JP3417490B2 - Calcium oxide porous granular composite and method for producing the same - Google Patents
Calcium oxide porous granular composite and method for producing the sameInfo
- Publication number
- JP3417490B2 JP3417490B2 JP06599493A JP6599493A JP3417490B2 JP 3417490 B2 JP3417490 B2 JP 3417490B2 JP 06599493 A JP06599493 A JP 06599493A JP 6599493 A JP6599493 A JP 6599493A JP 3417490 B2 JP3417490 B2 JP 3417490B2
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- Prior art keywords
- calcium oxide
- calcium
- oxide porous
- calcium carbonate
- temperature
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- 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.)
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- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Description
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明は、比表面積が大きく、し
かも粒度が大きくて取り扱いやすい、安定化された高活
性酸化カルシウム多孔質粒状複合体及びその製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a stabilized highly active calcium oxide porous granular composite having a large specific surface area, a large particle size and easy handling, and a method for producing the same.
【０００２】[0002]
【従来の技術】酸化カルシウムは、通常炭酸カルシウム
を焼成することによって製造されているが、このものは
焼成温度によって活性度が異なることが知られている。
すなわち、炭酸カルシウムの脱炭酸温度に近い焼成温度
で得られるものは軟焼生石灰といわれ活性に富むが、さ
らに高温で焼成されるものは硬焼生石灰といわれ活性が
低い。これは、酸化カルシウムの結晶の成長と焼締りに
より開口空隙率の低下、換言すると比表面積が低下する
ためである。例えば純粋品についていえば軟焼生石灰の
開口空隙率は約５０％、比表面積は約２ｍ２／ｇである
のに対し、硬焼生石灰の開口空隙率は約１０％、比表面
積は約０．０４ｍ２／ｇと非常に小さくなっている。2. Description of the Related Art Calcium oxide is usually produced by calcining calcium carbonate, which is known to have different activity depending on the calcining temperature.
That is, what is obtained at a firing temperature close to the decarbonation temperature of calcium carbonate is called soft-calcined quick lime and is rich in activity, but that which is calcined at a higher temperature is called hard-burned quick lime and has low activity. This is because the open porosity, in other words, the specific surface area, decreases due to the growth and compaction of calcium oxide crystals. For example, in the case of pure products, the open porosity of soft burned lime is about 50% and the specific surface area is about 2 m 2 / g, whereas the open porosity of hard burned lime is about 10% and the specific surface area is about 0. It is very small at 04 m 2 / g.
【０００３】これまで、高活性の酸化カルシウムを得る
ために、粉末度を小さくして、比表面積を大きくする試
みがなされてきたが、炭酸カルシウムの粉末を小さくす
ることには限度があるため、炭酸カルシウムを原料とし
て用いる限り、あまり比表面積を大きくすることができ
ず、常圧での焼成による酸化カルシウム粉末の最も大き
い比表面積は約３ｍ２／ｇ程度である。また、真空下で
の焼成により活性度を高めることも提案されているが、
設備上多くの問題があり、実用化されていない［「ギプ
サム・アンド・ライム（Ｇｙｐｓｕｍ ＆ Ｌｉｍ
ｅ）」、第１７８号、第３１〜４０ページ］。Up to now, attempts have been made to reduce the fineness of powder and increase the specific surface area in order to obtain highly active calcium oxide, but there is a limit to reducing the size of calcium carbonate powder. As long as calcium carbonate is used as a raw material, the specific surface area cannot be increased so much, and the largest specific surface area of the calcium oxide powder by firing at normal pressure is about 3 m 2 / g. Further, it has been proposed to increase the activity by firing under vacuum,
It has many problems in facilities and has not been put into practical use ["Gypsum & Lim (Gypsum & Lim
e) ", No. 178, pages 31-40].
