JP5661960B1 - Chemical heat storage material - Google Patents
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- JP5661960B1 JP5661960B1 JP2014093682A JP2014093682A JP5661960B1 JP 5661960 B1 JP5661960 B1 JP 5661960B1 JP 2014093682 A JP2014093682 A JP 2014093682A JP 2014093682 A JP2014093682 A JP 2014093682A JP 5661960 B1 JP5661960 B1 JP 5661960B1
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- 238000005338 heat storage Methods 0.000 claims abstract description 78
- 239000011232 storage material Substances 0.000 claims abstract description 53
- 239000000126 substance Substances 0.000 claims abstract description 49
- 238000006703 hydration reaction Methods 0.000 claims abstract description 36
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 27
- USOPFYZPGZGBEB-UHFFFAOYSA-N calcium lithium Chemical compound [Li].[Ca] USOPFYZPGZGBEB-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 239000000843 powder Substances 0.000 description 24
- 239000000292 calcium oxide Substances 0.000 description 23
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 23
- 235000012255 calcium oxide Nutrition 0.000 description 23
- 230000036571 hydration Effects 0.000 description 21
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 18
- 229940087373 calcium oxide Drugs 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 230000004580 weight loss Effects 0.000 description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 12
- 229910001947 lithium oxide Inorganic materials 0.000 description 12
- 239000000920 calcium hydroxide Substances 0.000 description 11
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 230000018044 dehydration Effects 0.000 description 10
- 230000020169 heat generation Effects 0.000 description 9
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000347 magnesium hydroxide Substances 0.000 description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- YMUYTQCKKRCJMP-UHFFFAOYSA-N aluminum;calcium;oxygen(2-) Chemical compound [O-2].[Al+3].[Ca+2] YMUYTQCKKRCJMP-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical class O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229960000869 magnesium oxide Drugs 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 229920000620 organic polymer Polymers 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
【解決手段】水和反応に基づく発熱可能温度が３０℃以下であり、かつ脱水反応に基づく蓄熱可能温度が２５０℃以下であることを特徴とする化学蓄熱材。この化学蓄熱材は、カルシウムリチウムアルミネートからなる。A chemical heat storage material characterized in that an exothermic temperature based on a hydration reaction is 30 ° C. or lower and a heat storage possible temperature based on a dehydration reaction is 250 ° C. or lower. This chemical heat storage material is made of calcium lithium aluminate.
Description
本発明は、低温での発熱、かつ低温での蓄熱が可能な化学蓄熱材に関する。 The present invention relates to a chemical heat storage material capable of generating heat at a low temperature and storing heat at a low temperature.
化学反応を利用して熱の吸収、放出を行なうことのできる物質である化学蓄熱材は、広く知られており、これを利用したケミカルヒートポンプは、排気熱として大気中へ放出されているエネルギーの回収および再利用の観点から有効である。例えば、各種エンジン（ガソリンエンジン、ガスエンジン、ディーゼルエンジン等）、鉄鋼や化学品等の製造工場、ごみ焼却場等からは多くの熱エネルギーが排出され、これらの排気熱源は未利用のまま排出されている場合が殆どで、化学蓄熱材を利用したこれら排気熱源からの排気熱の有効利用が検討されている。
代表的な化学蓄熱材である酸化カルシウム（ＣａＯ 分子量：５６．１）は、下式のように、水和反応により、水酸化カルシウム（ Ｃａ（ＯＨ）２ 分子量：７４．１）に変換される際、発熱（放熱）する。
＜水和反応＞ ＣａＯ ＋ Ｈ２Ｏ ⇒ Ｃａ（ＯＨ）２ ＋ Ｑ（熱量：１０９．２ｋＪ／モル）
また、水酸化カルシウムは、下式のように、脱水反応により、酸化カルシウムに変換される際、蓄熱（吸熱）する。
＜脱水反応＞ Ｃａ（ＯＨ）２ ＋ Ｑ（熱量：１０９．２ｋＪ／モル） ⇒ ＣａＯ ＋ Ｈ２Ｏ
この酸化カルシウムを蓄熱材として使用した場合は、先ず、前記酸化カルシウムの水和反応に基づく発熱がおこる。 次に、排気熱等を利用した蓄熱により、水酸化カルシウムは酸化カルシウムに再変換される。 この蓄熱の際、脱水分が減量する。 この減量率は、蓄熱材の質量あたりに蓄熱する熱量と直接、相関する値であり、蓄熱材の蓄熱性を示す重要な尺度となる。 例えば、水酸化カルシウムを、高温で処理し、脱水反応を行い、元の酸化カルシウムに戻す蓄熱操作を行った際の、減量率が３２．１質量％であると、酸化カルシウム１モル（５６．１ｇ）当たりの１０９．２ｋＪ熱量が完全に蓄熱されたことになる。 従い、例えば、ある温度で、脱水反応を行い、水酸化カルシウムの一部が脱水された時の減量率が３．２質量％であると、酸化カルシウム１モル（５６．１ｇ）当たりの１０．９ｋＪの熱量が蓄熱されたことになり、減量率が０質量％であると、全く蓄熱されていないことになる。
Chemical heat storage materials, which can absorb and release heat using chemical reactions, are widely known, and chemical heat pumps that use this are the sources of energy released into the atmosphere as exhaust heat. It is effective from the viewpoint of recovery and reuse. For example, a lot of heat energy is emitted from various engines (gasoline engines, gas engines, diesel engines, etc.), steel and chemical manufacturing factories, garbage incinerators, etc., and these exhaust heat sources are discharged unused. However, effective utilization of exhaust heat from these exhaust heat sources using chemical heat storage materials is being studied.
