JPH0733431A - Hydrocalumite production method - Google Patents
Hydrocalumite production methodInfo
- Publication number
- JPH0733431A JPH0733431A JP5180295A JP18029593A JPH0733431A JP H0733431 A JPH0733431 A JP H0733431A JP 5180295 A JP5180295 A JP 5180295A JP 18029593 A JP18029593 A JP 18029593A JP H0733431 A JPH0733431 A JP H0733431A
- Authority
- JP
- Japan
- Prior art keywords
- hydrocalumite
- cao
- producing
- anion
- nitrite
- 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
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
(57)【要約】
【目的】 本発明の目的は、安価で陰イオン交換能の高
いハイドロカルマイトを得るための製造方法を提供する
ことにある。
【構成】 本発明のハイドロカルマイトの製造方法は、
ＣａＯ−Ａｌ2Ｏ3系化合物と、可溶性カルシウム塩及び
／または消石灰とを液中で反応させ、、次いで結晶化さ
せて一般式
【化１】３ＣａＯ・Ａｌ2Ｏ3・ＣａＸ2/m・ｎＨ2Ｏ
(式中、Ｘは１価または２価のアニオンであり、ｍはア
ニオンの価数を表し、ｎは２０以下を示す)で表される
ハイドロカルマイトを得ることを特徴とする。(57) [Summary] [Object] An object of the present invention is to provide a production method for obtaining hydrocalumite which is inexpensive and has high anion exchange ability. [Structure] The method for producing hydrocalumite of the present invention comprises:
CaO-Al 2 O 3 compound and, a soluble calcium salt and / or slaked lime by ,, then crystallized reacted in a liquid formula ## STR1 ## 3CaO · Al 2 O 3 · CaX 2 / m · nH 2 O (wherein X is a monovalent or divalent anion, m is a valence of anion, and n is 20 or less).
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ハイドロカルマイトの
製造方法に関するものであり、更に詳しくはＣａＯ−Ａ
ｌ2Ｏ3系化合物と、可溶性カルシウム塩及び／または消
石灰とを出発原料として液中で反応させ、次いで結晶化
することにより工業的に有利にハイドロカルマイトを製
造するための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 method for producing hydrocalumite, more specifically CaO-A.
The present invention relates to a method for industrially advantageously producing hydrocalmite by reacting an l 2 O 3 -based compound with a soluble calcium salt and / or slaked lime in a liquid as a starting material and then crystallizing the mixture. .
【０００２】[0002]
【従来の技術】従来、ハイドロカルマイトは、一般式2. Description of the Related Art Conventionally, hydrocalumite has a general formula
【化２】３ＣａＯ・Ａｌ2Ｏ3・ＣａＸ2/m・ｎＨ2Ｏ (式中、Ｘは１価または２価のアニオンであり、ｍはア
ニオンの価数を表し、ｎは２０以下を示す)で表される
ものであるが、２価−３価金属複合水酸化物の形をとる
層状結晶化合物であり、アニオン交換性のあることが知
られている。このような化合物と同じカテゴリーに属す
るものとしてＭｇ−Ａｌ系複合水酸化物であるハイドロ
タルサイトがあり、例えば代表的には樹脂添加剤として
使用されている。Embedded image 3CaO · Al 2 O 3 · CaX 2 / m · nH 2 O (In the formula, X is a monovalent or divalent anion, m is the valence of the anion, and n is 20 or less. ), It is a layered crystal compound in the form of a divalent-trivalent metal composite hydroxide, and is known to have anion exchange properties. Hydrotalcite, which is a Mg-Al-based composite hydroxide, belongs to the same category as such compounds, and is typically used as a resin additive, for example.
【０００３】ハイドロカルマイトは、例えばコンクリー
ト構造物における塩害等による鉄筋の腐食を抑制するた
めに有効な塩素イオン捕集剤として提案されている(特
開平４−154648号公報)。その製造方法として、例えば
前記一般式のＸがＮＯ2 -である亜硝酸型ハイドロカルマ
イトの場合、アルミン酸ナトリウムの溶液に亜硝酸カル
シウム溶液を添加してゲルを析出させ、これを結晶化さ
せる方法が知られている。Hydrocalumite has been proposed as a chlorine ion scavenger effective for suppressing corrosion of reinforcing bars due to salt damage in concrete structures (Japanese Patent Laid-Open No. 4-154648). As a manufacturing method, for example, X in the general formula NO 2 - For a is nitrite type hydrocalumite, by adding calcium nitrite solution to a solution of sodium aluminate to precipitate a gel, is crystallized The method is known.
