JP2000302438A - Synthesis of calcium aluminate gel and anion scavenger - Google Patents
Synthesis of calcium aluminate gel and anion scavengerInfo
- Publication number
- JP2000302438A JP2000302438A JP11113854A JP11385499A JP2000302438A JP 2000302438 A JP2000302438 A JP 2000302438A JP 11113854 A JP11113854 A JP 11113854A JP 11385499 A JP11385499 A JP 11385499A JP 2000302438 A JP2000302438 A JP 2000302438A
- Authority
- JP
- Japan
- Prior art keywords
- aluminate
- calcium
- organic compound
- gel
- alkali metal
- 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、カルシウムアルミ
ネートゲルの合成方法及びカルシウムアルミネートゲル
を有効成分とするアニオン捕集剤に関するものでる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing a calcium aluminate gel and an anion scavenger containing calcium aluminate gel as an active ingredient.
【０００２】[0002]
【従来の技術】カルシウムアルミネートゲルは、カルシ
ウムアルミネート系水硬性物質の水和反応において生成
すると言われているが、カルシウムアルミネートゲルの
工業的な合成や利用は、これまでに行われていなかっ
た。一方、アニオン捕集剤として有用な無機化合物とし
て、ハイドロタルサイト類が実用化されている（宮田繁
雄,セッコウと石灰,No.187,pp.333〜339,1983、特公昭4
8-8394号公報、及び特開昭61-115089号公報等）。ハイ
ドロタルサイトは、無機化合物としては高価な材料であ
り、これに代わる安価な材料の開発が待たれているのが
実状である。又、ハイドロタルサイトと類似の化合物と
して、化学式3CaO・Al2O3・CaX・nH2O（但し、式中のXは１
価又は２価のアニオンであり、ｎは整数）で示されるハ
イドロカルマイト類が知られている。そして、前記Ｘの
内容が硝酸イオンや亜硝酸イオンのハイドロカルマイト
類が、コンクリート中の鉄筋の防錆を目的に、アニオ
ン、特に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）。2. Description of the Related Art Calcium aluminate gel is said to be formed by a hydration reaction of a calcium aluminate-based hydraulic substance. However, industrial synthesis and utilization of calcium aluminate gel have been performed so far. Did not. On the other hand, hydrotalcites have been put to practical use as an inorganic compound useful as an anion scavenger (Shigeo Miyata, Gypsum and Lime, No. 187, pp. 333-339, 1983;
8-8394 and JP-A-61-115089). Hydrotalcite is an expensive material as an inorganic compound, and the development of an inexpensive alternative material has been awaited. Further, as a compound similar to hydrotalcite, the chemical formula 3CaO.Al 2 O 3 .CaX.nH 2 O (where X in the formula is 1
Hydrocalumite represented by the following formula: is a monovalent or divalent anion, and n is an integer. Hydrocarbites in which the content of X is nitrate ion or nitrite ion have been proposed as an anion, especially a chloride ion collector, for the purpose of preventing rust of reinforcing steel in concrete (Japanese Patent Laid-Open No. 4-154648). No.).
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、カルシ
ウムアルミネートゲルを安定して合成することは困難で
あった。又、従来のアニオン捕集剤は、イオン交換反応
によってアニオンを捕集するものであり、目的とするア
ニオンは捕集できるが、それと交換して、他のアニオン
を系外へ放出するため、例えば、浄水処理等には利用で
きないという課題があった。本発明者らは、このような
状況を鑑み鋭意検討した結果、特定のカルシウムアルミ
ネートゲルの合成方法及びアニオン捕集剤により、前記
課題を解消できることを知見し、本発明を完成するに至
った。However, it has been difficult to stably synthesize a calcium aluminate gel. In addition, the conventional anion-collecting agent is for collecting anions by an ion-exchange reaction, and can collect a target anion, but exchanges it with another to release other anions to the outside of the system. However, there is a problem that it cannot be used for water purification and the like. The present inventors have conducted intensive studies in view of such a situation, and as a result, have found that the above-mentioned problems can be solved by a specific calcium aluminate gel synthesis method and an anion trapping agent, and have completed the present invention. .