【０００４】他方、水酸化カルシウムの微細粉末を原料
として用い、これを真空下３００〜３９０℃の温度で焼
成して１１０〜１３３ｍ２／ｇという大きい比表面積の
酸化カルシウム粉末を製造した例も知られているが
［「ジャーナル・オブ・ジ・アメリカン・セラミック・
ソサエティ（Ｊ．Ａｍ．Ｃｅｒａｍｉｃ Ｓｏ
ｃ．）」、第６４巻、第２号、第７４〜８０ページ］、
この方法により得られる粉末は、高活性ではあるとして
も、粒径１〜１０μｍと微細なものであるため、取り扱
いにくく、その利用分野が制限されるのを免れない。On the other hand, there is also known an example in which a fine powder of calcium hydroxide is used as a raw material, and this is fired at a temperature of 300 to 390 ° C. under vacuum to produce a calcium oxide powder having a large specific surface area of 110 to 133 m 2 / g. However, the [Journal of the American Ceramic
Society (J. Am. Ceramic So
c. ) ", Vol. 64, No. 2, pp. 74-80],
The powder obtained by this method has a fine particle size of 1 to 10 μm even though it is highly active, and therefore it is difficult to handle and the field of use thereof is inevitably limited.
【０００５】[0005]
【発明が解決しようとする課題】本発明者は、先に水酸
化カルシウム又は炭酸カルシウムの微粉末を造粒したの
ち、所定の加熱条件下、比較的低い温度で焼成して得た
酸化カルシウム多孔質体が大きい粒度であるにもかかわ
らず、高活性を示すことを見出し、この知見に基づい
て、少なくとも５ｍ２／ｇの比表面積及び少なくとも１
ｍｍの粒径をもつ水酸化カルシウム又は炭酸カルシウム
の造粒体焼成物から成る高活性酸化カルシウム多孔質体
を提案した（特願平４−３４５１５９号）。DISCLOSURE OF THE INVENTION The inventor of the present invention firstly granulates fine powder of calcium hydroxide or calcium carbonate and then calcinates it at a relatively low temperature under predetermined heating conditions to obtain a porous calcium oxide. Based on this finding, it was found that even though the particles have a large particle size, they exhibit a high activity and a specific surface area of at least 5 m 2 / g and at least 1
A highly active calcium oxide porous body composed of a calcined product of calcium hydroxide or calcium carbonate having a particle size of mm was proposed (Japanese Patent Application No. 4-345159).
【０００６】しかしながら、この酸化カルシウム多孔質
体は高活性のため、輸送や貯蔵の間に大気中の二酸化炭
素や水分と反応して、その活性を低下するという欠点が
ある。However, since this calcium oxide porous material has a high activity, it has a drawback that it reacts with carbon dioxide and moisture in the atmosphere during transportation and storage to lower its activity.
【０００７】本発明は、このような高活性酸化カルシウ
ム多孔質体のもつ欠点を改良し、長時間大気中において
も、その活性が低下しない粒状複合体を得ることを目的
としてなされたものである。[0007] The present invention has been made for the purpose of improving the drawbacks of such a highly active calcium oxide porous material and obtaining a granular composite whose activity does not decrease even in the atmosphere for a long time. .
【０００８】[0008]
【課題を解決するための手段】本発明者は、高活性酸化
カルシウム多孔質体の安定化について種々研究を重ねた
結果、この多孔質体の表面を炭酸カルシウム層で被覆す
ることにより、高活性酸化カルシウム多孔質体の活性を
そこなわずに、安定化しうることを見出し、この知見に
基づいて本発明をなすに至った。The present inventor has conducted various studies on the stabilization of a highly active calcium oxide porous body, and as a result, by coating the surface of this porous body with a calcium carbonate layer, a high activity is obtained. The present inventors have found that the calcium oxide porous material can be stabilized without impairing its activity, and have completed the present invention based on this finding.
【０００９】すなわち、本発明は、比表面積５ｍ２／ｇ
以上及び粒径１ｍｍ以上の高活性酸化カルシウム多孔質
粒子と、その表面に形成された炭酸カルシウム被覆層か
ら成る酸化カルシウム多孔質粒状複合体を提供するもの
である。That is, the present invention has a specific surface area of 5 m 2 / g.
