
The present invention will be described in further detail with reference to 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 by thermogravimetry/differential thermal analysis (TGD 9600, manufactured by ADVANCE RIKO). Specifically, the chemical heat-accumulative material as a sample was measured by an electronic balance, and 20mg was loaded in a platinum tank in the thermal balance. Next, an inert purge gas (argon) was introduced into the reactor at a flow rate of 100 mL/min, and the physically adsorbed water of the sample was dried and removed at 120 ℃. Thereafter, the sample of the magnesium-based chemical heat storage material was heated to 270 ℃ at a temperature rising rate of 20 ℃/min, and maintained for 1 hour to perform a dehydration reaction. A sample of the calcium-based chemical heat-accumulative material was heated to 350 ℃ at a rate of 20 ℃/min and maintained for 6 hours to carry out dehydration reaction.
The reaction rate of the chemical heat-accumulative material was calculated by setting the weight of the chemical heat-accumulative material at the time of raising the temperature to 200 ℃ as the starting weight and setting the reaction rate to 0% and the weight loss value assuming that all of the hydroxides of magnesium or calcium were oxides to be 100% in order to eliminate the influence of volatile components and the like.
The evaluation of the performance of the magnesium-based chemical heat storage material was carried out based on the reaction rate calculated from the following weight loss values: the weight loss value is a weight loss value at the time when 1,200 seconds have elapsed from the time when 200 ℃ was reached. That is, the present evaluation method compares the reaction rates at the time when the chemical heat-accumulative material is maintained at 270 ℃ which 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, and the larger the amount of stored heat, and the heat storage can be performed by the heat at the lower temperature. The numbers of the relative reaction rates in the table do not indicate absolute values, but indicate relative values when 1 is used as a reference for the reaction rate of comparative example 1.
The evaluation of the performance of the calcium-based chemical heat storage material was carried out based on the reaction rate calculated from the following weight loss values: the weight loss value is a weight loss value at the time when 3,600 seconds have elapsed from the time when 200 ℃. That is, the present evaluation method compares the reaction rates at the time when the chemical heat-accumulative material is maintained for a predetermined time at 350 ℃ which is a temperature at which thermal decomposition of calcium hydroxide does not substantially proceed. The higher the reaction rate, the faster the endothermic dehydration reaction proceeds, and the larger the amount of stored heat, and the heat storage can be performed by the heat at the lower temperature. The numbers of the relative reaction rates in the table do not indicate absolute values, but indicate relative values when the reaction rate of comparative example 4 is 1 as a reference.
(example 1)
2g of magnesium hydroxide (manufactured by Wako pure chemical industries, purity 99.9%) was weighed. Then, 0.207 g of lithium chloride monohydrate (Wako pure chemical industries, Ltd., purity 99.9%) was weighed, and 0.144 g of lithium hydroxide monohydrate (Wako pure chemical industries, purity 99.9%) was further weighed. The sample composition (molar ratio) at this time was magnesium hydroxide: lithium chloride: lithium hydroxide 100: 10: 10. the above weighed amounts of lithium chloride and lithium hydroxide were put into 50mL of deionized water to prepare an aqueous solution. Subsequently, magnesium hydroxide was put into the aqueous solution, and the resulting solution was stirred by a rotary evaporator (rotameter) to prepare a slurry. The slurry was further heated to evaporate water, and then dried in air at 120 ℃ for 12 hours or more by a dryer (ADVANTEC toyoyo DRA330 DA) to remove water, thereby preparing a chemical heat-accumulative 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.
(example 2)
Weighing reagents according to the molar ratio of 100: 20: 20, sample preparation and evaluation were carried out in the same manner as in example 1.
(example 3)
Weighing reagents according to the molar ratio of 100: 5: sample preparation and evaluation were carried out in the same manner as in example 1.
(example 4)
Weighing reagents according to the molar ratio of 100: 6: 12, sample preparation and evaluation were carried out in the same manner as in example 1.
Comparative example 1
The magnesium hydroxide used in example 1 was evaluated as a sample without adding a lithium compound.