【０００４】[0004]
【発明が解決しようとする課題】上記において、特に、
亜硝酸型ハイドロカルマイトは優れた塩素イオン捕捉能
と金属防錆能とが相俟って、コンクリート添加剤として
期待されている。しかしながら、アルミン酸ソーダや、
亜硝酸カルシウム等の可溶性カルシウム塩を使用した場
合、反応は比較的スムーズに進むが、その製造コストは
比較的高価なものになり、また、得られるハイドロカル
マイトの陰イオン交換能も充分でなく、例えばコンクリ
ート構造物用の塩素イオン捕集剤等に使用する場合好ま
しくないこともある。In the above, in particular,
Nitrite-type hydrocalumite is expected as a concrete additive because of its excellent chloride ion-capturing ability and metal anticorrosive ability. However, sodium aluminate,
When a soluble calcium salt such as calcium nitrite is used, the reaction proceeds relatively smoothly, but the production cost is relatively high, and the anion exchange capacity of the obtained hydrocalumite is not sufficient. However, it may not be preferable when used as a chlorine ion scavenger for concrete structures, for example.
【０００５】従って、本発明の目的は、安価で陰イオン
交換能の高いハイドロカルマイトを得るための製造方法
を提供することにある。Therefore, an object of the present invention is to provide a manufacturing method for obtaining hydrocalumite which is inexpensive and has a high anion exchange capacity.
【０００６】[0006]
【課題を解決するための手段】本発明者等は、叙上の問
題に鑑み、鋭意研究したところ、出発原料として上記ア
ルミン酸ソーダの代わりにＣａＯ−Ａｌ2Ｏ3系化合物を
用いて、可溶性カルシウム塩及び／または消石灰とを反
応させ、次いで結晶化することにより従来より安価で陰
イオン交換能が高いハイドロカルマイトを製造できる方
法を見出した。Means for Solving the Problems The inventors of the present invention have made extensive studies in view of the above problems, and found that a CaO--Al 2 O 3 -based compound was used as a starting material instead of the sodium aluminate as a starting material, and the solubility was improved. The inventors have found a method for producing hydrocalumite which is cheaper than conventional ones and has high anion exchange capacity by reacting with calcium salt and / or slaked lime and then crystallizing.
【０００７】即ち、本発明が提供しようとするハイドロ
カルマイトの製造方法は、ＣａＯ−Ａｌ2Ｏ3系化合物
と、可溶性カルシウム塩及び／または消石灰とを液中で
反応させ、次いで結晶化させて一般式That is, the method for producing hydrocalumite to be provided by the present invention is that a CaO--Al 2 O 3 -based compound is reacted with a soluble calcium salt and / or slaked lime in a liquid and then crystallized. General formula
【化３】３ＣａＯ・Ａｌ2Ｏ3・ＣａＸ2/m・ｎＨ2Ｏ (式中、Ｘは１価または２価のアニオンであり、ｍはア
ニオンの価数を表し、ｎは２０以下を示す)で表される
ハイドロカルマイトを製造することを構成上の特徴とす
るものである。## STR3 ## 3CaO · Al 2 O 3 · CaX 2 / m · nH 2 O ( wherein, X is a monovalent or divalent anion, m represents the valency of the anion, n represents shows the 20 following ) Is characterized in that the hydrocalumite represented by the formula is produced.
【０００８】以下、本発明につき説明する。本発明にお
いて使用する原料は、工業的に入手できるものであれ
ば、いずれでもよいが、ＣａＯ−Ａｌ2Ｏ3系化合物とし
ては、例えば化学式としてＣａＯ・Ａｌ2Ｏ3、５ＣａＯ
・３Ａｌ2Ｏ3、２ＣａＯ・Ａｌ2Ｏ3、３ＣａＯ・５Ａｌ
2Ｏ3、１２ＣａＯ・７Ａｌ2Ｏ3、３ＣａＯ・Ａｌ2Ｏ3等
の鉱物組成を有する微粉末が挙げられる。本発明におい
ては、特に、ＣａＯ・Ａｌ2Ｏ3、５ＣａＯ・３Ａｌ
2Ｏ3、２ＣａＯ・Ａｌ2Ｏ3等の鉱物組成で構成されるア
ルミナセメントが好ましい。The present invention will be described below. Raw material used in the present invention, as long as industrially available, may be any, CaO-Al 2 as the O 3 compounds, for example, CaO · Al 2 O 3 as Formula, 5CaO
・ 3Al 2 O 3 , 2CaO ・ Al 2 O 3 , 3CaO ・ 5Al
Fine powders having a mineral composition such as 2 O 3 , 12CaO · 7Al 2 O 3 , 3CaO · Al 2 O 3 can be mentioned. In the present invention, especially CaO.Al 2 O 3 , 5CaO.3Al
Alumina cement composed of a mineral composition such as 2 O 3 , 2CaO.Al 2 O 3 is preferable.
【０００９】また、可溶性カルシウム塩としては、例え
ば塩化物、硝酸塩、亜硝酸塩等の無機塩類が経済的に有
利であるが、必要に応じ有機酸塩も用いることができ、
また、その濃度は限定されない。As the soluble calcium salt, inorganic salts such as chlorides, nitrates, nitrites, etc. are economically advantageous, but organic acid salts can be used if necessary.
Moreover, the concentration is not limited.
【００１０】本発明に係る製造方法は、上記ＣａＯ−Ａ
ｌ2Ｏ3系化合物と、可溶性カルシウム塩及び／または消
石灰とを液中で反応させることが１つの特徴となってい
る。The manufacturing method according to the present invention is based on the above CaO-A.
One of the characteristics is to react the l 2 O 3 -based compound with a soluble calcium salt and / or slaked lime in a liquid.
【００１１】また、上記反応において必要に応じてアル
カリ金属塩の存在下で反応させてもよい。アルカリ金属
塩としては、例えば塩化ナトリウム、亜硝酸ソーダ、硝
酸ソーダ等が挙げられ、その濃度は特に限定されない。In the above reaction, if necessary, the reaction may be carried out in the presence of an alkali metal salt. Examples of the alkali metal salt include sodium chloride, sodium nitrite, sodium nitrate and the like, and the concentration thereof is not particularly limited.
【００１２】この反応における原料系の混合操作は、Ｃ
ａＯ−Ａｌ2Ｏ3系化合物と、可溶性カルシウム塩及び／
または消石灰とが液中に存在していればよく、その添加
方法は特に限定されるものではない。The mixing operation of the raw material system in this reaction is C
aO-Al 2 O 3 based compound, soluble calcium salt and / or
Alternatively, slaked lime may be present in the liquid, and its addition method is not particularly limited.
【００１３】ただし、この反応におけるＣａＯ／Ａｌ2
Ｏ3のモル比は、３.３〜４.２の範囲内に設定するのが
好ましい。この理由は、このモル比が、例えば３.３未
満の場合には、目的物の収率が極端に低くなるばかりで
なく、結晶化における熟成を行っても、非晶質の割合が
多くなり、結晶化度が低くなる。また、モル比が４.２
を超えると、ハイドロカルマイトは生成せず、Ｃａ(Ｏ
Ｈ)2や３ＣａＯ・Ａｌ2Ｏ3(以下、「Ｃ3Ａと呼ぶ」)の
不純物が生成するからである。However, CaO / Al 2 in this reaction
The molar ratio of O 3 is preferably set within the range of 3.3 to 4.2. The reason for this is that if the molar ratio is less than 3.3, for example, not only the yield of the desired product will be extremely low, but also the ratio of amorphous will increase even if aging in crystallization is performed. , The crystallinity becomes low. Also, the molar ratio is 4.2
When it exceeds the limit, hydrocalumite is not formed, and Ca (O
This is because impurities such as H) 2 and 3CaO.Al 2 O 3 (hereinafter, referred to as “C 3 A”) are generated.
