JP3314184B2 - Method for producing swellable silicate - Google Patents
Method for producing swellable silicateInfo
- Publication number
- JP3314184B2 JP3314184B2 JP18615094A JP18615094A JP3314184B2 JP 3314184 B2 JP3314184 B2 JP 3314184B2 JP 18615094 A JP18615094 A JP 18615094A JP 18615094 A JP18615094 A JP 18615094A JP 3314184 B2 JP3314184 B2 JP 3314184B2
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- Japan
- Prior art keywords
- reaction
- silicate
- magnesium
- water
- solution
- Prior art date
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- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、天然鉱物のヘクトライ
トとして知られている粘土鉱物に類似した構造を有する
ケイ酸塩の製造方法に関するものである。さらに詳しく
は、高性能で且つ高品質の膨潤性ケイ酸塩の製造方法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silicate having a structure similar to a clay mineral known as a natural mineral hectorite. More particularly, it relates to a method for producing a high-performance and high-quality swellable silicate.
【０００２】[0002]
【従来の技術】ヘクトライト型粘土鉱物の合成方法とし
ては従来より、各種の原料を用いた種々の反応方法が提
案されている。例えば、特開昭５８−１８５４３１号公
報では、ケイ酸塩溶液に硝酸、塩酸、硫酸などの鉱酸を
添加して酸性とし、マグネシウム塩溶液と混合して均質
混合液とし、これにアルカリ溶液を加えてケイ酸・マグ
ネシウム共沈物を形成させ副生溶解質を水洗除去した
後、アルカリイオンおよびフッ素イオンを添加して水熱
反応を行なう方法が記載されている。上記方法では、最
初に得られるケイ酸・マグネシウム共沈物の濾過が非常
に困難であり、副生溶解質を完全に且つ短時間で能率良
く除去するのが困難であるという問題がある。この問題
の解決策として、限外濾過膜モジュールを用いて、選択
された特定の運転条件下で副生溶解質除去のための洗浄
および共沈物の分離・濃縮する方法が提案されている
（特開平５−２７９０１２号公報参照）。2. Description of the Related Art As a method for synthesizing a hectorite-type clay mineral, various reaction methods using various raw materials have been conventionally proposed. For example, in JP-A-58-185431, a silicate solution is made acidic by adding a mineral acid such as nitric acid, hydrochloric acid or sulfuric acid, mixed with a magnesium salt solution to form a homogeneous mixed solution, and an alkali solution is added thereto. In addition, a method is described in which a co-precipitate of silicic acid / magnesium is formed to remove by-product solutes with water, and then an alkali ion and a fluorine ion are added to carry out a hydrothermal reaction. In the above method, there is a problem that it is very difficult to filter the silicic acid / magnesium coprecipitate obtained first, and it is difficult to remove by-product solutes completely and efficiently in a short time. As a solution to this problem, a method has been proposed in which an ultrafiltration membrane module is used to wash for removing by-product solutes and to separate and concentrate coprecipitates under selected specific operating conditions ( See JP-A-5-279012).
【０００３】最初の反応で得られるケイ酸・マグネシウ
ム共沈物の副生溶解質の除去が不充分である場合、次の
水熱反応により得られるケイ酸塩の性能、すなわち溶媒
中でのゲル形成能（増粘性、懸濁安定性、チクソトロピ
ィ付与性）が悪くなり、高品質の膨潤性ケイ酸塩が得ら
れないのでこの水洗除去工程は必須である。高品質のケ
イ酸塩を安定に能率よく製造するために、ケイ酸・マグ
ネシウム共沈物の溶解質を水洗除去および共沈物の分離
・濃縮を容易にできる対策が望まれている。If the removal of by-product solutes of the silicate-magnesium coprecipitate obtained in the first reaction is insufficient, the performance of the silicate obtained by the subsequent hydrothermal reaction, ie, the gel in a solvent, This water washing and removing step is indispensable because the forming ability (thickening property, suspension stability, thixotropy-imparting property) deteriorates and a high-quality swellable silicate cannot be obtained. In order to stably and efficiently produce high-quality silicate, there is a demand for a measure capable of easily removing a solute of a silicate / magnesium coprecipitate with water and separating / concentrating the coprecipitate.