Comparative example 2
Weighing reagents according to the molar ratio of 100: 20: 0, sample preparation and evaluation were carried out in the same manner as in example 1.
Comparative example 3
Weighing reagents according to the molar ratio of 100: 0: 20, sample preparation and evaluation were carried out in the same manner as in example 1.
(example 5)
2g of calcium hydroxide (manufactured by Wako pure chemical industries, purity 99.9%) was weighed. Then, 0.082 g of lithium chloride monohydrate (manufactured by Wako pure chemical industries, purity 99.9%) was weighed, and 0.057 g of lithium hydroxide monohydrate (manufactured by Wako pure chemical industries, purity 99.9%) was further weighed. The composition (molar ratio) of the sample at this time was calcium hydroxide: lithium chloride: lithium hydroxide 100: 5: 5. the above weighed amounts of lithium chloride and lithium hydroxide were put into 50mL of deionized water to prepare an aqueous solution. Then, calcium hydroxide was added to the aqueous solution, and the mixture was stirred by a rotary evaporator to prepare a slurry. The slurry was further heated to evaporate water, and then dried in air at 120 ℃ for 12 hours or more by a dryer (ADVANTEC toyoyo DRA330 DA) to remove water, thereby preparing a chemical heat-accumulative 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.
Comparative example 4
The calcium hydroxide used in example 5 was evaluated as a sample without adding a lithium compound.
Comparative example 5
Weighing reagents according to a molar ratio of 100: 10: 0, sample preparation and evaluation were carried out in the same manner as in example 5.
Comparative example 6
Weighing reagents according to a molar ratio of 100: 0: 10, sample preparation and evaluation were carried out in the same manner as in example 5.
[ Table 1]
[ Table 2]
Table 1 shows the numbers obtained by converting the reaction rates obtained in examples 1 to 4 and comparative examples 2 to 3 into relative reaction rates, based on the reaction rate (dehydration conversion rate) of the magnesium hydroxide monomer obtained in comparative example 1.
FIG. 1 is a graph showing the change with time of the reaction rate shown in examples 1 to 4 and comparative examples 1 to 3. The relative reaction rates shown in table 1 are relative values calculated based on the reaction rates at the time of 1,200 seconds in the graph shown in fig. 1.
The magnesium hydroxide monomer of comparative example 1 had a low dehydration reaction conversion rate under the evaluation conditions employed herein, and the endothermic dehydration reaction hardly proceeded. From table 1 and fig. 1, it can be confirmed that the chemical heat-storage materials of examples 1 to 4, which were prepared by adding lithium hydroxide and lithium chloride together at a predetermined ratio, have 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. It is understood from this that the chemical heat-accumulative materials of examples 1 to 4 have a larger accumulative amount of heat than the magnesium hydroxide monomer of comparative example 1 and can accumulate heat with heat of a lower temperature.
It is further understood that the chemical heat-accumulative materials of examples 1 to 4, in which lithium hydroxide and lithium chloride were added together at a predetermined ratio, had a larger heat-accumulative amount and were able to accumulate heat with heat at a lower temperature than the chemical heat-accumulative materials of comparative examples 2 and 3, in which lithium hydroxide or lithium chloride was added alone.
Table 2 shows the numbers obtained by converting the reaction rates obtained in example 5 and comparative examples 5 and 6 into relative reaction rates, based on the reaction rate (dehydration conversion rate) of the calcium hydroxide monomer obtained in comparative example 4.
FIG. 2 is a graph showing the change with time of the reaction rate shown in example 5 and comparative examples 4 to 6. The relative reaction rates shown in table 2 are relative values calculated based on the reaction rates at 3,600 seconds in the graph of fig. 2.
The calcium hydroxide monomer of comparative example 4 had a low dehydration reaction conversion rate under the evaluation conditions employed herein, and the endothermic dehydration reaction hardly proceeded. From table 2 and fig. 2, it can be confirmed that the chemical heat-accumulative material of example 5, which was prepared by adding lithium hydroxide and lithium chloride together at a predetermined ratio, has a significantly improved reaction rate and a rapidly proceeding endothermic dehydration reaction as compared with comparative example 4 under the same evaluation conditions as comparative example 4. From this fact, it is understood that the chemical heat-accumulative material of example 5 has a larger accumulative heat amount than the calcium hydroxide alone of comparative example 4, and can accumulate heat with heat of a lower temperature.