The present invention provides a calcium oxide porous granular composite comprising high activity calcium oxide porous particles having a particle diameter of 1 mm or more and a calcium carbonate coating layer formed on the surface thereof.
【００１０】この酸化カルシウム多孔質粒状複合体は、
例えば粒径３００μｍ以下の水酸化カルシウム粉末又は
炭酸カルシウム粉末を粒径１ｍｍ以上の顆粒に造粒し、
この造粒体を常圧下４００〜９５０℃の温度において３
０分ないし２時間焼成し、この焼成の後段において二酸
化炭素と接触させるか、あるいは焼成後さらに二酸化炭
素雰囲気中、４００〜７００℃において少なくとも炭酸
化率１０％になるまで処理することによって製造するこ
とができる。This calcium oxide porous granular composite is
For example, calcium hydroxide powder or calcium carbonate powder having a particle size of 300 μm or less is granulated into granules having a particle size of 1 mm or more,
The granules are heated at a temperature of 400 to 950 ° C. under normal pressure for 3 times.
Producing by calcination for 0 minutes to 2 hours and contacting with carbon dioxide in the latter stage of this calcination, or by further treating after calcination in a carbon dioxide atmosphere at 400 to 700 ° C. until the carbonation rate becomes at least 10%. You can
【００１１】この方法における、造粒体の焼成条件とし
ては、水酸化カルシウムの場合は３９０〜４８０℃の間
を少なくとも５分間かけて昇温するように、また、炭酸
カルシウムの場合は、７００〜７８０℃の間を少なくと
も５分間かけて昇温させるように選ぶのがよい。In this method, the firing conditions of the granules are as follows: in the case of calcium hydroxide, the temperature is raised between 390 and 480 ° C. over at least 5 minutes, and in the case of calcium carbonate, 700 to It is advisable to choose to raise the temperature between 780 ° C. over at least 5 minutes.
【００１２】この際に、原料として用いる水酸化カルシ
ウムは、市販水酸化カルシウム（消石灰）をそのまま用
いてもよいし、市販酸化カルシウム（生石灰）の水和生
成物を用いることもできるが、不純分が混入すると得ら
れる酸化カルシウムの活性度が低下するので、できるだ
け純度の高いものを用いるのが好ましい。この水酸化カ
ルシウムは、平均粒径１０〜３００μｍの粉末として用
いられる。In this case, as the calcium hydroxide used as a raw material, commercially available calcium hydroxide (slaked lime) may be used as it is, or a hydrated product of commercially available calcium oxide (quick lime) may be used. When calcium is mixed, the activity of the obtained calcium oxide is lowered, so that it is preferable to use the one having the highest purity. This calcium hydroxide is used as a powder having an average particle size of 10 to 300 μm.
【００１３】また、炭酸カルシウムは、軽質、重質のい
ずれでもよく、市販品をそのまま用いてもよいし、水酸
化カルシウム水溶液に二酸化炭素を通して製造したもの
を用いてもよい。The calcium carbonate may be light or heavy, and a commercially available product may be used as it is, or a product produced by passing carbon dioxide in an aqueous solution of calcium hydroxide may be used.
【００１４】次に、水酸化カルシウム粉末又は炭酸カル
シウム粉末の造粒は、これに水を加えて混練りし、慣用
の造粒機を用いて最小直径、少なくとも１ｍｍ、例えば
直径３〜６ｍｍ、長さ３〜６ｍｍ程度の円柱状顆粒に押
出し成形することによって行われる。この際添加する水
分の量としては、水酸化カルシウムの重量に基づき５〜
２５重量％の範囲が適当である。この造粒に際しては、
保形性を向上させるために、所望に応じ有機バインダー
を添加することもできる。この有機バインダーとして
は、カルボキシメチルセルロース（ＣＭＣ）、ポリビニ
ルアルコールなどの水溶性高分子物質が用いられる。こ
の有機バインダーの添加量は、水酸化カルシウムの重量
当り０．５〜５％の範囲が適当である。Next, in the granulation of calcium hydroxide powder or calcium carbonate powder, water is added to this and kneaded, and a minimum diameter of at least 1 mm, for example, 3 to 6 mm, long length is obtained using a conventional granulator. It is carried out by extrusion molding into cylindrical granules having a size of about 3 to 6 mm. The amount of water added at this time is 5 to 5 based on the weight of calcium hydroxide.
A range of 25% by weight is suitable. In this granulation,
If desired, an organic binder may be added to improve the shape retention. As the organic binder, a water-soluble polymer substance such as carboxymethyl cellulose (CMC) or polyvinyl alcohol is used. The amount of the organic binder added is appropriately in the range of 0.5 to 5% based on the weight of calcium hydroxide.
【００１５】このようにして得た造粒体は、次いで例え
ば電気炉を用いて焼成されるが、この焼成条件として
は、水酸化カルシウムの場合、３９０〜４８０℃の範囲
の間を少なくとも５分間、炭酸カルシウムの場合７００
〜７８０℃の範囲の間を少なくとも５分間かけて昇温さ
せることが必要である。これ以外の条件で焼成した場
合、比表面積５ｍ２／ｇ以上の高活性のものを得ること
ができない。The granules thus obtained are then calcined using, for example, an electric furnace. The calcining conditions are, in the case of calcium hydroxide, a temperature in the range of 390 to 480 ° C. for at least 5 minutes. , 700 for calcium carbonate
It is necessary to raise the temperature in the range of ˜780 ° C. for at least 5 minutes. When firing under other conditions, it is not possible to obtain a highly active material having a specific surface area of 5 m 2 / g or more.
【００１６】この際の昇温速度としては１〜１０℃／分
の範囲が好ましく、また水酸化カルシウムの場合４８０
℃、炭酸カルシウムの場合７８０℃の上限に達したなら
ば、できるだけ早く加熱を停止するのが好ましい。細孔
分布スペクトルを測定すると、この時点において、０．
０２〜０．２μｍ付近でピークが認められる。In this case, the temperature rising rate is preferably in the range of 1 to 10 ° C./minute, and in the case of calcium hydroxide, 480.
In case of calcium carbonate and calcium carbonate, when the upper limit of 780 ° C. is reached, it is preferable to stop heating as soon as possible. When the pore distribution spectrum was measured, at this point,
A peak is recognized around 02 to 0.2 μm.
【００１７】大量処理の際は、仕込原料の完全な焼成を
はかるために、さらに昇温を続行させることが必要にな
るが、この場合は９５０℃を超えない温度でしかも活性
の低下を生じないように注意しなければならない。In the case of large-scale treatment, it is necessary to further raise the temperature in order to complete the firing of the charged raw material, but in this case, the temperature does not exceed 950 ° C. and the activity does not decrease. You have to be careful.
【００１８】上記の焼成に際しては、フッ化カルシウム
のような低温で分解する還元剤を添加することにより、
焼成時間を短縮することができる。In the above firing, by adding a reducing agent such as calcium fluoride which decomposes at a low temperature,
The firing time can be shortened.
【００１９】また本発明方法によれば、上記の製造条件
を選択することにより、活性度を所望の程度に調整され
た酸化カルシウムを得ることができる。According to the method of the present invention, it is possible to obtain calcium oxide whose activity is adjusted to a desired degree by selecting the above production conditions.
【００２０】このようにして、比表面積が５ｍ２／ｇ以
上、通常は１０〜６０ｍ２／ｇの高活性酸化カルシウム
多孔質体が、径１〜６ｍｍの粒状体として得られる。[0020] Thus, specific surface area of 5 m 2 / g or more, usually highly active calcium oxide porous body of 10 to 60 m 2 / g is obtained as granules of diameter 1 to 6 mm.
【００２１】このようにして得られた高活性酸化カルシ
ウム多孔質体の表面に炭酸カルシウム被覆を形成させる
には、この多孔質体を４００〜７００℃、好ましくは５
００〜６２０℃の温度に加熱し、二酸化炭素ガスと接触
させる。この際の二酸化炭素は、二酸化炭素単独でもよ
いが通常は窒素のような不活性ガスで希釈したものを継
続的に供給することによって行われる。この際の二酸化
炭素濃度は少なくとも３％にするのが好ましく、一般に
濃度が高いほど処理時間は短縮される。In order to form a calcium carbonate coating on the surface of the thus obtained highly active calcium oxide porous body, this porous body is 400 to 700 ° C., preferably 5
It is heated to a temperature of 00 to 620 ° C. and brought into contact with carbon dioxide gas. The carbon dioxide at this time may be carbon dioxide alone, but it is usually supplied by continuously supplying it diluted with an inert gas such as nitrogen. The carbon dioxide concentration at this time is preferably at least 3%, and generally, the higher the concentration, the shorter the treatment time.
【００２２】この際の供給速度としては、二酸化炭素濃
度５〜２０％で１００〜２００ｍｌ／分程度が適当であ
る。At this time, a suitable supply rate is about 100 to 200 ml / min at a carbon dioxide concentration of 5 to 20%.
【００２３】この炭酸カルシウム被覆の形成は、水酸化
カルシウムを焼成して高活性酸化カルシウム多孔質体を
製造する際の焼成工程の後段において、二酸化炭素を供
給し、接触させることによっても行うことができる。The formation of this calcium carbonate coating can also be carried out by supplying and contacting carbon dioxide in the latter stage of the firing step when firing calcium hydroxide to produce a highly active calcium oxide porous body. it can.
【００２４】高活性酸化カルシウム多孔質体の表面にお
ける炭酸カルシウム被覆の形成は、少なくとも炭酸化率
１０％、好ましくは２０〜４０％に対応する被覆が得ら
れるまで行うことが必要である。これよりも炭酸化の割
合が少ないと、安定化効果が不十分になるし、またこれ
よりも炭酸化が進むと、酸化カルシウムの活性が低下す
る。ここでいう炭酸化率とは、多孔質体全量に対する生
成した炭酸カルシウム重量の百分比である。The formation of the calcium carbonate coating on the surface of the highly active calcium oxide porous body must be carried out until a coating corresponding to a carbonation rate of at least 10%, preferably 20-40% is obtained. If the proportion of carbonation is lower than this, the stabilizing effect will be insufficient, and if the proportion of carbonation is higher than this, the activity of calcium oxide will decrease. The carbonation rate referred to here is the percentage of the weight of calcium carbonate produced relative to the total amount of the porous body.
【００２５】この炭酸カルシウム被覆の形成のために要
する処理時間は、炭酸化の条件に左右されるが、処理温
度５００〜６５０℃で５〜６０分程度である。The treatment time required for forming this calcium carbonate coating depends on the carbonation conditions, but it is about 5 to 60 minutes at a treatment temperature of 500 to 650 ° C.
【００２６】[0026]
【発明の効果】本発明によると、触媒、排気ガス吸着
剤、製鋼用保温剤、製鋼用フラックスなどとして有用な
高活性酸化カルシウム多孔質体の活性を維持したまま、
長期間にわたって水分その他の反応性ガスに対し良好な
安定性を示す新規な複合体が得られる。According to the present invention, while maintaining the activity of the highly active calcium oxide porous body useful as a catalyst, an exhaust gas adsorbent, a heat retaining agent for steelmaking, a flux for steelmaking,
A new complex is obtained which exhibits good stability to moisture and other reactive gases over a long period of time.
【００２７】[0027]
【実施例】次に実施例により本発明をさらに詳細に説明
する。EXAMPLES The present invention will be described in more detail with reference to examples.