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、ケイ
酸・マグネシウム共沈物中の溶解質の充分な水洗除去お
よび共沈物の分離・濃縮を容易に能率よく実施すること
を可能にし、高性能且つ高品質の膨潤性ケイ酸塩を安定
に生産性よく製造する方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to make it possible to carry out sufficient washing of a solute in a silicic acid / magnesium coprecipitate with sufficient water and to separate and concentrate the coprecipitate easily and efficiently. An object of the present invention is to provide a method for stably producing a high-performance and high-quality swellable silicate with high productivity.
【０００５】[0005]
【課題を解決するための手段】本発明者は、膨潤性ケイ
酸塩の合成反応に注目して鋭意研究した結果、シリカ成
分の出発原料として鉱酸を添加していないケイ酸ナトリ
ウム溶液を用い、これにマグネシムウ塩溶液をアルカリ
性水性媒体中で反応させると、濾過・水洗が容易に実施
できるケイ酸・マグネシウム共沈物が得られることを見
い出し、さらに得られた共沈物に水酸化リチウムおよび
／または水酸化ナトリウムを添加して水熱反応を行なっ
て得られたケイ酸塩は高性能且つ高品質であることを見
出し本発明に到達した。Means for Solving the Problems The present inventors have conducted intensive studies focusing on the synthesis reaction of a swellable silicate, and as a result, using a sodium silicate solution to which no mineral acid has been added as a starting material for a silica component. It was found that when the magnesium salt solution was reacted with the magnesium salt solution in an alkaline aqueous medium, a silicic acid-magnesium coprecipitate that could be easily filtered and washed was obtained, and further, lithium hydroxide and lithium hydroxide were added to the obtained coprecipitate.
The present inventors have found that a silicate obtained by performing a hydrothermal reaction by adding sodium hydroxide has high performance and high quality, and reached the present invention.
【０００６】なすわち、本発明は下記工程、 （１）ケイ酸ナトリウムおよびマグネシウム塩をアルカ
リ性水性媒体中で反応させてケイ酸・マグネシウム共沈
物を沈澱させる工程、 （２）該沈澱物を濾過および水洗して副生溶解質を除去
する工程、 （３）かくして得られた沈澱物に水酸化リチウムおよび
／または水酸化ナトリウムを添加し、さらに必要により
フッ素イオンを添加し１００℃〜３００℃の温度で水熱
反応せしめる工程および （４）得られた反応生成物を乾燥する工程、よりなるこ
とを特徴とする下記一般式That is, the present invention provides the following steps: (1) a step of reacting sodium and magnesium silicates in an alkaline aqueous medium to precipitate a coprecipitate of silicate and magnesium; (2) (3) Lithium hydroxide and / or sodium hydroxide are added to the precipitate thus obtained, and if necessary, fluorine ions are added. A hydrothermal reaction at a temperature of (4) and (4) a step of drying the obtained reaction product.