It is further understood that the chemical heat-storage material of example 5 in which lithium hydroxide and lithium chloride were added together at a predetermined ratio has a larger heat-storage amount and can store heat with heat at a lower temperature than the chemical heat-storage materials of comparative examples 5 and 6 in which lithium hydroxide or lithium chloride was added alone.
Claims (4)
1. A chemical heat-storage material is characterized by comprising a hydroxide and/or oxide of calcium and/or magnesium, a hydroxide of lithium and a chloride of lithium;
the total amount of the hydroxide of lithium and the chloride of lithium is 1 to 50 mol% relative to the hydroxide and/or oxide of calcium and/or magnesium;
the molar ratio of the lithium hydroxide to the lithium chloride is within the range of 025-4.
2. The chemical heat storage material according to claim 1, further comprising a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron, and zinc;
the amount of the metal is 0.1 to 40 mol% based on the hydroxide and/or oxide of calcium and/or magnesium.
3. A method for producing a chemical heat-accumulative material, comprising the step of mixing a hydroxide and/or oxide of calcium and/or magnesium, a hydroxide of lithium and a chloride of lithium;
the total amount of the hydroxide of lithium and the chloride of lithium is 1 to 50 mol% relative to the hydroxide and/or oxide of calcium and/or magnesium;
the molar ratio of the lithium hydroxide to the lithium chloride is in the range of 0.25 to 4.
4. The method according to claim 3, wherein the step of mixing further mixes a compound of at least one metal selected from the group consisting of nickel, cobalt, copper, aluminum, iron, and zinc;
the amount of the metal is 0.1 to 40 mol% based on the hydroxide and/or oxide of calcium and/or magnesium.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-025571 | 2018-02-16 | ||
| JP2018025571 | 2018-02-16 | ||
| PCT/JP2019/004259 WO2019159791A1 (en) | 2018-02-16 | 2019-02-06 | Chemical heat storage material and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111684039A CN111684039A (en) | 2020-09-18 |
| CN111684039B true CN111684039B (en) | 2021-12-28 |
Family
ID=67621020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980013119.3A Active CN111684039B (en) | 2018-02-16 | 2019-02-06 | Chemical heat storage material and preparation method thereof |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP7248989B2 (en) |
| KR (1) | KR102697677B1 (en) |
| CN (1) | CN111684039B (en) |
| WO (1) | WO2019159791A1 (en) |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6558568B1 (en) * | 1995-09-07 | 2003-05-06 | Claude Q. C. Hayes | Heat absorbing temperature control devices and method |
| ATE277755T1 (en) * | 1997-09-04 | 2004-10-15 | Claude Q C Hayes | HEAT CONTROL DEVICE |
| EP1242239B1 (en) * | 1999-07-14 | 2011-04-06 | Claude Q.C. Hayes | Thermal control composite |
| CN1157460C (en) * | 2001-12-28 | 2004-07-14 | 昆明理工大学 | Prepn process of composite heat accumualting material and composite filled heat accumulating chamber |
| JP4765072B2 (en) * | 2006-05-17 | 2011-09-07 | 国立大学法人東京工業大学 | Chemical heat pump |
| KR20080032498A (en) * | 2006-10-10 | 2008-04-15 | 박봉화 | Heating element composition and apparatus for heating food the same |
| JP5177386B2 (en) * | 2008-02-07 | 2013-04-03 | 国立大学法人東京工業大学 | Chemical heat pump |
| US7971437B2 (en) * | 2008-07-14 | 2011-07-05 | Bell Independent Power Corporation | Thermal energy storage systems and methods |
| JP2012201528A (en) * | 2011-03-24 | 2012-10-22 | Tateho Chemical Industries Co Ltd | Method for producing magnesium oxide sintered body |
| JP5935987B2 (en) * | 2012-04-06 | 2016-06-15 | 株式会社豊田中央研究所 | Chemical heat storage material, reaction device, heat storage device, and vehicle |