【００１４】その反応系のスラリー濃度は、５〜３０重
量％の範囲が工業的に適当であり、例えば３０重量％を
超える場合、反応系の粘度が高くなり、撹拌が困難にな
り、また、５重量％未満では生産性が悪いことによる。
従って、その濃度の設定は、上記範囲内で経済的理由に
より設定すればよい。The slurry concentration of the reaction system is industrially suitable in the range of 5 to 30% by weight. For example, when it exceeds 30% by weight, the viscosity of the reaction system becomes high, stirring becomes difficult, and If it is less than 5% by weight, productivity is poor.
Therefore, the concentration may be set within the above range for economic reasons.
【００１５】また、本発明において、可溶性カルシウム
塩と消石灰を使用する場合、その割合は製造条件及びア
ニオンの種類により限定することはできないが、ｓ−Ｃ
ａＯ／Ｉｎｓ−ＣａＯ(ｓ−ＣａＯは可溶性カルシウム
塩をＣａＯ換算した量、Ｉｎｓ−ＣａＯは石灰等をＣａ
Ｏ換算した量を表す)で示されるモル比が０〜３の範囲
であり、好ましくは０.１〜２である。In the present invention, when soluble calcium salt and slaked lime are used, the ratio thereof cannot be limited depending on the production conditions and the type of anion.
aO / Ins-CaO (s-CaO is the amount of soluble calcium salt converted to CaO, Ins-CaO is lime etc.
The molar ratio represented by O) is in the range of 0 to 3, and preferably 0.1 to 2.
【００１６】反応温度は６０℃以下であればよく、好ま
しくは３０℃以下である。また、反応時間は０.５時間
以上であれば特に限定されるものではない。この反応に
より、ゲル状の沈澱物が生成し、この系の均一化と生成
物の熟成も含めて、上記条件で行うのがよい。The reaction temperature may be 60 ° C. or lower, preferably 30 ° C. or lower. The reaction time is not particularly limited as long as it is 0.5 hours or more. A gel-like precipitate is formed by this reaction, and it is preferable to carry out the above-mentioned conditions including homogenization of this system and aging of the product.
【００１７】次いで、反応終了後、ハイドロカルマイト
の結晶粒子を生成させるべく結晶化を行う。この時、結
晶化の温度は高くとも７０℃、好ましくは４０〜６５℃
の範囲に設定することが重要である。結晶化の温度を、
７０℃を超える温度で行う場合、ハイドロカルマイトは
生成するが、陰イオン交換能の低いものとなってしま
う。また、Ｃａ(ＯＨ)2とＣ3Ａが生成する副反応が生じ
る傾向となるので好ましくない。Next, after completion of the reaction, crystallization is carried out so as to generate hydrocalumite crystal particles. At this time, the crystallization temperature is at most 70 ° C, preferably 40 to 65 ° C.
It is important to set within the range. The crystallization temperature,
When the temperature is higher than 70 ° C., hydrocalumite is produced, but the anion exchange capacity is low. In addition, a side reaction of Ca (OH) 2 and C 3 A tends to occur, which is not preferable.
【００１８】更に、本発明の製造方法において、上記結
晶化反応では常圧でもよいが減圧により一部水を除去さ
せながら、結晶化を行う減圧晶析を行ってもよい。この
方法では、反応系の濃度を濃縮させると共にハイドロカ
ルマイト中の陰イオンの取り込まれ量が増え、その陰イ
オン交換能が著しく増加する傾向が見られるためであ
る。なお、結晶化の時間は２時間以上であればよい。Further, in the production method of the present invention, the crystallization reaction may be carried out under normal pressure, but may be carried out under reduced pressure for crystallization while partially removing water by reducing pressure. This is because, in this method, the concentration of the reaction system is concentrated and the amount of anions incorporated in the hydrocalumite increases, and the anion exchange capacity tends to remarkably increase. The crystallization time may be 2 hours or more.
【００１９】結晶化終了後、沈澱を常法により濾過、洗
浄、乾燥する。乾燥後、必要に応じて粉砕分級を行うこ
とができる。After completion of crystallization, the precipitate is filtered, washed and dried by a conventional method. After drying, pulverization and classification can be carried out if necessary.