【０００４】[0004]
【課題を解決するための手段】即ち、本発明は、酸化カ
ルシウム及び／又は水酸化カルシウムとアルミン酸アル
カリ金属塩と有機化合物とを水の存在下で反応させるこ
とを特徴とするカルシウムアルミネートゲルの合成方法
であり、該カルシウムアルミネートゲルを有効成分とす
るアニオン捕集剤である。That is, the present invention provides a calcium aluminate gel characterized by reacting calcium oxide and / or calcium hydroxide with an alkali metal aluminate and an organic compound in the presence of water. Which is an anion scavenger containing the calcium aluminate gel as an active ingredient.
【０００５】[0005]
【発明の実施の形態】以下、本発明を詳細に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
【０００６】本発明のカルシウムアルミネートゲル（以
下、ＣＡＧという）とは、ＣａＯ、Ａｌ2Ｏ3及びＨ2Ｏ
を主成分とする、非晶質の物質を総称するものである。
非晶質とは、例えば、粉末Ｘ線回折法により明瞭な回折
線を得ることのできない物質である。[0006] The calcium aluminate gel (hereinafter referred to as CAG) of the present invention refers to CaO, Al 2 O 3 and H 2 O.
Is a general term for an amorphous substance whose main component is.
An amorphous substance is a substance for which a clear diffraction line cannot be obtained by a powder X-ray diffraction method, for example.
【０００７】本発明のＣＡＧの合成方法は、酸化カルシ
ウム及び／又は水酸化カルシウムとアルミン酸アルカリ
金属塩と有機化合物とを水中で反応させるものである。
本発明では、酸化カルシウム及び／又は水酸化カルシウ
ムが使用可能であるが、得られるＣＡＧの品質が安定す
ることから、又、安全性の面から、水酸化カルシウムを
使用することが好ましい。反応温度は、特に限定される
ものではないが、温度が高いと結晶質のカルシウムアル
ミネート水和物が生成し易く、通常、２０℃以下が好ま
しく、５〜１５℃がより好ましい。未反応物の残存量を
低減するためには、熟成することが好ましい。The CAG synthesis method of the present invention comprises reacting calcium oxide and / or calcium hydroxide with an alkali metal aluminate and an organic compound in water.
In the present invention, calcium oxide and / or calcium hydroxide can be used, but it is preferable to use calcium hydroxide because the quality of the obtained CAG is stable and from the viewpoint of safety. The reaction temperature is not particularly limited, but when the temperature is high, crystalline calcium aluminate hydrate is easily generated, and usually, preferably 20 ° C or lower, more preferably 5 to 15 ° C. In order to reduce the remaining amount of unreacted substances, aging is preferred.
【０００８】本発明のＣＡＧは、特に限定されるもので
はないが、ＣａＯ／Ａｌ2Ｏ3モル比（以下、Ｃ/Ａモル
比という）が０．５〜６．０の範囲にあるものが好まし
く、Ｃ/Ａモル比が１．０〜３．０の範囲にあるものが
より好ましい。Ｃ/Ａモル比が前記範囲外では十分なア
ニオン捕集能が得られない場合がある。The CAG of the present invention is not particularly limited, but one having a CaO / Al 2 O 3 molar ratio (hereinafter referred to as C / A molar ratio) in the range of 0.5 to 6.0. More preferably, the C / A molar ratio is in the range of 1.0 to 3.0. If the C / A molar ratio is out of the above range, sufficient anion collecting ability may not be obtained.
【０００９】本発明のアルミン酸アルカリ金属塩（以
下、アルミン酸塩という）とは、化学式Ａｌ2Ｏ3・ｍＲ
2Ｏ（Ｒはアルカリ金属、ｍは通常、０．５〜２程度）
で示されるものであり、特に限定されるものではなく、
その具体例としては、アルミン酸ナトリウム、アルミン
酸カリウム及びアルミン酸リチウム等が挙げられ、本発
明ではこれらのうちの一種又は二種以上が使用可能であ
る。又、アルミン酸塩は、１０モル以下の範囲で結晶水
を有するものがあり、本発明では何れも使用可能であ
る。The alkali metal aluminate of the present invention (hereinafter referred to as aluminate) has the chemical formula of Al 2 O 3 .mR
2 O (R is an alkali metal, m is usually about 0.5 to 2)
It is shown in, is not particularly limited,
Specific examples thereof include sodium aluminate, potassium aluminate, and lithium aluminate, and one or more of these can be used in the present invention. Some aluminates have water of crystallization in a range of 10 mol or less, and any of them can be used in the present invention.