【００２８】なお、各例中に示す比表面積は、以下のよ
うにして求めたものである。
比表面積；各試料０．５ｇを、モノソープ比表面積測定
装置（湯浅アイオニクス社製）を用いて、ＢＥＴ庶点法
により測定したのち、得られた測定値を２倍して１ｇ当
りの表面積とした。The specific surface area shown in each example is obtained as follows. Specific surface area: 0.5 g of each sample was measured by a BET common point method using a monosoap specific surface area measuring device (manufactured by Yuasa Ionics Co., Ltd.), and then the obtained measured value was doubled to obtain a surface area per 1 g. And
【００２９】実施例１
水酸化カルシウム粉末［鈴木工業（株）製、工業用消石
灰、純度９５．９％、粒度３００μｍ以下］に水２５重
量％を加え、ディスクペレター［（株）不二パウダル
製］を用いて直径３ｍｍ、長さ３ｍｍの顆粒に造粒し
た。Example 1 Calcium hydroxide powder [manufactured by Suzuki Kogyo Co., Ltd., industrial slaked lime, purity 95.9%, particle size 300 μm or less] was added with 25% by weight of water to prepare a disk pelleter [Fuji Paudal Co., Ltd.]. Manufactured] to granulate into granules having a diameter of 3 mm and a length of 3 mm.
【００３０】この造粒体を電気炉に入れ、昇温速度１℃
／分で４７０℃まで加熱し、４７０℃に達したとき、た
だちに電気炉より取り出し、放冷した。この際の３９０
℃から４８０℃までの昇温時間は９０分であった。This granule was placed in an electric furnace and the temperature rising rate was 1 ° C.
The temperature was increased to 470 ° C./min, and when the temperature reached 470 ° C., the sample was immediately taken out of the electric furnace and allowed to cool. 390 at this time
The temperature rising time from ° C to 480 ° C was 90 minutes.
【００３１】このものの細孔分布を細孔分布計（マイク
ロメディックス社製ＰＯＲＥＳＩＺＥＲ９３１０）を用
いて測定したところ、０．０２〜２μｍの範囲の細孔を
有することが分った。また、このものの比表面積は１
４．４ｍ２／ｇであった。The pore distribution of this product was measured by using a pore distribution meter (PORESIZER9310 manufactured by Micromedix Co., Ltd.), and it was found to have pores in the range of 0.02 to 2 μm. The specific surface area of this product is 1
It was 4.4 m 2 / g.
【００３２】次にこのようにして得た酸化カルシウム多
孔質体５ｇを管状反応器に装入し、窒素で希釈した二酸
化炭素（濃度９．９２％）を１００ｍｌ／分の速度で３
０分間供給し、二酸化炭素の反応率と反応温度との関係
を調べた。この結果をグラフとして図１に示す。このグ
ラフから明らかなように、炭酸カルシウム被覆を形成す
る際の反応温度としては、４００〜７００℃、特に５０
０〜６２０℃が好適である。Next, 5 g of the calcium oxide porous material thus obtained was charged into a tubular reactor, and carbon dioxide (concentration 9.92%) diluted with nitrogen was added at a rate of 100 ml / min.
After supplying for 0 minutes, the relationship between the reaction rate of carbon dioxide and the reaction temperature was investigated. The results are shown as a graph in FIG. As is clear from this graph, the reaction temperature for forming the calcium carbonate coating is 400 to 700 ° C., especially 50.
0-620 degreeC is suitable.
【００３３】実施例２
実施例１で得た酸化カルシウム多孔質体５ｇを、実施例
１と同様にして６００℃において二酸化炭素で処理し、
炭酸化率の経時的変化を調べた。この結果をグラフとし
て図２に示す。このグラフから明らかなように、二酸化
炭素濃度約１０％の希釈ガスを用いた場合に、所要の炭
酸カルシウム被覆を形成するのに必要な時間は、５〜６
０分間である。Example 2 5 g of the calcium oxide porous body obtained in Example 1 was treated with carbon dioxide at 600 ° C. in the same manner as in Example 1,
The change in carbonation rate with time was examined. The results are shown as a graph in FIG. As is apparent from this graph, the time required to form the required calcium carbonate coating is 5 to 6 when a diluent gas having a carbon dioxide concentration of about 10% is used.