| JP6123183B2 (en) * | 2012-07-24 | 2017-05-10 | 株式会社デンソー | Chemical heat storage material, reactor and heat storage device |
| US20140358206A1 (en) * | 2013-05-31 | 2014-12-04 | Laurie HIROKANE | Therapeutic heating and cooling packs comprising decorative elements |
| JP5661960B1 (en) * | 2014-04-30 | 2015-01-28 | 株式会社山陽テクノ | Chemical heat storage material |
| CN104129834B (en) * | 2014-07-16 | 2015-07-29 | 国家电网公司 | A kind of method of molten salt electrochemistry process polychlorobiphenyl |
| JP6582356B2 (en) * | 2015-06-12 | 2019-10-02 | 国立大学法人東京工業大学 | Chemical heat storage material |
| JP7036335B2 (en) * | 2016-03-31 | 2022-03-15 | タテホ化学工業株式会社 | Chemical heat storage granulation and its manufacturing method |
| 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 |
-
2019
- 2019-02-06 JP JP2020500433A patent/JP7248989B2/en active Active
- 2019-02-06 CN CN201980013119.3A patent/CN111684039B/en active Active
- 2019-02-06 KR KR1020207023039A patent/KR102697677B1/en active IP Right Grant
- 2019-02-06 WO PCT/JP2019/004259 patent/WO2019159791A1/en active Application Filing
Also Published As
| Publication number | Publication date |
|---|---|
| KR102697677B1 (en) | 2024-08-23 |
| JP7248989B2 (en) | 2023-03-30 |
| CN111684039A (en) | 2020-09-18 |
| KR20200121305A (en) | 2020-10-23 |
| WO2019159791A1 (en) | 2019-08-22 |
| JPWO2019159791A1 (en) | 2021-02-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5177386B2 (en) | Chemical heat pump | |
| JP4765072B2 (en) | Chemical heat pump | |
| Kubota et al. | Enhancement of hydration rate of LiOH by combining with mesoporous carbon for Low-temperature chemical heat storage | |
| KR101859112B1 (en) | Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same | |
| KR102599491B1 (en) | Chemical heat storage material and its manufacturing method, and chemical heat pump and its operating method | |
| KR102599490B1 (en) | Chemical heat storage material and its manufacturing method, and chemical heat pump and its operating method | |
| CN111684039B (en) | Chemical heat storage material and preparation method thereof | |
| Palacios et al. | Water sorption-based thermochemical storage materials: A review from material candidates to manufacturing routes | |
| JP7332316B2 (en) | Method for producing granules for chemical heat storage | |
| JP6901726B2 (en) | Chemical heat storage material and its manufacturing method | |
| JP6815915B2 (en) | Chemical heat storage material and its manufacturing method | |
| WO2021106881A1 (en) | Chemical heat storage material and method for producing same, and chemical heat pump | |
| JP2018168223A (en) | Chemical thermal storage medium and method for producing the same | |
| Xu et al. | Activity enhancement of MgCO3/MgO for thermochemical energy storage by nitrate-promoted and morphology modification | |
| CN112354512A (en) | Bifunctional alkali metal nitrate modified CdO-MgCO3Material and preparation method | |
| WO2021221128A1 (en) | Chemical heat storage material and method for producing same | |
| JP6798917B2 (en) | Chemical heat storage material and its manufacturing method | |
| JP2019142988A (en) | Chemical thermal storage medium, and method for producing chemical thermal storage medium | |
| EP3591023A1 (en) | Heat storage material comprising metal salt of cyanuric acid | |
| Gao et al. | Analysis of the Variable Influence and Energy Storage Performance in Preparation of Solar Energy Storage Materials via Modification of Carbide Slag Using MnO2 through Wet Doping | |
| JP2019182922A (en) | Chemical thermal storage material | |
| Tawalbeh et al. | International Journal of Thermofluids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |