JPH01225686A - Chemical heat storage material and its manufacture - Google Patents
Chemical heat storage material and its manufactureInfo
- Publication number
- JPH01225686A JPH01225686A JP63049521A JP4952188A JPH01225686A JP H01225686 A JPH01225686 A JP H01225686A JP 63049521 A JP63049521 A JP 63049521A JP 4952188 A JP4952188 A JP 4952188A JP H01225686 A JPH01225686 A JP H01225686A
- Authority
- JP
- Japan
- Prior art keywords
- heat storage
- quicklime
- chemical heat
- limestone
- storage material
- 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.)
- Granted
Links
- 238000005338 heat storage Methods 0.000 title claims abstract description 44
- 239000000126 substance Substances 0.000 title claims abstract description 43
- 239000011232 storage material Substances 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 235000019738 Limestone Nutrition 0.000 claims abstract description 33
- 239000006028 limestone Substances 0.000 claims abstract description 33
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 100
- 239000000292 calcium oxide Substances 0.000 claims description 51
- 235000012255 calcium oxide Nutrition 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 21
- 230000035939 shock Effects 0.000 abstract description 5
- 229910052573 porcelain Inorganic materials 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 description 19
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007789 gas Substances 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000017525 heat dissipation Effects 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000567 combustion gas Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 235000008853 Zanthoxylum piperitum Nutrition 0.000 description 1
- 244000131415 Zanthoxylum piperitum Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は化学蓄熱装置に用いる化学蓄熱材、特に生石灰
を主体とした化学蓄熱材及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a chemical heat storage material used in a chemical heat storage device, particularly to a chemical heat storage material mainly composed of quicklime, and a method for manufacturing the same.
化学蓄熱装置は、第１１図に示すように１反応材すなわ
ち化学蓄熱材（たとえば生石灰）３を収納した第１容器
１、被反応材（たとえば水）４を収納した第２容器２、
それらを結ぶバイブ５、バイブ５の途中に設けたバルブ
６から構成されている。そして被反応材４の蒸気をバイ
ブ５を介して第１容器１内に導入して化学蓄熱材３と反
応させて発熱させ、この熱を取出して給湯、暖房、プロ
セス加熱等に利用するものである。この化学蓄熱装置に
おいて、最も重要なことは、化学蓄熱材３が常に安定に
動作し、くり返し使えることができるということである
。生石灰を生体とした化学蓄熱材３に関する公知例とし
ては、特開昭６１−１９９８２２号、特開昭６２−３０
１８１′号なるものがあるが、くり返して何回も使用す
ることを目的としたものではない、また生石灰に関連す
る他の公知例として特開昭５８−８３１９８号があるが
、これは５００℃以下でも水酸化カルシウムが熱分解し
て元の酸化カルシウム（生石灰）に再生でき、その再生
率を上げるための添加剤に関する発明である。As shown in FIG. 11, the chemical heat storage device includes a first container 1 containing a reactant, that is, a chemical heat storage material (e.g. quicklime) 3, a second container 2 containing a reactant material (e.g. water) 4,
It consists of a vibrator 5 that connects them, and a valve 6 provided in the middle of the vibrator 5. Then, the steam of the reacted material 4 is introduced into the first container 1 via the vibrator 5 and reacts with the chemical heat storage material 3 to generate heat, and this heat is extracted and used for hot water supply, space heating, process heating, etc. be. In this chemical heat storage device, the most important thing is that the chemical heat storage material 3 always operates stably and can be used repeatedly. Known examples of the chemical heat storage material 3 using quicklime as a living body include JP-A-61-199822 and JP-A-62-30.
There is a product called No. 181', but it is not intended to be used repeatedly. Another known example related to quicklime is JP-A No. 58-83198, which is not intended for repeated use over and over again. In the following, calcium hydroxide can be thermally decomposed and regenerated into the original calcium oxide (quicklime), and the invention relates to an additive for increasing the regeneration rate.
上記従来技術においては、生石灰（酸化力ルシラム）を
化学蓄熱材として、くり返して長期にわたって使用でき
るように改質するための技術に関しては開示されていな
い。The above-mentioned prior art does not disclose a technique for modifying quicklime (oxidized luciram) so that it can be used repeatedly over a long period of time as a chemical heat storage material.
ナ
本発明の目的は、長期にわたってくり返し使残ることの
できる化学蓄熱材及びその製造方法を得ることにある。An object of the present invention is to obtain a chemical heat storage material that can be used repeatedly over a long period of time, and a method for manufacturing the same.
従来用いていた非晶質生石灰に対し、本発明では特に粒
径が０．３〜４ｍｍの範囲の結晶質の生石灰を用いる。In contrast to the conventionally used amorphous quicklime, the present invention uses crystalline quicklime having a particle size in the range of 0.3 to 4 mm.
結晶質生石灰を作る原料として結晶質の石灰石（炭酸カ
ルシウム）を用い、これを所定の方法で焼きながら生石
灰に変える。この過程において、生石灰の表面からその
内部にわたって、多数の穴（気孔）が生成される。この
ようにして多孔質状の生石灰が得られ、二オレを主体と
した化学蓄熱材を得ることができる。Crystalline limestone (calcium carbonate) is used as the raw material for making crystalline quicklime, and is converted into quicklime by burning it using a prescribed method. In this process, many holes (pores) are generated from the surface of quicklime to its interior. In this way, porous quicklime can be obtained, and a chemical heat storage material mainly composed of diolet can be obtained.
上記結晶質石灰石の加熱過程において、加熱温度は８５
０℃〜１１００℃の範囲に加熱することにより、穴径０
．１μｍ〜０，５μｍの範囲の気孔を作ることができる
。In the heating process of the crystalline limestone mentioned above, the heating temperature is 85
By heating in the range of 0°C to 1100°C, the hole diameter can be reduced to 0.
．． Pores in the range of 1 μm to 0.5 μm can be created.
さらに、前記多孔質状の生石灰に粒径１〜１０ｍの範囲
の結晶質の石灰石を５〜３０重量％添加して製造した化
学蓄熱材も有効である。Furthermore, a chemical heat storage material manufactured by adding 5 to 30% by weight of crystalline limestone with a particle size of 1 to 10 m to the porous quicklime is also effective.
生石灰の表面から内部に生じた穴（気孔）は。 Holes (pores) are formed inside the surface of quicklime.
化学蓄熱装置内にて被反応材である水蒸気と反応する際
の蒸気通路となる。水蒸気は容易にこの穴を通りながら
、生石灰内部に浸入して反応し、高温度の熱を発生する
。穴（気孔）の無い、従来の化学蓄熱材は、生石灰の表
面から水蒸気との水和反応が始まり、徐々に内部の反応
面が移動していくので、反応速度が遅く、また穴（気孔
）のような余剰空間が全くないので、生石灰（酸化カル
シウム）から消石炭（水酸化カルシウム）に変化する過
程における体積膨張を吸収する場所が無く。It becomes a steam passage when reacting with water vapor, which is a reactant material, in a chemical heat storage device. Water vapor easily passes through these holes, penetrates inside the quicklime, reacts, and generates high-temperature heat. In conventional chemical heat storage materials, which have no holes (pores), the hydration reaction with water vapor starts from the surface of quicklime, and the reaction surface inside gradually moves, so the reaction rate is slow and there are no holes (pores). Since there is no surplus space, there is no place to absorb the volume expansion during the process of changing from quicklime (calcium oxide) to slaked coal (calcium hydroxide).
生石灰の粒子が破壊し、最後には粉化し、使用に耐えな
くなる。これに対して、本発明の化学蓄熱材は、多数の
気孔を有するので生石灰粒子の破壊が無く、長期間にわ
たって使用できる・〔実施例〕
以下１本発明の実施例について説明する１本発明の化学
蓄熱材の原料としては、結晶質の石灰石（寒水など）を
用いる０石灰石より生石灰を作る方法として、従来は立
がま、ロータリーキリン。The quicklime particles break down and eventually turn into powder, making it unusable. In contrast, the chemical heat storage material of the present invention has a large number of pores, so there is no destruction of quicklime particles, and it can be used for a long period of time. As a raw material for chemical heat storage materials, crystalline limestone (such as cold water) is used to make quicklime from limestone.
流動式乾燥器、カルシマチック焼成がま等を用い。Using a fluidized dryer, calcimatic kiln, etc.
コークス、石炭、ガス等を燃焼し、その燃焼ガスを石灰
石中に吹込んで、それを焼きながら生石灰を得るという
方法をとっていた。このような方法では多孔質状の生石
灰を作ることはできない。The method used was to burn coke, coal, gas, etc., blow the combustion gas into limestone, and burn it to obtain quicklime. Porous quicklime cannot be made using this method.
第１図を用いて、本発明の化学蓄熱材としての生石灰を
得る方法について説明する。炉＜ｍ気炉。A method for obtaining quicklime as a chemical heat storage material of the present invention will be explained with reference to FIG. Furnace < m air furnace.
マツクル炉）７中に平形の皿８（たとえば磁製皿。A flat dish 8 (for example, a porcelain dish) is placed in a Matsukuru furnace 7.
素焼き皿）を設け、この上に原料としての石灰石３を乗
せる１石灰石３の粒径としては０．３〜４Ｉの範囲のも
のを選定し、これを皿８に乗せた時の層厚さは２０■以
下と薄くする。炉７の内壁から石灰石３への伝熱は、主
として輻射伝熱によって行なわれるが、内部に存在する
気体（主として空気）の対流伝熱も、それに加わる９本
発明では、従来用いていた不純物質を含む燃焼ガスの強
制対流伝熱は、全く利用しない、炉７により１石灰石３
を８５０℃〜１１００℃の温度範囲で、２時間から７時
間（好ましくは３〜５時間）にわたって加熱する。その
後温度を下げ、５００℃から６００℃の温度範囲で１時
間以上（好ましくは２〜４時間）加熱する。そして、好
ましくはこの温度に加熱された原料を、そのまま真空容
器内または五酸化リン等の強力乾燥材が入っている。大
形容器内に移して徐冷する。このような過程を経て、本
目的とする化学蓄熱材（生石灰）が得られる。炉７によ
る原料（石灰石３）を８５０℃から１１００℃の高温度
で加熱する時間は、炉７の長さと、ローラー１０によっ
て駆動されるコンベヤー９の速度によって決定される。1. The particle size of the limestone 3 is selected to be in the range of 0.3 to 4I, and the layer thickness when placed on the plate 8 is as follows: Make it thinner than 20cm. Heat transfer from the inner wall of the furnace 7 to the limestone 3 is mainly carried out by radiation heat transfer, but convective heat transfer from the gas (mainly air) existing inside is also added. The forced convection heat transfer of the combustion gases containing
is heated at a temperature range of 850°C to 1100°C for 2 to 7 hours (preferably 3 to 5 hours). Thereafter, the temperature is lowered and the mixture is heated in a temperature range of 500°C to 600°C for 1 hour or more (preferably 2 to 4 hours). Preferably, the raw material heated to this temperature is placed in a vacuum container or in a strong drying material such as phosphorus pentoxide. Transfer to a large container and cool slowly. Through such a process, the desired chemical heat storage material (quicklime) is obtained. The time for heating the raw material (limestone 3) by the furnace 7 at a high temperature of 850° C. to 1100° C. is determined by the length of the furnace 7 and the speed of the conveyor 9 driven by the rollers 10.
そして炉７から原料３が出た後、大気中にて放冷される
過程において、５００℃〜６００℃の低温度範囲で保持
される時間帯がある。保持時間を長くするためには、ト
ンネル状の断熱カバーでコンベヤー９の周りを囲うのが
よい、この実施例において、磁製皿８を連続的気孔を有
する素焼き皿にすると石灰石３より炭酸ガスが抜は易く
、加熱時間を短かくできる。素焼き皿を金網また焼結金
属皿にしても同様の効果が得られる。After the raw material 3 comes out of the furnace 7, there is a period of time during which the raw material 3 is kept in a low temperature range of 500°C to 600°C in the process of being left to cool in the atmosphere. In order to extend the holding time, it is better to surround the conveyor 9 with a tunnel-shaped heat insulating cover. In this embodiment, if the porcelain plate 8 is an unglazed plate with continuous pores, carbon dioxide gas is absorbed more than the limestone 3. It is easy to remove and the heating time can be shortened. A similar effect can be obtained by replacing the clay plate with a wire mesh or sintered metal plate.
第２図は別の製造方法を示す図である。前記方法では原
料を５００℃から６００℃の低温度範囲で１時間から３
時間加熱する工程を十分うまく行なえない場合がある。FIG. 2 is a diagram showing another manufacturing method. In the above method, raw materials are heated in a low temperature range of 500°C to 600°C for 1 to 3 hours.
In some cases, the time heating step may not be carried out well enough.
第２図の方法では、炉７の隣りに別の低温度に加熱する
ための炉１１を設け。In the method shown in FIG. 2, a separate furnace 11 for heating to a low temperature is provided next to the furnace 7.
前記低温度範囲での加熱工程を十分うまく行なえるよう
にしたものである。加熱時間は炉１１の長さを変えて調
整する。炉７と炉１１との間に、空間部（非加熱部）１
２を設ければ、高温度から低温度へ下げることが容易に
行なえる。しかしながら、原料の温度の下げ方は、原料
そのものに熱衝撃を与えて亀裂が入らない範囲で行なわ
ねばならない。The heating process in the low temperature range can be carried out satisfactorily. The heating time is adjusted by changing the length of the furnace 11. Between the furnace 7 and the furnace 11, a space part (non-heating part) 1
2, the temperature can be easily lowered from a high temperature to a low temperature. However, the temperature of the raw material must be lowered within a range that does not cause thermal shock to the raw material itself and cause cracks.
原料を高温度から低温度に下げる方法として。As a method of lowering raw materials from high temperature to low temperature.
バッチ処理法を用いてもよい、すなわち第２図において
コンベヤー９を除去し、炉７中にて原料を高温度（８５
０℃〜１１００℃）に保持した後、炉７への入力を下げ
、炉７そのものを低温度（５００℃〜６００℃）にする
ものである。第３図は、このバッチ処理法を、さらに発
展させたものである。A batch processing method may also be used, ie conveyor 9 is removed in FIG. 2 and the raw material is brought to a high temperature (85
After maintaining the temperature at 0° C. to 1100° C., the input to the furnace 7 is lowered to bring the temperature of the furnace 7 itself to a low temperature (500° C. to 600° C.). FIG. 3 shows a further development of this batch processing method.
台１４とベルジャ１３によって構成される真空容器内の
回転テーブル１５上に複数個の皿８を乗せ、その内部に
原料としての石灰石３を入れておく。A plurality of plates 8 are placed on a rotary table 15 in a vacuum container constituted by a table 14 and a bell jar 13, and limestone 3 as a raw material is placed inside the rotary table 15.
皿８の上部に高温加熱体７と低温加熱体１１を設けて、
回転テーブル１５を回転させることにより高温加熱をし
た後低温加熱を行う。７′と１１′は加熱体７と１１を
加熱するヒーターであるが、面状発熱体を利用してもよ
い。石灰石３から発生する炭酸ガスはバルブ１６を開い
て、パイプ１７を介して真空排気すれば効率よく生石灰
が得られる。全加熱作業が終了すれば、このまま真空ベ
ルジャ１３内で放冷する。A high temperature heating element 7 and a low temperature heating element 11 are provided on the upper part of the dish 8,
By rotating the rotary table 15, high temperature heating is performed and then low temperature heating is performed. 7' and 11' are heaters that heat the heating elements 7 and 11, but sheet heating elements may also be used. By opening the valve 16 and evacuating the carbon dioxide gas generated from the limestone 3 through the pipe 17, quicklime can be efficiently obtained. When all the heating work is completed, it is left to cool in the vacuum bell jar 13 as it is.
第４図は本発明に用いる原料すなわち結晶質の石灰石（
寒水）を走査形電子顕微鏡で撮影した写真（５０００倍
）であり１表面は独特の光沢を帯びている。第５図は前
述した本発明の焼成法で石灰石を焼いて生石灰を作り、
これを同様の方法で撮影した写真である。多数の黒い点
は１表面から内部に向って生じた気孔で、その大きさは
０．１μｍから０．５ μｍの範囲にある。Figure 4 shows the raw material used in the present invention, namely crystalline limestone (
This is a photograph (5,000x magnification) of cold water) taken with a scanning electron microscope, and the surface has a unique luster. Figure 5 shows how limestone is burned to produce quicklime using the above-described baking method of the present invention.
This photo was taken using the same method. A large number of black dots are pores generated from one surface toward the inside, and the size thereof is in the range of 0.1 μm to 0.5 μm.
第６図は従来の方法で作った非晶質生石灰を走査形電子
顕微鏡で１０００倍に拡大した写真であり、第７図はそ
れを５ｏｏｏ倍に拡大した写真である。表面は光沢がな
く、火山灰のように荒れていて、第５図に見られるよう
な気孔は全くない。Figure 6 is a photograph of amorphous quicklime made by the conventional method, magnified 1000 times with a scanning electron microscope, and Figure 7 is a photograph magnified 500 times. The surface is matte and rough, resembling volcanic ash, and there are no pores as seen in Figure 5.
また従来の方法で結晶質の石灰石を焼いても、第５図に
見られるような気孔は生じない。Furthermore, even when crystalline limestone is fired using conventional methods, pores as seen in FIG. 5 do not occur.
第８図は、本発明に用いる結晶質の石灰石の粘径ｄと、
本発明の方法で焼いて得ることのできる生石灰の生成率
εとの関係を示したものである。FIG. 8 shows the viscous diameter d of the crystalline limestone used in the present invention,
This figure shows the relationship between the production rate ε of quicklime that can be obtained by baking according to the method of the present invention.
生石灰の生成率εは、重量法によって測定した。The production rate ε of quicklime was measured by gravimetric method.
すなわち石灰石（ＣａＣＯｓ）を焼くと炭酸ガス（ＣＯ
ｚ）が抜けて生石灰（Ｃａ Ｏ）を生ずるが、最初の原
料として石灰石の重量と焼いて軽くなった生石灰の重量
を測定し、炭酸ガスが完全に抜けて生石灰のみになった
時の理論的重量より算出して求めた１石灰石の粒径ｄが
４ｍ以上になると生成率εは著しく小さくなるが、これ
は原料である石灰石の深部では炭酸ガスが抜けなく、完
全に生石灰に変化しないものと考えられる。また粒径４
Ｉ以上になると、表面に著しく亀裂が生じ、化学蓄熱材
として使用した時、熱衝撃に弱いものとなる０粒径が０
．３ ｗｍから４ｍの範囲では、生成率Ｃはほぼ１００
％で、第５図に示すような微細な気孔が多数生じ、化学
蓄熱材として良質の生石灰が得られる。粒径が０．３
ｒｒｘｓ以下では、生石灰の生成率転が著しく小さくな
る。これは、第１図に示すように、磁性皿８上に薄く石
灰石３を乗せて加熱するものの、石灰石３より炭酸ガス
が抜は出しにくくなることによるものと考えられる。も
ともと炭酸ガスは空気より重いので、自然対流や拡散に
よって１石灰石３の上方に移動しにくい０粒径が小さく
なると自然対流や拡散は、著しく抑制され、結果として
石灰石３中より炭酸ガスは抜けなくなり、生石灰の生成
率εは激減する。In other words, when limestone (CaCOs) is burned, carbon dioxide gas (CO
Z) is removed and quicklime (CaO) is produced, but by measuring the weight of limestone as the first raw material and the weight of the quicklime that has been lightened by baking, we can calculate the theoretical value when carbon dioxide gas is completely removed and only quicklime is left. When the particle size d of one limestone calculated from the weight becomes 4 m or more, the production rate ε becomes significantly smaller, but this is because carbon dioxide gas cannot escape from the deep part of the raw limestone and it does not completely change to quicklime. Conceivable. Also, particle size 4
If the particle size exceeds I, significant cracks will occur on the surface, making it vulnerable to thermal shock when used as a chemical heat storage material.
．． In the range from 3wm to 4m, the production rate C is approximately 100
%, a large number of fine pores as shown in Fig. 5 are formed, and high quality quicklime can be obtained as a chemical heat storage material. Particle size is 0.3
Below rrxs, the rate of production of quicklime becomes significantly smaller. This is thought to be because, as shown in FIG. 1, although a thin layer of limestone 3 is placed on a magnetic plate 8 and heated, it is more difficult to extract carbon dioxide gas than from the limestone 3. Since carbon dioxide gas is originally heavier than air, it is difficult for it to move upwards through natural convection and diffusion.If the grain size becomes smaller, natural convection and diffusion will be significantly suppressed, and as a result, carbon dioxide will no longer escape from the limestone. , the production rate ε of quicklime is drastically reduced.
第９図は、原料の加熱温度Ｔと生石灰の生成率εとの関
係を示したものである。８５０℃以下では生成率εは著
しく小さくなる。１１００℃以上になると、第５図に示
す気孔と気孔間に亀裂が生じ始め、化学蓄熱材として熱
衝撃に弱くなる。FIG. 9 shows the relationship between the heating temperature T of the raw material and the production rate ε of quicklime. At temperatures below 850°C, the production rate ε becomes significantly smaller. When the temperature exceeds 1100° C., cracks begin to form between the pores shown in FIG. 5, and the material becomes vulnerable to thermal shock as a chemical heat storage material.
第１０図は、第１１図の化学蓄熱装置内に本発明の化学
蓄熱材（寒水を焼いて生石灰にしたもの）を入れて水蒸
気と反応させた時の化学蓄熱材の温度上昇特性を測定し
た結果を示したものである。Figure 10 shows the temperature rise characteristics of the chemical heat storage material when the chemical heat storage material of the present invention (made by burning cold water into quicklime) was placed in the chemical heat storage device shown in Figure 11 and reacted with water vapor. The results are shown below.
第１容器１の内容積は約２Ｑで、この空間部の９０％を
利用して、本発明の化学蓄熱材を充填した。化学蓄熱材
３及び第２容器内の被反応材（水）４を、約１００℃に
加熱しておき、その後バルブ６を開いて、第２容器２か
ら水蒸気をパイプ５を介して第１容器１内に導入し、化
学蓄熱材と反応させた。第１０図の実線に示すように１
反応直後。The internal volume of the first container 1 was approximately 2Q, and 90% of this space was utilized to fill the chemical heat storage material of the present invention. The chemical heat storage material 3 and the reactant material (water) 4 in the second container are heated to about 100° C., and then the valve 6 is opened to allow water vapor to flow from the second container 2 through the pipe 5 to the first container. 1 and reacted with the chemical heat storage material. 1 as shown in the solid line in Figure 10.
Immediately after the reaction.
化学蓄熱材３の温度は急上昇し、理論的に予測される平
衡温度的５００℃に達する。この温度は、そのまま長時
間にわたって維持される。この放熱過程が終了後、ヒー
ターで化学蓄熱材を再生し。The temperature of the chemical heat storage material 3 rises rapidly and reaches the theoretically predicted equilibrium temperature of 500°C. This temperature is maintained for a long time. After this heat dissipation process is completed, the chemical heat storage material is regenerated using a heater.
同様に放熱させるという試験を１００回行なったが、化
学蓄熱材の温度特性は、第１０図の実線とほぼ同じであ
った。なおこの生石灰中に粒径ＩＩから１０＋ｍの範囲
の結晶質の原料（石灰石）を５から３０重量パーセント
ー様に混合すると生石灰粒子間の焼付きが少なく、特に
温度立上り特性の低下が全く見られなかった。Similar heat dissipation tests were conducted 100 times, and the temperature characteristics of the chemical heat storage material were almost the same as the solid line in FIG. Furthermore, when a crystalline raw material (limestone) with a particle size ranging from II to 10+ m is mixed into this quicklime at a ratio of 5 to 30% by weight, there is little seizure between quicklime particles, and in particular, no deterioration in temperature rise characteristics is observed. Ta.
本発明の化学蓄熱材を従来の化学蓄熱材に変えて、同様
の実験を行なった。温度上昇特性は、破線に示す通りで
あり、立上りは実線より緩やかで。A similar experiment was conducted by replacing the chemical heat storage material of the present invention with a conventional chemical heat storage material. The temperature rise characteristics are as shown by the broken line, and the rise is more gradual than the solid line.
また５００℃一定に持続する時間帯は、実線より短かか
った。この従来の試料をヒーターで再生し。Also, the time period in which the temperature remained constant at 500°C was shorter than that of the solid line. Regenerate this conventional sample with a heater.
再び放熱実験を行なった所、試料の温度は５００℃まで
上昇せず、約３００℃に達した後、すぐに温度低下し始
めた。すなわち化学蓄熱材としては、十分機能しなくな
った。When the heat dissipation experiment was conducted again, the temperature of the sample did not rise to 500°C, and after reaching about 300°C, the temperature began to decrease immediately. In other words, it no longer functions adequately as a chemical heat storage material.
以上説明したように１本発明の化学蓄熱材は、熱衝撃及
び熱サイクルに強く、化学蓄熱装置に組込んで使用した
時、長期にわたってくり返し使用しても性能低下のない
化学蓄熱材を得ることができる。As explained above, (1) the chemical heat storage material of the present invention is resistant to thermal shock and thermal cycles, and when incorporated into a chemical heat storage device and used, it is possible to obtain a chemical heat storage material that does not deteriorate in performance even when used repeatedly over a long period of time. Can be done.
第１図は本発明の化学蓄熱材を生成する方法の一実施例
を示す図、第２図及び第３図はそれぞれ他の実施例を示
す図、第４図は本発明に用いる原料（結晶質石灰石）の
結晶の構造を示す電子顕微鏡写真、第５図は本発明で得
られた生石灰の結晶の構造を示す電子顕微鏡写真、第６
図は従来の非晶質生石灰の結晶の構造を示す電子［微鏡
写真。
第７図は第６図と同一の生石灰の結晶の構造を更に拡大
して示す＊＊＊写真、第８図は原料（石灰石）の粒径と
本発明における生石灰の生成率との関係を示す線図、第
９図は本発明の原料（石灰石）の加熱温度と生石灰の生
成率との関係を示す線図、第１０図は化学蓄熱材を化学
蓄熱装置内に入れて動作させた時の昇温特性を示す線図
、第１１図は化学蓄熱装置の構成図である。
１・・・第１容器、２・・・第２容器、３・・・反応材
（化学蓄熱材）、４・・・被反応材、５・・・パイプ、
６・・・バルブ、７．１１・・・炉、８・・・皿（磁製
皿、素焼き皿など）、９・・・コンベヤー、１０．１０
’ ・・・ローラー、１２・・・空間部（非加熱部）、
１３・・・ペルジャー、１４・・・台、１５・・・回転
テーブル、１６・・・バルブ、＄＋ｅ
第３ 図
察４０ 粁品更石灰石（ぢ０００／香）’ｆａｓｒｈ
鞘＆’ｌＩＬ石＆（５ｏｏｏ４）ｓ、、ＢＥ ＝−ｉ
ｂａ−らｄ４”ｐ ＋ｚ向フＩＫ−じしり（５ｇＯ１１
％” 〜０．９物η先孔
第ら６已 Ｊト番ｉｓ？偏り石）こ （（ｏｏｏＡ含
）・ 肴ヒ尋−μゴ漆ｑの 等品情馨ム石及（ｙｏｏｏ
４奮）−＃利第 ３ 口
畠占晶算石仄る。１９ずｌイ苧ｄ（＾気）第 ７ 凹
力り介〜シ造鷹丁（”ｃ）FIG. 1 is a diagram showing one embodiment of the method for producing the chemical heat storage material of the present invention, FIGS. 2 and 3 are diagrams each showing other embodiments, and FIG. Fig. 5 is an electron micrograph showing the crystal structure of quicklime obtained in the present invention;
The figure is an electron micrograph showing the crystal structure of conventional amorphous quicklime. Figure 7 is a further enlarged photo showing the same quicklime crystal structure as in Figure 6, and Figure 8 shows the relationship between the particle size of the raw material (limestone) and the production rate of quicklime in the present invention. Figure 9 is a diagram showing the relationship between the heating temperature of the raw material (limestone) of the present invention and the production rate of quicklime, and Figure 10 is a diagram showing the relationship between the heating temperature of the raw material (limestone) of the present invention and the production rate of quicklime. A diagram showing temperature increase characteristics, FIG. 11 is a configuration diagram of a chemical heat storage device. DESCRIPTION OF SYMBOLS 1... First container, 2... Second container, 3... Reactant material (chemical heat storage material), 4... Reacted material, 5... Pipe,
6... Valve, 7.11... Furnace, 8... Plate (porcelain plate, unglazed plate, etc.), 9... Conveyor, 10.10
'...roller, 12...space part (non-heating part),
13...Pelger, 14...stand, 15...rotary table, 16...valve, $+e 3rd diagram 40 熁品药石(〢000/ incense)'fasrh
Scabbard &'lIL stone & (5ooo4)s, BE =-i
ba-ra d4”p +z-direction IK-jishiri (5gO11
%" ~ 0.9 thing η first hole number 6th J to number is? biased stone) this ((oooA included), appetizer Hi-μgo lacquer, etc. item information about the stone and (yooo
4) - #Ritai 3 Kuchibatake Sansho Sanseki is here. 19zu l i 苧d (＾ki) No. 7 Kokoro Risuke ~ Shizou Takacho (”c)
Claims (1)
る生石灰を主体とした化学蓄熱材。 ２、粒径０．３〜４ｍｍの範囲の結晶質の石灰石を８５
０〜１１００℃の温度範囲で所定時間加熱し、次に前記
石灰石を５００〜６００℃の温度範囲で所定時間加熱し
、表面から内部に向う多数の気孔を有する生石灰を作る
ことを特徴とした化学蓄熱材の製造方法。[Scope of Claims] 1. A chemical heat storage material mainly composed of quicklime and having a large number of pores formed from the surface toward the inside. 2. Crystalline limestone with a particle size of 0.3 to 4 mm is 85
A chemistry characterized by heating the limestone at a temperature range of 0 to 1100°C for a predetermined time, and then heating the limestone at a temperature range of 500 to 600°C for a predetermined time to produce quicklime having a large number of pores extending from the surface to the inside. Method for manufacturing heat storage material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4952188A JP2539480B2 (en) | 1988-03-04 | 1988-03-04 | Chemical heat storage material and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4952188A JP2539480B2 (en) | 1988-03-04 | 1988-03-04 | Chemical heat storage material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01225686A true JPH01225686A (en) | 1989-09-08 |
| JP2539480B2 JP2539480B2 (en) | 1996-10-02 |
Family
ID=12833441
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4952188A Expired - Fee Related JP2539480B2 (en) | 1988-03-04 | 1988-03-04 | Chemical heat storage material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2539480B2 (en) |
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| Publication number | Publication date |
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| JP2539480B2 (en) | 1996-10-02 |
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