0 minutes.
【００３４】実施例３
炭酸カルシウム粉末［備北粉化（株）製、純度９８％、
粒度１５０μｍ以下］を直径３ｍｍ、長さ３ｍｍの顆粒
に造粒し、この造粒体を電気炉に入れ、室温から７８０
℃まで、昇温速度１℃／分で加熱し、７８０℃に達する
と同時に電気炉より取り出し、放冷した。この際の７０
０℃から７８０℃までの昇温時間は８０分であった。こ
のものの比表面積は３５．８６ｍ２／ｇであった。Example 3 Calcium carbonate powder [manufactured by Bihoku Powder Co., Ltd., purity 98%,
Granules of 150 μm or less] are granulated into granules having a diameter of 3 mm and a length of 3 mm, and the granules are placed in an electric furnace and heated from room temperature to 780
The sample was heated up to 0 ° C at a temperature rising rate of 1 ° C / min, and at the same time when it reached 780 ° C, it was taken out of the electric furnace and allowed to cool. 70 at this time
The heating time from 0 ° C. to 780 ° C. was 80 minutes. The specific surface area of this product was 35.86 m 2 / g.
【００３５】次に、このようにして得た酸化カルシウム
多孔質体を実施例１と同じ希釈二酸化炭素ガスを用い、
６００℃において５分間炭酸化処理したところ、炭酸化
率２０％をもつ炭酸カルシウム被覆酸化カルシウム多孔
質複合体が得られた。Next, using the same diluted carbon dioxide gas as in Example 1, the calcium oxide porous body thus obtained was
Upon carbonation at 600 ° C. for 5 minutes, a calcium carbonate-coated calcium oxide porous composite having a carbonation rate of 20% was obtained.
【００３６】参考例
実施例１で得た比表面積１４．４ｍ２／ｇをもつ酸化カ
ルシウム多孔質体（Ａ）と、この表面に１０％の炭酸化
率で炭酸カルシウム被覆を施した粒状複合体（Ｂ）につ
いて、湿度６６％、温度２０℃の大気中に放置したとき
の水分吸収率の経時的変化を調べた。この水分吸収率は
数１に従って求めたものである。Reference Example Calcium oxide porous body (A) having a specific surface area of 14.4 m 2 / g obtained in Example 1 and a granular composite having the surface coated with calcium carbonate at a carbonation rate of 10%. Regarding (B), the time-dependent change in the water absorption rate when left in the air at a humidity of 66% and a temperature of 20 ° C. was examined. This water absorption rate is obtained according to Equation 1.
【００３７】[0037]
【数１】 [Equation 1]
【００３８】このようにして、求めたそれぞれの結果を
表１に示す。The results thus obtained are shown in Table 1.
【００３９】[0039]
【表１】 [Table 1]
【図１】 炭酸化処理における反応率と反応温度の関係
を示すグラフ。FIG. 1 is a graph showing the relationship between reaction rate and reaction temperature in carbonation treatment.
【図２】 炭酸化処理における炭酸化率の経時的変化を
示すグラフ。FIG. 2 is a graph showing changes with time of carbonation rate in carbonation treatment.
Claims (2)
以上の高活性酸化カルシウム多孔質粒子と、その表面に
形成された炭酸カルシウム被覆層から成る酸化カルシウ
ム多孔質粒状複合体。1. A specific surface area of 5 m 2 / g or more and a particle size of 1 mm
A calcium oxide porous granular composite comprising the above-mentioned highly active calcium oxide porous particles and a calcium carbonate coating layer formed on the surface thereof.