【００２０】本発明の製造方法において得られた白色結
晶は、一般式The white crystals obtained by the production method of the present invention have the general formula
【化４】３ＣａＯ・Ａｌ2Ｏ3・ＣａＸ2/m・ｎＨ2Ｏ (式中、Ｘは１価または２価のアニオンであり、ｍはア
ニオンの価数を表し、ｎは２０以下を示す)で表される
ハイドロカルマイトであり、その結晶は層状構造を有す
る微粉末で、高い陰イオン交換能を有している。Embedded image 3CaO · Al 2 O 3 · CaX 2 / m · nH 2 O ( wherein, X is a monovalent or divalent anion, m represents the valency of the anion, n represents shows the 20 following ), The crystal thereof is a fine powder having a layered structure and has a high anion exchange ability.
【００２１】従って、本発明に係るハイドロカルマイト
は、特に亜硝酸型ハイドロカルマイトにあっては、コン
クリートの防錆顔料、樹脂添加剤としての用途が期待さ
れるものである。Therefore, the hydrocalumite according to the present invention is expected to be used as a rust preventive pigment for concrete and as a resin additive, especially in the case of nitrite type hydrocalumite.
【００２２】[0022]
【実施例】本発明を更に具体的に説明するために、実施
例をもって以下に説明する。 実施例１：亜硝酸型ハイドロカルマイトの製造 Ａｌ2Ｏ3：５４.８９重量％、ＣａＯ：３４.５９重量％
を含有するアルミナセメント５ｋｇと、亜硝酸カルシウ
ム１水塩４.０４ｋｇ、消石灰３.６９ｋｇ、水４０ｋｇ
を加え、２５℃で２４時間反応を行ったところ、ゲル状
の沈澱物が生成した。次いで、このスラリーを６０℃に
加温して常圧で４時間撹拌を続けながら結晶化を行っ
た。得られた沈澱物を常法により濾過、洗浄した後、乾
燥したところ１７ｋｇの白色固体を得た。得られた白色
固体を粉砕し、１５０メッシュ以下の白色粉末を得た。
白色粉末をＸ線回折、化学分析、赤外線吸収スペクト
ル、電子顕微鏡写真で解析した結果、不純物として少量
のＣａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏを含有する層状亜硝酸
型ハイドロカルマイトであることを確認した。EXAMPLES In order to describe the present invention more specifically, examples will be described below. Example 1: Production of nitrite type hydrocalumite Al 2 O 3 : 54.89% by weight, CaO: 34.59% by weight
Alumina cement containing 5kg, calcium nitrite monohydrate 4.04kg, slaked lime 3.69kg, water 40kg
Was added and the reaction was carried out at 25 ° C. for 24 hours, and a gel-like precipitate was formed. Next, this slurry was heated to 60 ° C. and crystallized while continuing stirring at normal pressure for 4 hours. The obtained precipitate was filtered and washed by a conventional method and then dried to obtain 17 kg of a white solid. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less.
The white powder was analyzed by X-ray diffraction, chemical analysis, infrared absorption spectrum, and electron micrograph. As a result, it was confirmed that it was a layered nitrite-type hydrocalumite containing a small amount of Ca (OH) 2 and C 3 A · 6H 2 O as impurities. I confirmed that there is.
【００２３】実施例２：亜硝酸型ハイドロカルマイトの
製造 反応終了後、減圧蒸留により水を全体の重量に対して約
５重量％除去し、減圧下で結晶化を行った他は、実施例
１と同様に行った結果、１８ｋｇの白色固体を得た。得
られた白色固体を粉砕し、１５０メッシュ以下の白色粉
末を得た。白色粉末を実施例１と同様に解析した結果、
不純物として少量のＣａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏを含
有する層状亜硝酸型ハイドロカルマイトであることを確
認した。Example 2 Production of Nitrite-type Hydrocalumite After the reaction was completed, about 5% by weight of water was removed by distillation under reduced pressure, and crystallization was performed under reduced pressure. As a result of performing in the same manner as in 1, 18 kg of a white solid was obtained. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less. As a result of analyzing the white powder in the same manner as in Example 1,
It was confirmed to be a layered nitrite type hydrocalumite containing a small amount of Ca (OH) 2 and C 3 A.6H 2 O as impurities.