Calcium oxide (CaO 2 molecular weight: 56.1), which is a typical chemical heat storage material, is converted to calcium hydroxide (Ca (OH) 2 molecular weight: 74.1) by a hydration reaction as shown in the following formula. At that time, it generates heat (heat radiation).
<Hydration reaction> CaO + H 2 O ⇒ Ca (OH) 2 + Q (calorie: 109.2 kJ / mol)
Calcium hydroxide stores heat (endothermic) when it is converted to calcium oxide by a dehydration reaction as shown in the following formula.
<Dehydration reaction> Ca (OH) 2 + Q (calorie: 109.2 kJ / mol) ⇒ CaO + H 2 O
When this calcium oxide is used as a heat storage material, first, heat is generated based on the hydration reaction of the calcium oxide. Next, calcium hydroxide is reconverted to calcium oxide by heat storage using exhaust heat or the like. During this heat storage, the amount of dehydration is reduced. This weight loss rate is a value that directly correlates with the amount of heat stored per mass of the heat storage material, and is an important measure of the heat storage performance of the heat storage material. For example, when the weight loss rate is 32.1% by mass when calcium hydroxide is treated at a high temperature, subjected to a dehydration reaction and returned to the original calcium oxide, 1 mol of calcium oxide (56. The amount of heat of 109.2 kJ per 1 g) is completely stored. Therefore, for example, when a dehydration reaction is performed at a certain temperature and the weight loss rate when a part of calcium hydroxide is dehydrated is 3.2 mass%, 10.10 g per 1 mol (56.1 g) of calcium oxide. A heat amount of 9 kJ is stored, and if the weight loss rate is 0% by mass, no heat is stored.
酸化カルシウムは、３０℃以下の低温で水和反応が起こるので、発熱性は良好である。 しかし、これを化学蓄熱材として使用した場合、水和反応により生成した水酸化カルシウムの脱水反応を起こさせるために、５００℃以上の高温が必要である。 従い、排熱源として有効利用が期待されている、例えば２５０℃以下の低温度領域の熱源では、数時間加熱を続けても、その前記減量率は、１質量％にも満たず、このような低温度領域では、実質的に蓄熱が不可能であった。 逆に、例えば、水酸化ニッケルは、２３０℃程度の低温で、脱水反応を起こすので、この温度での蓄熱は可能であるが、蓄熱により生成する酸化ニッケルは、１１０℃程度のような高温の水蒸気でも、水和反応が起こらず、３０℃のような低温度領域では、実質的に発熱が不可能であった。 Since calcium oxide undergoes a hydration reaction at a low temperature of 30 ° C. or less, the exothermic property is good. However, when this is used as a chemical heat storage material, a high temperature of 500 ° C. or higher is required in order to cause a dehydration reaction of calcium hydroxide generated by the hydration reaction. Therefore, in a heat source in a low temperature region of, for example, 250 ° C. or less, which is expected to be effectively used as an exhaust heat source, even if heating is continued for several hours, the weight loss rate is less than 1% by mass. In the low temperature region, heat storage was practically impossible. Conversely, for example, nickel hydroxide undergoes a dehydration reaction at a low temperature of about 230 ° C., so heat storage at this temperature is possible, but nickel oxide generated by heat storage has a high temperature of about 110 ° C. Even with water vapor, a hydration reaction did not occur, and heat generation was substantially impossible in a low temperature region such as 30 ° C.
そこで、より低温での発熱と、より低温での蓄熱との両立を目指した化学蓄熱材が種々提案されている。 例えば、酸化アルミニウムカルシウムと水酸化カルシウムの混合物（特許文献１）、４５０℃以下で仮焼した水酸化マグネシウム（特許文献２）、マグネシウムと、ニッケル、コバルト、銅、アルミニウム等との複合酸化物 （特許文献３）、吸湿性金属塩を添加したマグネシウムまたはカルシウムの水酸化物 （特許文献４）、 表面に膨張化グラファイトを担持したカルシウムやマグネシウムの水酸化物（特許文献５）、アルカリ金属の塩化物が化学的に結合したカルシウムやマグネシウムの水酸化物（特許文献６）等がより低温で発熱および蓄熱が可能な化学蓄熱材として提案されている。 Therefore, various chemical heat storage materials have been proposed that aim to achieve both heat generation at a lower temperature and heat storage at a lower temperature. For example, a mixture of aluminum calcium oxide and calcium hydroxide (patent document 1), magnesium hydroxide calcined at 450 ° C. or less (patent document 2), composite oxide of magnesium and nickel, cobalt, copper, aluminum or the like ( Patent Document 3), Magnesium or Calcium Hydroxide with Addition of Hygroscopic Metal Salt (Patent Document 4), Calcium or Magnesium Hydroxide with Expanded Graphite on the Surface (Patent Document 5), Alkali Metal Chloride Hydroxides of calcium and magnesium (Patent Document 6) and the like in which chemicals are chemically bonded have been proposed as chemical heat storage materials capable of generating heat and storing heat at lower temperatures.