【００１０】本発明では、酸化カルシウム及び／又は水
酸化カルシウムとアルミン酸塩をＣ/Ａモル比が０．５
〜６．０の範囲になるように配合することが好ましい。
又、酸化カルシウム及び／又は水酸化カルシウムとアル
ミン酸塩は、各々１リットルの水に０．１モル〜６モル
の範囲で配合することが好ましい。０．１モル未満では
ＣＡＧの合成量が少なくなり、工業的に有益でなく、６
モルを超えるような高濃度では、反応液の粘性が極めて
強くなり、混合・撹拌が困難となる場合がある。In the present invention, calcium oxide and / or calcium hydroxide and aluminate are mixed at a C / A molar ratio of 0.5.
It is preferable to mix them so as to be in the range of 6.0 to 6.0.
Further, it is preferable that calcium oxide and / or calcium hydroxide and aluminate are mixed in 1 liter of water in a range of 0.1 mol to 6 mol. If the amount is less than 0.1 mol, the amount of CAG synthesized becomes small, which is not industrially useful.
If the concentration is higher than the molar concentration, the viscosity of the reaction solution becomes extremely strong, and mixing and stirring may be difficult.
【００１１】前記の方法により、ＣＡＧを合成する際、
副生物として水酸化アルミニウムが生成し、又、未反応
物として水酸化カルシウムが残存する場合があるが、本
発明の効果を実質的に阻害しない範囲、具体的にはこれ
らの総量が５０重量％以下であれば特に問題とはならな
い。When synthesizing CAG by the above method,
Aluminum hydroxide may be produced as a by-product and calcium hydroxide may remain as an unreacted substance. However, the total amount of these substances is 50% by weight in a range that does not substantially impair the effects of the present invention. There is no problem if it is below.
【００１２】本発明では、酸化カルシウム及び／又は水
酸化カルシウムとアルミン酸塩の他に有機化合物を使用
する。有機化合物を使用しない場合は、ＣＡＧは得られ
ない。In the present invention, an organic compound is used in addition to calcium oxide and / or calcium hydroxide and an aluminate. When no organic compound is used, CAG cannot be obtained.
【００１３】本発明の有機化合物とは、特に限定される
ものではないが、その具体例としては、しょ糖、ブドウ
糖及び麦芽糖等の糖類、乳酸、ギ酸、リンゴ酸、クエン
酸、グルコン酸、酢酸、コハク酸、酒石酸及びサリチル
酸等の有機酸又はこれらの塩、モノエタノールアミン、
ジエタノールアミン及びトリエタノールアミン等のアミ
ン類、グリシン等のアミノ酸、尿素、並びにヘキサメチ
レンテトラミン等が挙げられ、これらのうちの一種又は
二種以上が使用可能であるが、比較的安価な糖類又は有
機酸若しくはその塩を使用することが好ましい。The organic compound of the present invention is not particularly limited, but specific examples thereof include sugars such as sucrose, glucose and maltose, lactic acid, formic acid, malic acid, citric acid, gluconic acid, acetic acid, and the like. Organic acids such as succinic acid, tartaric acid and salicylic acid or salts thereof, monoethanolamine,
Amines such as diethanolamine and triethanolamine; amino acids such as glycine; urea; and hexamethylenetetramine. One or more of these can be used, but relatively inexpensive sugars or organic acids. Alternatively, it is preferable to use a salt thereof.
【００１４】有機化合物の溶液濃度は、特に限定される
ものではないが、通常、１０重量％以下の範囲が好まし
く、１〜５重量％がより好ましい。１０重量％を超えて
使用しても更なる効果の向上が期待できない。The solution concentration of the organic compound is not particularly limited, but is usually preferably 10% by weight or less, more preferably 1 to 5% by weight. Use of more than 10% by weight cannot be expected to further improve the effect.