【００２４】実施例３：亜硝酸型ハイドロカルマイトの
製造 Ａｌ2Ｏ3：５４.８９重量％、ＣａＯ：３４.５９重量％
を含有するアルミナセメント５ｋｇと、亜硝酸ソーダ
３.７１ｋｇ、消石灰５.６８ｋｇ、水４０ｋｇとを加
え、２５℃で２４時間反応を行った他は、実施例１と同
様に行ったところ１７ｋｇの白色固体を得た。得られた
白色固体を粉砕し、１５０メッシュ以下の白色粉末を得
た。白色粉末を実施例１と同様に解析した結果、不純物
として少量のＣａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏを含有する
層状亜硝酸型ハイドロカルマイトであることを確認し
た。Example 3: Production of nitrous acid type hydrocalumite Al 2 O 3 : 54.89% by weight, CaO: 34.59% by weight
Alumina cement containing 5 kg, 3.71 kg of sodium nitrite, 5.68 kg of slaked lime, and 40 kg of water were added, and the reaction was carried out at 25 ° C. for 24 hours. A solid was obtained. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less. As a result of analyzing the white powder in the same manner as in Example 1, it was confirmed that the white powder was a layered nitrite type hydrocalumite containing a small amount of Ca (OH) 2 and C 3 A · 6H 2 O as impurities.
【００２５】実施例４：亜硝酸型ハイドロカルマイトの
製造 実施例１で使用したアルミナセメント５ｋｇと、亜硝酸
カルシウム１水塩１１.５１ｋｇ、水４０ｋｇとを加
え、２５℃で２４時間反応し、実施例１と同様の操作を
行ったところ、１７.２ｋｇの白色固体を得た。得られ
た白色固体を粉砕し、１５０メッシュ以下の白色粉末を
得た。白色粉末を実施例１と同様に解析した結果、層状
亜硝酸型ハイドロカルマイトであることを確認した。Example 4 Production of Nitrite-Type Hydrocalumite 5 kg of the alumina cement used in Example 1, 11.51 kg of calcium nitrite monohydrate and 40 kg of water were added and reacted at 25 ° C. for 24 hours, When the same operation as in Example 1 was performed, 17.2 kg of a white solid was obtained. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less. As a result of analyzing the white powder in the same manner as in Example 1, it was confirmed to be layered nitrite-type hydrocalumite.
【００２６】実施例５：亜硝酸型ハイドロカルマイトの
製造 実施例１で使用したアルミナセメント５ｋｇと、消石灰
５.６８ｋｇ、亜硝酸ソーダ３.７１ｋｇ、水４０ｋｇと
を加え、２５℃で２４時間反応し、実施例１と同様の操
作を行ったところ、１７.２ｋｇの白色固体を得た。得
られた白色固体を粉砕し、１５０メッシュ以下の白色粉
末を得た。白色粉末を実施例１と同様に解析した結果、
不純物として少量のＣａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏを含
有する層状亜硝酸型ハイドロカルマイトであることを確
認した。Example 5: Production of nitrous acid type hydrocalumite 5 kg of the alumina cement used in Example 1, 5.68 kg of slaked lime, 3.71 kg of sodium nitrite and 40 kg of water were added and reacted at 25 ° C. for 24 hours. Then, the same operation as in Example 1 was carried out to obtain 17.2 kg of a white solid. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less. As a result of analyzing the white powder in the same manner as in Example 1,
It was confirmed to be a layered nitrite type hydrocalumite containing a small amount of Ca (OH) 2 and C 3 A.6H 2 O as impurities.
【００２７】実施例６：硝酸型ハイドロカルマイトの製
造 実施例５の亜硝酸ソーダの代わりに硝酸ソーダ４.５７
ｋｇを使用した他は、実施例５と同様に行った結果、１
７.２ｋｇの白色固体を得た。得られた白色固体を粉砕
し、１５０メッシュ以下の白色粉末を得た。白色粉末を
実施例１と同様に解析した結果、不純物として少量のＣ
ａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏを含有する層状硝酸型ハイ
ドロカルマイトであることを確認した。Example 6: Preparation of nitric acid type hydrocalumite Sodium nitrate 4.57 instead of sodium nitrite of Example 5.