しかしながら、前記した公知の蓄熱材では、３０℃以下のような低温で発熱させ、かつ、２５０℃以下のような低温で畜熱させることができなかった。 すなわち、このような低温で、発熱と蓄熱とが両立して可能となるような蓄熱材は知られていなかった。 したがい、公知の蓄熱材を、前記した広範な用途でのケミカルヒートポンプに適応することは難しかった。 However, the above-described known heat storage material cannot generate heat at a low temperature such as 30 ° C. or less and cannot heat the animal at a low temperature such as 250 ° C. or less. That is, no heat storage material has been known that enables both heat generation and heat storage at such a low temperature. Therefore, it has been difficult to apply the known heat storage material to the chemical heat pump in the wide range of applications described above.
そこで本発明は、上記課題を解決するものであって、低温での発熱、かつ低温での蓄熱が両立可能な化学蓄熱材の提供を目的とする。 Then, this invention solves the said subject, Comprising: It aims at provision of the chemical heat storage material in which heat_generation | fever at low temperature and heat storage at low temperature are compatible.
本発明者らは、特定の組成を有する金属酸化物からなる化学蓄熱材により上記課題が解決されることを見出し、本発明の完成に至った。 The present inventors have found that the above problem can be solved by a chemical heat storage material made of a metal oxide having a specific composition, and have completed the present invention.
すなわち、本発明は下記を趣旨とするものである。
カルシウムリチウムアルミネートからなり、水和反応に基づく発熱可能温度が３０℃以下であり、かつ脱水反応に基づく蓄熱可能温度が２５０℃以下であることを特徴とする化学蓄熱材。
That is, the present invention has the following purpose.
A chemical heat storage material comprising calcium lithium aluminate, having a heat generating temperature based on a hydration reaction of 30 ° C or lower and a heat storage temperature based on a dehydration reaction of 250 ° C or lower.
本発明の化学蓄熱材は、穏和な条件での、発熱および蓄熱が可能なので、これを用いたケミカルヒートポンプは、未利用のまま排出されている排気熱源に幅広く利用することができる。 Since the chemical heat storage material of the present invention can generate heat and store heat under mild conditions, a chemical heat pump using the chemical heat storage material can be widely used as an exhaust heat source that is discharged without being used.
以下、本発明について詳細に説明する。
本発明の化学蓄熱材は、水和反応に基づく発熱可能温度が３０℃以下であり、かつ脱水反応に基づく蓄熱可能温度が２５０℃以下である。
Hereinafter, the present invention will be described in detail.
The chemical heat storage material of the present invention has a heat generating temperature based on a hydration reaction of 30 ° C. or lower, and a heat storage temperature based on a dehydration reaction of 250 ° C. or lower.
ここで、水和反応に基づく発熱可能温度の判定は以下の手順で行うことができる。 すなわち、所定の温度とした試料１８ｇをガラス製試験管（寸法：内径３０ｍｍ、高さ２００ｍｍ）に投入し、これに所定の温度とした水２０ｇを注入し、注入直後からの水温を測定する。 水を注入した直後から３０分以内に、上昇した水温の最高値と注入した水の水温との差が３０℃以上であり、かつ水温差が３０℃以上の水温の持続時間が１０分以上である場合、その温度で発熱可能と判定する。 Here, the determination of the heat generating temperature based on the hydration reaction can be performed by the following procedure. That is, 18 g of a sample having a predetermined temperature is put into a glass test tube (dimensions: inner diameter 30 mm, height 200 mm), 20 g of water having a predetermined temperature is poured therein, and the water temperature immediately after the injection is measured. Within 30 minutes immediately after injecting water, the difference between the maximum value of the increased water temperature and the water temperature of the injected water is 30 ° C. or more, and the duration of the water temperature with the water temperature difference of 30 ° C. or more is 10 minutes or more. If there is, it is determined that heat can be generated at that temperature.
また、脱水反応に基づく蓄熱可能温度の判定は以下のようにして行うことができる。すなわち、水和反応に基づく発熱が終了した試料を乾燥後、以下の手順で、所定温度での脱水反応に基づく減量率を算出し、この減量率が１０％以上であれば、この温度で、蓄熱可能と判定される。
（イ） 試料である発熱後の化学蓄熱材約４０ｍｇを熱天秤（ＴＧ）測定用のセル（直径５ｍｍ、高さ５ｍｍの白金製円筒容器）に投入する。
（ロ） このセルを熱天秤測定装置（株式会社リガク製 差動型示差熱天秤/ＴＧ８１２０に設置し、乾燥窒素気流中で１２０℃、１２０分処理することにより、化学蓄熱材に物理的に吸着していた水分を除去した際の質量Ａを読み取る。
（ハ） 前記１２０℃で６０分の処理後、引き続きＴＧ測定装置内で、窒素気流中、約１０分でセル温度を所定温度（２４０〜２５０℃）まで昇温し、その後、この所定温度とした定温で６０分処理する。（この処理で部分的もしくは完全に脱水反応が起こり蓄熱される） この処理でのＴＧ曲線を取得し、前記処理後の試料の質量Ｂを読み取り、化学蓄熱材の減量率を、以下の計算式を用いて算出する。
減量率（質量％）＝１００×（Ａ−Ｂ）／Ａ
Moreover, the determination of the heat storage possible temperature based on a dehydration reaction can be performed as follows. That is, after drying the sample that has generated heat based on the hydration reaction, the weight loss rate based on the dehydration reaction at a predetermined temperature is calculated according to the following procedure, and if this weight loss rate is 10% or more, at this temperature, It is determined that heat can be stored.
(A) About 40 mg of the chemical heat storage material after heat generation as a sample is put into a thermobalance (TG) measurement cell (platinum cylindrical container having a diameter of 5 mm and a height of 5 mm).
(B) This cell is physically adsorbed to a chemical heat storage material by installing it on a thermobalance measuring device (Differential differential thermal balance / TG8120 manufactured by Rigaku Corporation) and treating it in a dry nitrogen stream at 120 ° C for 120 minutes. The mass A when the moisture that has been removed is removed is read.
(C) After the treatment at 120 ° C. for 60 minutes, the cell temperature is continuously raised to a predetermined temperature (240 to 250 ° C.) in about 10 minutes in a TG measurement device, and then the predetermined temperature and Process for 60 minutes at the constant temperature. (This process partially or completely causes a dehydration reaction to store heat) Obtains a TG curve in this process, reads the mass B of the sample after the process, and calculates the weight loss rate of the chemical heat storage material as Calculate using.
Weight loss rate (mass%) = 100 × (A−B) / A
本発明の化学蓄熱材は、前記発熱可能温度が、３０℃以下であることが必須要件であるが、２０℃以下であることが好ましい。このようにすることにより、低温度領域での優れた発熱性が確保される。 In the chemical heat storage material of the present invention, it is essential that the heat generating temperature is 30 ° C. or lower, but it is preferably 20 ° C. or lower. By doing in this way, the exothermic property in the low temperature range is ensured.
また、本発明の化学蓄熱材は、前記蓄熱可能温度が２５０℃以下であることが必須要件であるが、２４０℃以下であることが好ましい。このようにすることにより、低温度領域での優れた蓄熱性が確保される。 In addition, the chemical heat storage material of the present invention has an essential requirement that the heat storage possible temperature is 250 ° C. or lower, but is preferably 240 ° C. or lower. By doing in this way, the outstanding thermal storage property in a low temperature area is ensured.
前記したような特性を有する本発明の化学蓄熱材は、酸化カルシウム、酸化アルミニウム、酸化リチウムの複合酸化物からなるカルシウムリチウムアルミネートであり、酸化カルシウム、酸化アルミニウム、酸化リチウムの一部または全部が固溶化したカルシウムリチウムアルミネートからなるものであることが好ましい。 The chemical heat storage material of the present invention having the characteristics as described above is a calcium lithium aluminate composed of a composite oxide of calcium oxide, aluminum oxide, and lithium oxide, and a part or all of calcium oxide, aluminum oxide, and lithium oxide are included. It is preferably made of a solid solution calcium lithium aluminate .
本発明で用いられるカルシウムリチウムアルミネートは、例えば以下のようなプロセスで製造することができる。すなわち、質量比で、ＣａＯ：Ａｌ２Ｏ３が２：８〜８：２である酸化カルシウムと酸化アルミニウムとの混合物１００質量部に、１〜２０質量部の酸化リチウムを加え、均一な混合物として後、これを１０００℃以上、好ましくは１４００℃以上の温度に加熱して、これらの混合物の一部または全部を固溶化させ、これを、冷却、粉砕することにより粉体状として得ることができる。 本発明の化学蓄熱材には、このような乾式プロセスに基づくカルシウムリチウムアルミネートを好ましく用いることができる。 The calcium lithium aluminate used in the present invention can be produced, for example, by the following process. That is, 1 to 20 parts by mass of lithium oxide is added to 100 parts by mass of a mixture of calcium oxide and aluminum oxide having a mass ratio of CaO: Al 2 O 3 of 2: 8 to 8: 2 to obtain a uniform mixture. Thereafter, this is heated to a temperature of 1000 ° C. or higher, preferably 1400 ° C. or higher, so that a part or all of the mixture is solid solution, and cooled and pulverized to obtain a powder. . For the chemical heat storage material of the present invention, calcium lithium aluminate based on such a dry process can be preferably used.
また、前記カルシウムリチウムアルミネートは、予め、質量比で、ＣａＯ：Ａｌ２Ｏ３が２：８〜８：２の酸化カルシウムと酸化アルミニウムとの均一な混合物を１０００℃以上、好ましくは１４００℃以上の温度に加熱して、冷却、粉砕して、カルシウムアルミネート粉体を製造しておき、これに酸化リチウムを均一に添加混合し、３００℃以上の高温で熱処理することによっても得ることができる。 なお、前記カルシウムアルミネート粉体は、アルミナセメントとして市販されている粉体も好ましく用いることができる。 すなわちこのアルミナセメントに酸化リチウムを均一に添加混合し、加熱処理をすることによってもカルシウムリチウムアルミネートを得ることができる。 In addition, the calcium lithium aluminate is a mass mixture of CaO: Al 2 O 3 of 2: 8 to 8: 2 in a uniform mixture of calcium oxide and aluminum oxide at 1000 ° C. or higher, preferably 1400 ° C. or higher. It is also possible to obtain calcium aluminate powder by heating to a temperature of, cooled and pulverized, uniformly adding lithium oxide to this, and heat-treating at a high temperature of 300 ° C. or higher. . In addition, the said calcium aluminate powder can also use preferably the powder marketed as an alumina cement. That is, calcium lithium aluminate can also be obtained by uniformly adding and mixing lithium oxide to the alumina cement, followed by heat treatment.
前記カルシウムリチウムアルミネート粉体製造過程において、前記した混合物を固溶化した後、冷却する際、冷却速度を調整することにより、結晶質もしくは非晶質いずれのカルシウムリチウムアルミネートでも製造することが出来るが、本発明の化学蓄熱材に使用されるカルシウムリチウムアルミネートは結晶質であっても、非晶質であっても良い。 In the calcium lithium aluminate powder manufacturing process, after cooling the above-mentioned mixture, when cooling, the crystalline lithium lithium aluminate can be manufactured by adjusting the cooling rate. However, the calcium lithium aluminate used in the chemical heat storage material of the present invention may be crystalline or amorphous.
カルシウムリチウムアルミネート粉体の粒度に制限はないが、体積基準の平均粒径が、３００μｍ以下のものが好ましく用いられ、１５０μｍ以下のものがより好ましく、１００μｍ以下のものがさらに好ましい。ここで、平均粒子径が３００μｍより大きい場合、水和反応が遅れ、発熱が遅くなる傾向がある。 Although there is no restriction | limiting in the particle size of calcium lithium aluminate powder, that whose average particle diameter of a volume basis is 300 micrometers or less is used preferably, 150 micrometers or less are more preferable, and 100 micrometers or less are more preferable. Here, when the average particle size is larger than 300 μm, the hydration reaction tends to be delayed and the heat generation tends to be delayed.
カルシウムリチウムアルミネート粉体の原料となる酸化カルシウム、酸化アルミニウム、酸化リチウム粉体の混合方法に制限はなく、公知の乾式法や湿式法を用いることができる。 There are no limitations on the method of mixing calcium oxide, aluminum oxide, and lithium oxide powder, which are raw materials for the calcium lithium aluminate powder, and a known dry method or wet method can be used.
乾式法で均一混合するには、前記原料粉体を、ボールミル、ビーズミル、Ｖ型ブレンダー、ナウターミキサー、パン型ミキサー、オムニミキサー等の混合機を用いて均一混合すればよい。 In order to uniformly mix by the dry method, the raw material powder may be uniformly mixed using a mixer such as a ball mill, a bead mill, a V-type blender, a nauter mixer, a pan-type mixer, or an omni mixer.
また、湿式法で均一混合するには、前記原料粉体を、アルコールや水等の媒体中に分散して撹拌することにより均一に混合後、媒体であるアルコールや水を留去すれば良い。 Further, in order to uniformly mix by a wet method, the raw material powder may be dispersed in a medium such as alcohol or water and stirred to uniformly mix, and then the alcohol or water as the medium may be distilled off.
バインダ成分を少量配合し、カルシウムリチウムアルミネート粉体を造粒して用いることもできる。ここで用いられるバインダとしては、２５０℃では分解しないポリイミドやポリアミドイミド等耐熱性を有する有機高分子や無機バインダである粘土等を用いることが好ましい。 A small amount of a binder component can be blended, and calcium lithium aluminate powder can be granulated and used. As the binder used here, it is preferable to use a heat-resistant organic polymer such as polyimide or polyamideimide that does not decompose at 250 ° C., or clay that is an inorganic binder.
前記カルシウムリチウムアルミネートには、本発明の効果を実質的に喪失させない範囲で他の成分を配合することができる。 これらの成分の例としては、鉄粉、アルミ粉等の金属粉体やカーボン粉体などの熱伝導性改良材が挙げられる。 The calcium lithium aluminate can be blended with other components within a range that does not substantially lose the effects of the present invention. Examples of these components include metal powders such as iron powder and aluminum powder, and thermal conductivity improving materials such as carbon powder.
以上述べたように、本発明の化学蓄熱材は、３０℃以下の低温で、水和反応に基づく発熱が可能であり、かつ２５０℃以下の低温で、脱水反応に基づく蓄熱が可能であるので、これを用いたケミカルヒートポンプは、これまで排熱の回収、再利用が難しかった様々な分野で幅広く利用することができる。 As described above, the chemical heat storage material of the present invention can generate heat based on a hydration reaction at a low temperature of 30 ° C. or lower, and can store heat based on a dehydration reaction at a low temperature of 250 ° C. or lower. The chemical heat pump using this can be widely used in various fields where it has been difficult to recover and reuse exhaust heat.
以下、実施例に基づき本発明を更に具体的に説明するが、本発明はこれらの実施例のみに限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited only to these Examples.
実施例における発熱性の評価は以下の手順で行った。
測定雰囲気を所定温度（２０℃〜３０℃）とし、試料１８ｇをガラス製試験管（寸法：内径３０ｍｍ、高さ２００ｍｍ）に投入し、これに所定の温度とした水２０ｇを注入し、注入直後からの水温を測定する。 水を注入した直後から３０分以内に、上昇した水温の最高値と注入した水の水温との差が３０℃以上であり、かつ水温差が３０℃以上の水温の持続時間が１０分以上である場合、その温度で発熱可能と判定した。
The exothermic evaluation in the examples was performed according to the following procedure.
The measurement atmosphere is set to a predetermined temperature (20 ° C. to 30 ° C.), 18 g of a sample is put into a glass test tube (dimension: inner diameter 30 mm, height 200 mm), and 20 g of water at a predetermined temperature is injected into the glass test tube. Measure the water temperature from Within 30 minutes immediately after injecting water, the difference between the maximum value of the increased water temperature and the water temperature of the injected water is 30 ° C. or more, and the duration of the water temperature with the water temperature difference of 30 ° C. or more is 10 minutes or more. In some cases, it was determined that heat could be generated at that temperature.