【００１５】[0015]
【実施例】以下、実施例により本発明を詳細に説明す
る。The present invention will be described below in detail with reference to examples.
【００１６】実施例１ 酸化カルシウム、水酸化カルシウム及びアルミン酸塩Ａ
を表１に示すような割合で各々１リットルの水に配合
し、これらと有機化合物−イの３重量％水溶液１リット
ルを混合し、１０℃で反応させてゲル状沈殿物を得た。
この反応液を撹拌しながら７日間熟成した後、吸引濾過
によって固液分離し、固相を純水で充分に洗浄した後、
アセトンにより余剰水を除去して４０℃で乾燥した。得
られた生成物について、非晶質であることを粉末Ｘ線回
折法により同定し、Ｃ/Ａモル比を化学分析により測定
した。その結果を表１に示す。 ＜使用材料＞ 酸化カルシウム：試薬１級 水酸化カルシウム：試薬１級 アルミン酸塩Ａ：試薬１級アルミン酸ナトリウム 有機化合物−イ：試薬１級しょ糖 水：純水Example 1 Calcium oxide, calcium hydroxide and aluminate A
Were mixed with 1 liter of water at the ratios shown in Table 1, and 1 liter of a 3% by weight aqueous solution of organic compound-a was mixed and reacted at 10 ° C. to obtain a gel-like precipitate.
After aging the reaction solution for 7 days while stirring, it was subjected to solid-liquid separation by suction filtration, and the solid phase was sufficiently washed with pure water.
Excess water was removed with acetone and dried at 40 ° C. The obtained product was identified as being amorphous by powder X-ray diffraction method, and the C / A molar ratio was measured by chemical analysis. Table 1 shows the results. <Materials> Calcium oxide: Reagent 1st grade Calcium hydroxide: Reagent 1st grade Aluminate A: Reagent 1st grade sodium aluminate Organic compound-A: Reagent 1st grade sucrose Water: Pure water
【００１７】[0017]
【表１】 [Table 1]
【００１８】本発明のＣＡＧは、何れも非晶質である。Each of the CAGs of the present invention is amorphous.
【００１９】実施例２ 水酸化カルシウム及び有機化合物−イを使用し、アルミ
ン酸塩の種類を変えたこと以外は、実施例１と同様に行
った。その結果を表２に示す。 ＜使用材料＞ アルミン酸塩Ａ：試薬１級アルミン酸ナトリウム アルミン酸塩Ｂ：試薬１級アルミン酸カリウム アルミン酸塩Ｃ：試薬１級アルミン酸リチウムExample 2 Example 2 was repeated except that calcium hydroxide and organic compound I were used and the type of aluminate was changed. Table 2 shows the results. <Materials> Aluminate A: Reagent primary sodium aluminate Aluminate B: Reagent primary potassium aluminate Aluminate C: Reagent primary lithium aluminate
【００２０】[0020]
【表２】 [Table 2]
【００２１】本発明のＣＡＧは、何れも非晶質であるこ
とを示している。Each of the CAGs of the present invention is shown to be amorphous.
【００２２】実施例３ 水酸化カルシウム及びアルミン酸塩Ａを使用し、有機化
合物の種類と水溶液濃度を表３に示すように変えたこと
以外は、実施例１と同様に行った。その結果を表３に示
す。 ＜使用材料＞ 有機化合物−イ：試薬１級しょ糖 有機化合物−ロ：試薬１級クエン酸 有機化合物−ハ：試薬１級乳酸 有機化合物−ニ：試薬１級グルコン酸ナトリウム 有機化合物−ホ：試薬１級トリエタノールアミンExample 3 The procedure of Example 1 was repeated, except that calcium hydroxide and aluminate A were used, and the type of organic compound and the concentration of the aqueous solution were changed as shown in Table 3. Table 3 shows the results. <Materials Used> Organic compound-A: Reagent primary sucrose Organic compound-B: Reagent primary citric acid Organic compound-C: Reagent primary lactic acid Organic compound-D: Reagent primary sodium gluconate Organic compound-E: Reagent 1 Grade triethanolamine
【００２３】[0023]
【表３】 [Table 3]
【００２４】有機化合物を配合していない比較例（実験
No.3-1,3-2）では、生成物は結晶質であり、有機化合物
を配合した本発明のＣＡＧは、非晶質であることを示し
ている。Comparative Example not containing an organic compound (experiment
Nos. 3-1 and 3-2) show that the product is crystalline, and that the CAG of the present invention containing an organic compound is amorphous.