As a result of performing in the same manner as in Example 5 except that kg was used, 1
7.2 kg of white solid was obtained. The white solid obtained was crushed to obtain a white powder having a size of 150 mesh or less. As a result of analyzing the white powder in the same manner as in Example 1, a small amount of C as an impurity was obtained.
It was confirmed to be a layered nitric acid type hydrocalumite containing a (OH) 2 and C 3 A.6H 2 O.
【００２８】比較例１ 反応温度を６５℃、結晶化を７５℃で行う他は、実施例
１と同様にして白色粉末を回収した。この白色粉末を実
施例１と同様に解析したところ、亜硝酸型ハイドロカル
マイトは生成せず、Ｃａ(ＯＨ)2とＣ3Ａ・６Ｈ2Ｏの混
合物であることが判った。Comparative Example 1 A white powder was recovered in the same manner as in Example 1 except that the reaction temperature was 65 ° C. and the crystallization was 75 ° C. When this white powder was analyzed in the same manner as in Example 1, it was found that nitrite-type hydrocalumite was not formed and it was a mixture of Ca (OH) 2 and C 3 A.6H 2 O.
【００２９】陰イオン交換能の測定 実施例１〜５で得られたハイドロカルマイトの陰イオン
交換能を次の測定方法により行い、表１の結果を得た。 測定方法 ０.１規定ＮａＣｌ溶液１００ｍｌに実施例で得られた
ハイドロカルマイトの試料粉末１０ｇを添加し、４時間
撹拌した後、溶液中に放出された陰イオンの量を測定す
る。例えば、亜硝酸型ハイドロカルマイトの場合、放出
された亜硝酸根の量(ｍｇ)を(ｍｇ−ｅｑ／ｇ)として計
算し、陰イオン交換能として表す。Measurement of anion exchange capacity The anion exchange capacity of the hydrocalumite obtained in Examples 1 to 5 was measured by the following measuring method, and the results shown in Table 1 were obtained. Measuring method To 100 ml of 0.1 N NaCl solution, 10 g of the hydrocalumite sample powder obtained in the example was added, and after stirring for 4 hours, the amount of anions released in the solution was measured. For example, in the case of nitrite type hydrocalumite, the amount (mg) of released nitrite is calculated as (mg-eq / g) and expressed as anion exchange capacity.
【００３０】[0030]
【表１】表１ 実施例 陰イオン交換能(ｍｇ−ｅｑ／ｇ) １ １.５５ ２ １.７０ ３ １.３５ ４ ２.７５ ５ １.３０ ６ １.２７[Table 1] Table 1 Example Anion exchange capacity (mg-eq / g) 1 1.55 2 1.70 3 1.35 4 2.75 5 1.30 6 1.27
【００３１】[0031]
【発明の効果】以上の通り、本発明に係る製造方法は、
ＣａＯ−Ａｌ2Ｏ3系化合物と、可溶性カルシウム塩及び
／または消石灰とを液中で反応させ、次いで、結晶化す
ることを特徴とするものであるが、本発明方法によれ
ば、安価で陰イオン交換能の高いハイドロカルマイトを
得ることができる。As described above, the manufacturing method according to the present invention is
The method is characterized by reacting a CaO-Al 2 O 3 -based compound with a soluble calcium salt and / or slaked lime in a liquid, and then crystallizing the compound. Hydrocalumite having a high ion exchange capacity can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 立松 英信 東京都国分寺市光町２丁目８番地38 財団 法人鉄道総合技術研究所内 (72)発明者 高田 潤 東京都国分寺市光町２丁目８番地38 財団 法人鉄道総合技術研究所内 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Innovator Hidenobu Tatematsu 2-8, Hikarimachi, Kokubunji, Tokyo 38 Inside Railroad Technical Research Institute (72) Inventor Jun Takada 2-8, Hikarimachi, Kokubunji, Tokyo 38 Inside the Railway Technical Research Institute
Claims (6)
ルシウム塩及び／または消石灰とを液中で反応させ、、
次いで結晶化させて一般式 【化１】３ＣａＯ・Ａｌ2Ｏ3・ＣａＸ2/m・ｎＨ2Ｏ (式中、Ｘは１価または２価のアニオンであり、ｍはア
ニオンの価数を表し、ｎは２０以下を示す)で表される
ハイドロカルマイトを得ることを特徴とするハイドロカ
ルマイトの製造方法。1. A CaO—Al 2 O 3 compound and a soluble calcium salt and / or slaked lime are reacted in a liquid,
Then, it is crystallized and represented by the general formula: 3CaO.Al 2 O 3 .CaX 2 /m.nH 2 O (In the formula, X represents a monovalent or divalent anion, and m represents a valence of the anion. , N is 20 or less), a method for producing hydrocalumite, characterized in that hydrocalumite represented by the formula (1) is obtained.
下で行われる請求項１記載のハイドロカルマイトの製造
方法。2. The method for producing hydrocalumite according to claim 1, wherein the reaction in the liquid is carried out in the presence of an alkali metal salt.
は２記載のハイドロカルマイトの製造方法。3. The method for producing hydrocalumite according to claim 1, wherein the crystallization is performed under reduced pressure.
メントである請求項１ないし３のいずれか１項に記載の
ハイドロカルマイトの製造方法。4. The method for producing hydrocalumite according to claim 1, wherein the CaO—Al 2 O 3 based compound is alumina cement.
３〜４.２の範囲内である請求項１ないし４のいずれか
１項に記載のハイドロカルマイトの製造方法。5. The molar ratio of CaO / Al 2 O 3 in the liquid is 3.
The method for producing hydrocalumite according to any one of claims 1 to 4, which is in the range of 3 to 4.2.
らなる群から選択される少なくとも１種である請求項１
ないし５のいずれか１項に記載のハイドロカルマイトの
製造方法。6. X is at least one selected from the group consisting of OH − , Cl − , NO 3 − and NO 2 −.
6. The method for producing hydrocalumite according to any one of items 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5180295A JP2787974B2 (en) | 1993-07-21 | 1993-07-21 | Method for producing hydrocalumite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5180295A JP2787974B2 (en) | 1993-07-21 | 1993-07-21 | Method for producing hydrocalumite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0733431A true JPH0733431A (en) | 1995-02-03 |
| JP2787974B2 JP2787974B2 (en) | 1998-08-20 |
Family
ID=16080718
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5180295A Expired - Fee Related JP2787974B2 (en) | 1993-07-21 | 1993-07-21 | Method for producing hydrocalumite |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2787974B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336002A (en) * | 2004-05-26 | 2005-12-08 | Nippon Chem Ind Co Ltd | Nitrite ion type hydrotalcite powder, production method thereof, rust preventive composition and rust preventive coating composition |
| JP2007191385A (en) * | 2005-12-20 | 2007-08-02 | Hiroko Ishikuri | Hydrocalumite, method for producing the same, chlorine ion scavenger, heavy metal-containing ion scavenger, coating material composition and cement composition containing them |
| JP2013184857A (en) * | 2012-03-08 | 2013-09-19 | Nippon Chem Ind Co Ltd | Method for producing nitrite-type hydrocalumite composition |
-
1993
- 1993-07-21 JP JP5180295A patent/JP2787974B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336002A (en) * | 2004-05-26 | 2005-12-08 | Nippon Chem Ind Co Ltd | Nitrite ion type hydrotalcite powder, production method thereof, rust preventive composition and rust preventive coating composition |
| JP2007191385A (en) * | 2005-12-20 | 2007-08-02 | Hiroko Ishikuri | Hydrocalumite, method for producing the same, chlorine ion scavenger, heavy metal-containing ion scavenger, coating material composition and cement composition containing them |
| JP2013184857A (en) * | 2012-03-08 | 2013-09-19 | Nippon Chem Ind Co Ltd | Method for producing nitrite-type hydrocalumite composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2787974B2 (en) | 1998-08-20 |
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