実施例における蓄熱性の評価は以下の様に行った。
前記発熱性試験で得られた発熱後の蓄熱材を含む水分散体を、減圧下、３０℃以下の温度で乾燥して、大部分の水を蒸発させたのち、以下の手順（イ）〜（ハ）に従って熱天秤（TG）を測定した。
（イ） 試料である発熱後の化学蓄熱材約４０ｍｇを熱天秤（ＴＧ）測定用のセル（直径５ｍｍ、高さ５ｍｍの白金製円筒容器）に投入する。
（ロ） このセルを熱天秤測定装置（株式会社リガク製 差動型示差熱天秤/ＴＧ８１２０）に設置し、乾燥窒素気流中で１２０℃、６０分処理することにより、化学蓄熱材に物理的に吸着していた水分を除去した際の質量Ａを読み取る。
（ハ） 前記１２０℃で６０分の処理後、引き続きＴＧ測定装置内で、窒素気流中、約１０分でセル温度を所定温度（２５０℃以下）まで昇温し、この温度とした定温で６０分処理する。この処理でのＴＧ曲線を取得し、前記処理後の試料の質量Ｂを読み取り、化学蓄熱材の減量率を、以下の計算式を用いて算出する。
減量率（質量％）＝１００×（Ａ−Ｂ）／Ａ
この減量率が１０％以上の時、その温度で蓄熱可能と判定した。
Evaluation of the heat storage property in the examples was performed as follows.
The water dispersion containing the heat storage material after heat generation obtained in the exothermic test is dried at a temperature of 30 ° C. or less under reduced pressure to evaporate most of the water. A thermobalance (TG) was measured according to (c).
(A) About 40 mg of the chemical heat storage material after heat generation as a sample is put into a thermobalance (TG) measurement cell (platinum cylindrical container having a diameter of 5 mm and a height of 5 mm).
(B) By installing this cell in a thermobalance measuring device (Differential differential thermal balance / TG8120, manufactured by Rigaku Corporation) and treating it in a dry nitrogen stream at 120 ° C. for 60 minutes, it is physically applied to a chemical heat storage material. The mass A when the adsorbed moisture is removed is read.
(C) After the treatment at 120 ° C. for 60 minutes, the cell temperature is raised to a predetermined temperature (250 ° C. or lower) in about 10 minutes in a TG measurement apparatus in about 10 minutes. Process for minutes. A TG curve in this process is acquired, the mass B of the sample after the process is read, and the weight loss rate of the chemical heat storage material is calculated using the following calculation formula.
Weight loss rate (mass%) = 100 × (A−B) / A
When this weight loss rate was 10% or more, it was determined that heat could be stored at that temperature.
なお、体積基準の平均粒径は、株式会社堀場製作所製レーザ回折式粒度分布測定装置ＬＡ−９１０を用い、それぞれの粉体をエタノール中に分散させて測定した。 The volume-based average particle diameter was measured by dispersing each powder in ethanol using a laser diffraction particle size distribution measuring apparatus LA-910 manufactured by Horiba, Ltd.
［実施例１］
酸化カルシウム８質量部、酸化アルミニウム１２質量部、酸化リチウム１質量部とをボールミルで均一に混合し、坩堝に投入後、１５００℃で１時間加熱した後、冷却して生成した固溶体を坩堝から取出し、これをボールミルで粉砕して、平均粒径３２μｍのカルシウムリチウムアルミネート粉体からなる化学蓄熱材Ｐ−１を得た。Ｐ−１の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 1]
8 parts by mass of calcium oxide, 12 parts by mass of aluminum oxide, and 1 part by mass of lithium oxide are uniformly mixed with a ball mill, put into a crucible, heated at 1500 ° C. for 1 hour, and then cooled to take out the solid solution produced. This was pulverized with a ball mill to obtain a chemical heat storage material P-1 made of calcium lithium aluminate powder having an average particle size of 32 μm. P-1 exothermicity (hydration temperature 30 ° C.) and heat storage (dehydration temperature 250 ° C.) were measured according to the procedure described above. The results are shown in Table 1.
［実施例２］
酸化カルシウム粉体１２質量部と酸化アルミニウム粉体８質量部としたこと以外は、前記と同様にして、平均粒径３５μｍのカルシウムリチウムアルミネート粉体からなる化学蓄熱材Ｐ−２を得た。Ｐ−２の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 2]
A chemical heat storage material P-2 made of calcium lithium aluminate powder having an average particle size of 35 μm was obtained in the same manner as described above except that 12 parts by mass of calcium oxide powder and 8 parts by mass of aluminum oxide powder were used. The exothermic property (hydration temperature 30 ° C.) and heat storage property (dehydration temperature 250 ° C.) of P-2 were measured according to the procedure described above. The results are shown in Table 1.
［実施例３］
市販のアルミナセメント２０質量部と酸化リチウム１質量部をボールミルで均一に混合し、３００℃で２時間処理した。 これを粉砕して、平均粒径４１μｍのカルシウムリチウムアルミネート粉体からなる化学蓄熱材Ｐ−３を得た。Ｐ−３の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。なお、ここで用いた市販のアルミナセメントの組成は酸化カルシウム３６質量％、酸化アルミニウム５５質量％、その他成分９質量％であり、カルシウムリチウムアルミネート含有量は９１質量％であった。
[Example 3]
20 parts by mass of commercially available alumina cement and 1 part by mass of lithium oxide were uniformly mixed by a ball mill and treated at 300 ° C. for 2 hours. This was pulverized to obtain a chemical heat storage material P-3 made of calcium lithium aluminate powder having an average particle size of 41 μm. The exothermic property (hydration temperature 30 ° C.) and heat storage property (dehydration temperature 250 ° C.) of P-3 were measured according to the procedure described above. The results are shown in Table 1. The composition of the commercially available alumina cement used here was 36% by mass of calcium oxide, 55% by mass of aluminum oxide, 9% by mass of other components, and the content of calcium lithium aluminate was 91% by mass.
［実施例４］
Ｐ−３の発熱性（水和温度２０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 4]
The exothermic property (hydration temperature 20 ° C.) and heat storage property (dehydration temperature 250 ° C.) of P-3 were measured according to the procedure described above. The results are shown in Table 1.
［実施例５］
Ｐ−３の発熱性（水和温度３０℃）および蓄熱性（脱水温度２４０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 5]
The exothermic property (hydration temperature 30 ° C.) and heat storage property (dehydration temperature 240 ° C.) of P-3 were measured according to the procedure described above. The results are shown in Table 1.
［実施例６］
酸化リチウムの配合量を１．５質量部としたこと以外は実施例３と同様に行い、化学蓄熱材Ｐ−４を得た。Ｐ−４の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 6]
Except having made the compounding quantity of lithium oxide into 1.5 mass parts, it carried out similarly to Example 3 and obtained the chemical heat storage material P-4. P-4 exothermic properties (hydration temperature 30 ° C.) and heat storage properties (dehydration temperature 250 ° C.) were measured according to the procedure described above. The results are shown in Table 1.
［実施例７］
酸化リチウムの配合量を２．０質量部としたこと以外は実施例３と同様に行い、化学蓄熱材Ｐ−５を得た。Ｐ−５の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 7]
Except having made the compounding quantity of lithium oxide into 2.0 mass parts, it carried out similarly to Example 3 and obtained the chemical heat storage material P-5. P-5 exothermic properties (hydration temperature 30 ° C.) and heat storage properties (dehydration temperature 250 ° C.) were measured according to the procedure described above. The results are shown in Table 1.
［比較例１］
実施例１で用いたものと同様の組成とした原料を、固溶化させることなく混合し、ボールミルで均一に混合することにより、平均粒径が２８μｍの混合粉体からなる化学蓄熱材Ｃ−１を得た。 Ｃ−１の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 1]
A raw material having the same composition as that used in Example 1 was mixed without solid solution, and mixed uniformly by a ball mill, whereby a chemical heat storage material C-1 comprising a mixed powder having an average particle size of 28 μm. Got. The exothermic properties (hydration temperature 30 ° C.) and heat storage properties (dehydration temperature 250 ° C.) of C-1 were measured according to the procedure described above. The results are shown in Table 1.
［比較例２］
酸化リチウムを用いなかったこと以外は実施例１と同様にして平均粒径が２１μｍの粉体からなる化学蓄熱材Ｃ−２を得た。Ｃ−２の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 2]
A chemical heat storage material C-2 made of powder having an average particle size of 21 μm was obtained in the same manner as in Example 1 except that lithium oxide was not used. The exothermicity of C-2 (hydration temperature 30 ° C.) was measured according to the procedure described above. The results are shown in Table 1.
［比較例３］
酸化リチウムを用いなかったこと以外は実施例３で用いたアルミナセメントのみ（Ｃ−３とする）の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 3]
Except that lithium oxide was not used, the exothermic property (hydration temperature 30 ° C.) of only the alumina cement used in Example 3 (referred to as C-3) was measured according to the procedure described above. The results are shown in Table 1.
［比較例４］
特許文献６の実施例１の記載に従い、水酸化カルシウムと塩化リチウムの粉体とを乾式で均一に混合し、この混合物を、３００℃で３００分処理することにより、粉体の全質量に対する塩化リチウムの配合量を６．８質量％とした粉体からなる化学蓄熱材Ｃ−４を得た。 Ｃ−４の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 4]
According to the description in Example 1 of Patent Document 6, calcium hydroxide and lithium chloride powder are uniformly mixed in a dry process, and this mixture is treated at 300 ° C. for 300 minutes, whereby the total mass of the powder is chlorinated. A chemical heat storage material C-4 made of powder with a lithium content of 6.8% by mass was obtained. The exothermicity of C-4 (hydration temperature 30 ° C.) was measured according to the procedure described above. The results are shown in Table 1.
［比較例５］
特許文献１の記載を参考に、水酸化カルシウムに、７質量％のアルミニウム粉末と水を加えることにより得られた反応物を５００℃で処理し、これを粉砕することにより、化学蓄熱材Ｃ−５を得た。Ｃ−５の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 5]
With reference to the description in Patent Document 1, a reaction product obtained by adding 7% by mass of aluminum powder and water to calcium hydroxide is treated at 500 ° C. and pulverized to obtain a chemical heat storage material C- 5 was obtained. The exothermicity of C-5 (hydration temperature 30 ° C.) was measured according to the procedure described above. The results are shown in Table 1.
［比較例６］
特許文献２の実施例１の記載に従い、水酸化マグネシウム３５０℃で１２０分仮焼することにより、酸化マグネシウム粉体（粒径１０〜３０μｍ）からなる化学蓄熱材Ｃ−６を得た。Ｃ−６の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 6]
According to the description in Example 1 of Patent Document 2, the heat storage material C-6 made of magnesium oxide powder (particle size: 10 to 30 μm) was obtained by calcining at 350 ° C. for 120 minutes. The exothermicity of C-6 (hydration temperature 30 ° C.) was measured according to the procedure described above. The results are shown in Table 1.