【００２５】実施例４ 実験No.1-6のＣＡＧを使用し、ＣＡＧ１ｇを表４に示す
０．１モル/リットルの各種電解質溶液１００ミリリッ
トル中に浸漬し、３時間マグネチックスターラーで撹拌
した。その後、濾過して固液分離し、固相の同定を粉末
Ｘ線回折法により、液相の分析を滴定により行った。そ
の結果を表４に示す。Example 4 Using CAG of Experiment No. 1-6, 1 g of CAG was immersed in 100 ml of 0.1 mol / l of various electrolyte solutions shown in Table 4 and stirred with a magnetic stirrer for 3 hours. Thereafter, the mixture was filtered to be separated into solid and liquid, and the solid phase was identified by powder X-ray diffraction and the liquid phase was analyzed by titration. Table 4 shows the results.
【００２６】[0026]
【表４】 [Table 4]
【００２７】本発明のＣＡＧは、何れも顕著なアニオン
捕集能を示している。Each of the CAGs of the present invention has a remarkable anion collecting ability.
【００２８】[0028]
【発明の効果】本発明により、カルシウムアルミネート
ゲルを安定して合成することが可能となる。更に、カル
シウムアルミネートゲルを有効成分とするアニオン捕集
剤は、他のアニオンを系外へ放出することがなく、浄水
処理等広範に使用することができる。According to the present invention, it is possible to stably synthesize a calcium aluminate gel. Furthermore, the anion scavenger containing calcium aluminate gel as an active ingredient does not release other anions to the outside of the system, and can be widely used in water purification treatment and the like.
Claims (2)
ムとアルミン酸アルカリ金属塩と有機化合物とを水中下
で反応させることを特徴とするカルシウムアルミネート
ゲルの合成方法。1. A method for synthesizing a calcium aluminate gel comprising reacting calcium oxide and / or calcium hydroxide with an alkali metal aluminate and an organic compound in water.
するアニオン捕集剤。2. An anion scavenger comprising calcium aluminate gel as an active ingredient.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11385499A JP3929201B2 (en) | 1999-04-21 | 1999-04-21 | Method for synthesizing calcium aluminate gel and anion scavenger |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11385499A JP3929201B2 (en) | 1999-04-21 | 1999-04-21 | Method for synthesizing calcium aluminate gel and anion scavenger |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2000302438A true JP2000302438A (en) | 2000-10-31 |
| JP3929201B2 JP3929201B2 (en) | 2007-06-13 |
Family
ID=14622749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11385499A Expired - Fee Related JP3929201B2 (en) | 1999-04-21 | 1999-04-21 | Method for synthesizing calcium aluminate gel and anion scavenger |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008126217A (en) * | 2006-11-24 | 2008-06-05 | Denki Kagaku Kogyo Kk | Fluorine capturing material and method for cleaning water by using the same |
| JP2017088481A (en) * | 2015-11-04 | 2017-05-25 | 多木化学株式会社 | Alumina colloid-containing aqueous solution |
-
1999
- 1999-04-21 JP JP11385499A patent/JP3929201B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008126217A (en) * | 2006-11-24 | 2008-06-05 | Denki Kagaku Kogyo Kk | Fluorine capturing material and method for cleaning water by using the same |
| JP4718420B2 (en) * | 2006-11-24 | 2011-07-06 | 電気化学工業株式会社 | Fluorine collecting material and water purification method using the same |
| JP2017088481A (en) * | 2015-11-04 | 2017-05-25 | 多木化学株式会社 | Alumina colloid-containing aqueous solution |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3929201B2 (en) | 2007-06-13 |
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