粉末又は炭酸カルシウム粉末を粒径１ｍｍ以上の顆粒に
造粒し、この造粒体を常圧下４００〜９５０℃の温度に
おいて３０分ないし２時間焼成し、この焼成の後段にお
いて二酸化炭素と接触させるか、あるいは焼成後さらに
二酸化炭素雰囲気中、４００〜７００℃において少なく
とも炭酸化率１０％になるまで処理することを特徴とす
る炭酸カルシウム被覆層を有する酸化カルシウム多孔質
粒状複合体の製造方法。2. Calcium hydroxide powder or calcium carbonate powder having a particle size of 300 μm or less is granulated into granules having a particle size of 1 mm or more, and the granulated product is calcined at a temperature of 400 to 950 ° C. for 30 minutes to 2 hours. However, it has a calcium carbonate coating layer characterized by being brought into contact with carbon dioxide in the latter stage of this firing or further treated after firing in a carbon dioxide atmosphere at 400 to 700 ° C. until at least a carbonation rate of 10% is reached. A method for producing a calcium oxide porous granular composite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP06599493A JP3417490B2 (en) | 1992-03-03 | 1993-03-03 | Calcium oxide porous granular composite and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-82680 | 1992-03-03 | ||
| JP8268092 | 1992-03-03 | ||
| JP06599493A JP3417490B2 (en) | 1992-03-03 | 1993-03-03 | Calcium oxide porous granular composite and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH069215A JPH069215A (en) | 1994-01-18 |
| JP3417490B2 true JP3417490B2 (en) | 2003-06-16 |
Family
ID=26407154
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP06599493A Expired - Lifetime JP3417490B2 (en) | 1992-03-03 | 1993-03-03 | Calcium oxide porous granular composite and method for producing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3417490B2 (en) |
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|---|---|---|---|---|
| CN1384263A (en) * | 2001-05-02 | 2002-12-11 | 山英建设株式会社 | Carbon plate |
| WO2006106878A1 (en) * | 2005-03-30 | 2006-10-12 | Ube Material Industries, Ltd. | Granular material comprising porous particles containing calcium and/or magnesium |
| JP2007155087A (en) * | 2005-12-08 | 2007-06-21 | Matsushita Electric Ind Co Ltd | Vacuum heat insulating material |
| JP5227537B2 (en) * | 2006-05-08 | 2013-07-03 | 節夫 小林 | Magnesium-based slow dissolving agent for neutralization of dialysis machine washing wastewater |
| KR100722464B1 (en) * | 2006-07-14 | 2007-05-28 | 주식회사 두산 | Getter for packaging, highly active calcium oxide, and method for preparing highly active calcium oxide |
| JP2012066952A (en) * | 2010-09-22 | 2012-04-05 | Denki Kagaku Kogyo Kk | Slaked lime briquette and application of the same |
| CN102225780B (en) * | 2011-04-19 | 2013-08-28 | 上海彭浦冶金辅料有限公司 | High-activity calcium oxide and production method thereof |
| KR20130074608A (en) * | 2011-12-26 | 2013-07-04 | (주)엘지하우시스 | Vacuum insulation including getter having high specific surface area |
| CN103058246B (en) * | 2012-12-24 | 2016-03-30 | 刘立文 | A kind of calcium sulfate produces the method for high-purity calcium oxide |
| CN105217670B (en) * | 2015-08-24 | 2017-08-15 | 成都理工大学 | A kind of production method of high carbonate-free lime |
| CN109384255A (en) * | 2018-11-30 | 2019-02-26 | 武汉科技大学 | A kind of calcium oxide spherolite and preparation method thereof |
| JP7218866B2 (en) * | 2019-03-27 | 2023-02-07 | 太平洋セメント株式会社 | Chemical heat storage material for chemical heat pump coated with inorganic porous material and manufacturing method thereof |
| JP2021137767A (en) * | 2020-03-09 | 2021-09-16 | 株式会社Ｍｃラボ | desiccant |
| IT202100026225A1 (en) * | 2021-10-13 | 2023-04-13 | Unicalce S P A | GRANULAR MATERIAL BASED ON QUICK LIME, ITS PREPARATION PROCESS AND ITS USES. |
-
1993
- 1993-03-03 JP JP06599493A patent/JP3417490B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH069215A (en) | 1994-01-18 |
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