［比較例７］
特許文献３の段落番号[００１４］の記載に従い、１０モル％の塩化リチウムが配合された水酸化マグネシウム粉体を得た。これを坩堝に投入し、２５０℃で１２０分処理して脱水することにより、化学蓄熱材Ｃ−７を得た。Ｃ−７の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 7]
In accordance with the description in paragraph [0014] of Patent Document 3, magnesium hydroxide powder containing 10 mol% lithium chloride was obtained. This was put into a crucible, treated at 250 ° C. for 120 minutes and dehydrated to obtain a chemical heat storage material C-7. The exothermicity of C-7 (hydration temperature 30 ° C.) was measured according to the procedure described above. The results are shown in Table 1.
［実施例８］
実施例３の発熱試験で得られたＰ−３を含むスラリを３０℃の減圧乾燥機で乾燥を行い大部分の水を蒸発させたのち、これを、ステンレス製の容器に入れ、１００℃で減圧乾燥を行い、Ｐ−３に含まれていた吸着水を除去した。これをステンレス製の容器に移し替え、窒素ガス雰囲気下、２５０℃で２時間処理し、脱水反応を行い、再生された蓄熱材Ｐ−６を得た。 Ｐ−６の発熱性（水和温度３０℃）および蓄熱性（脱水温度２５０℃）を前記した手順に従って測定した。結果を表１に示す。
[Example 8]
The slurry containing P-3 obtained in the exothermic test of Example 3 was dried with a vacuum dryer at 30 ° C. to evaporate most of the water, and then put in a stainless steel container at 100 ° C. The adsorbed water contained in P-3 was removed by drying under reduced pressure. This was transferred to a stainless steel container, treated in a nitrogen gas atmosphere at 250 ° C. for 2 hours, subjected to a dehydration reaction, and a regenerated heat storage material P-6 was obtained. P-6 exothermic properties (hydration temperature 30 ° C.) and heat storage properties (dehydration temperature 250 ° C.) were measured according to the procedure described above. The results are shown in Table 1.
［比較例８］
実施例８で用いた吸着水を除去したのみで、２５０℃での脱水を行わなかった試料（Ｃ−８とする）の発熱性（水和温度３０℃）を前記した手順に従って測定した。結果を表１に示す。
[Comparative Example 8]
The exothermic property (hydration temperature 30 ° C.) of a sample (denoted as C-8) in which only the adsorbed water used in Example 8 was removed but not dehydrated at 250 ° C. was measured according to the procedure described above. The results are shown in Table 1.
実施例１〜７で示した様に、本発明の化学蓄熱材は、３０℃以下という低温度領域で、水和による発熱反応が進行し、水温が２０℃以上上昇することが判る。また、２５０℃以下という低温度領域で、１０質量％以上の減量率を有しており、このような低温でも充分に脱水反応が進行することが判る。 さらに、実施例８で示した様に、２５０℃で脱水され蓄熱された本発明の蓄熱材は、３０℃以下という低温度領域で、再び、水和による発熱反応が進行し、水温が３０℃以上上昇することが判る。これにより、この脱水反応で化学蓄熱材は再生され、再び水和反応を行うことができ、本発明の蓄熱材は再生使用可能であることが判る。 これに対し、比較例１で示した様に、酸化カルシウムそのものを発熱材として利用したものは、３０℃以下という低温度領域で、水和による発熱が可能であっても、２５０℃以下の低温では殆ど脱水されないことが判る。 また、比較例３で示した様に、カルシウムアルミネートのみでは、３０℃以下という低温度領域では、殆ど水和による発熱反応が進行ないことが判る。 さらに、公知の化学蓄熱材では、３０℃以下という低温度領域では、殆ど水和による発熱反応が進行ないことが判る。 As shown in Examples 1 to 7, it can be seen that the chemical heat storage material of the present invention undergoes an exothermic reaction due to hydration in a low temperature region of 30 ° C. or less, and the water temperature rises by 20 ° C. or more. Moreover, it has a weight loss rate of 10% by mass or more in a low temperature region of 250 ° C. or less, and it can be seen that the dehydration reaction proceeds sufficiently even at such a low temperature. Furthermore, as shown in Example 8, the heat storage material of the present invention dehydrated and stored at 250 ° C. has an exothermic reaction due to hydration again in a low temperature region of 30 ° C. or less, and the water temperature is 30 ° C. It turns out that it rises more. Thus, the chemical heat storage material is regenerated by this dehydration reaction, and the hydration reaction can be performed again, and it can be seen that the heat storage material of the present invention can be recycled. On the other hand, as shown in Comparative Example 1, the one using calcium oxide itself as a heat generating material has a low temperature of 250 ° C. or less even if heat generation by hydration is possible in a low temperature region of 30 ° C. or less. It turns out that it is hardly dehydrated. In addition, as shown in Comparative Example 3, it can be seen that with only calcium aluminate, an exothermic reaction due to hydration hardly proceeds in a low temperature region of 30 ° C. or lower. Furthermore, it can be seen that in known chemical heat storage materials, the exothermic reaction due to hydration hardly proceeds in a low temperature region of 30 ° C. or lower.
以上述べたように、本発明の化学蓄熱材は、穏和な条件での、発熱および蓄熱が可能なので、これを用いたケミカルヒートポンプは、未利用のまま排出されている排気熱源に幅広く利用することができる。
表１
As described above, since the chemical heat storage material of the present invention can generate heat and store heat under mild conditions, a chemical heat pump using this can be widely used as an exhaust heat source that is discharged unused. Can do.
Table 1
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