【０００７】[0007]
【数２】 (Equation 2)
【０００８】［式中、ｘおよびｙは、０≦ｘ≦２、０≦
ｙ≦４、Ｍ+は１価の陽イオンを示す］で表わされるヘ
クトライト型粘土鉱物に類似した構造を有する膨潤性ケ
イ酸塩の製造方法である。Wherein x and y are 0 ≦ x ≦ 2, 0 ≦
y ≦ 4, and M + represents a monovalent cation.] This is a method for producing a swellable silicate having a structure similar to a hectorite-type clay mineral represented by the formula:
【０００９】本発明の第１工程において、ケイ酸ナトリ
ウムおよびマグネシウム塩をアルカリ性水性溶媒中で反
応させる場合、具体的方法としては例えば攪拌下に、マ
グネシウム塩の水溶液中に、ケイ酸ナトリウムおよびア
ルカリ水溶液を加えて沈澱させてもよく、またその逆の
順序に滴下してもよく、さらにまた３種類の溶液を同時
に滴下して混合してもよい。ケイ酸ナトリウムとマグネ
シウム塩の混合割合は前記一般式を満足するような化学
量論的割合であるのが好ましいがいずれか一方を過剰に
用いることもできる。また用いるアルカリ水溶液の量は
３種類の反応溶液を混合後の反応母液のｐＨが９.０か
ら１１.０、特に好ましくは９.５から１０.５の範囲に
あることが望ましい。生成したケイ酸・マグネシウム共
沈物は濾過・水洗により副生した溶解質不純物を除去す
る。In the first step of the present invention, when the sodium silicate and the magnesium salt are reacted in an alkaline aqueous solvent, specific methods include, for example, stirring the aqueous solution of the sodium silicate and the aqueous alkali solution in an aqueous solution of the magnesium salt. May be added to cause precipitation, or the mixture may be added dropwise in the reverse order, or three kinds of solutions may be added simultaneously and mixed. The mixing ratio of the sodium silicate and the magnesium salt is preferably a stoichiometric ratio that satisfies the above general formula, but any one of them can be used in excess. The amount of the aqueous alkali solution used is preferably such that the pH of the reaction mother liquor after mixing the three reaction solutions is in the range of 9.0 to 11.0, particularly preferably in the range of 9.5 to 10.5. The generated silicic acid / magnesium coprecipitate removes by-product solute impurities by filtration and washing with water.
【００１０】前記した条件下に反応させることにより生
成したケイ酸・マグネシウム共沈物は、濾過が容易であ
り水洗により副生した溶解質不純物が簡単に除去され
る。前記ケイ酸・マグネシウム共沈物は、その中に副生
溶解質不純物が実質的存在しないものであることが望ま
しく、そのため水洗は、水洗濾過中の塩素イオン、硫酸
イオンなどのイオンが実質的に認められなくなるまで行
うのが適当である。The coprecipitate of silicate and magnesium produced by the reaction under the above-mentioned conditions is easy to filter, and solute impurities by-produced by washing with water are easily removed. It is desirable that the silicic acid / magnesium coprecipitate contains substantially no by-product solute impurities therein. Therefore, washing with water is substantially free of ions such as chloride ions and sulfate ions during washing and filtration. It is appropriate to do this until it is no longer recognized.
【００１１】かくして濾過・水洗を行うことにより、精
製・濃縮されたケイ酸・マグネシウム共沈物を得、これ
に水、リチウムイオン、１価陽イオン要すればフッ素イ
オンを添加したスラリーをオートクレーブに仕込み１０
０℃ないし３００℃の温度条件下で水熱反応を行う。本
発明で用いる水熱反応条件として、反応温度は１００℃
ないし３００℃、特に好ましくは１７０℃ないし２５０
℃、圧力は０ないし１００ｋｇ／ｃｍ2（ゲージ圧）、
特に好ましくは６〜４０ｋｇ／ｃｍ2（ケージ圧）の圧
力下で行なうのがよく、反応時間は１ないし２４時間で
充分である。本発明で用いられる出発原料のうち、ケイ
酸ナトリウムとしてはメタケイ酸ソーダおよび１号ない
し４号水ガラスを使用することができ、アルカリ性水性
媒体としては、水酸化ナトリウム、水酸化カリウム、ア
ンモニア、炭酸ナトリウムまたは水酸化リチウム等の水
溶液を使用することができる。またマグネシウム塩とし
ては、塩化マグネシウム、硝酸マグネシウム、硫酸マグ
ネシウム等のマグネシウムの鉱酸塩を使用することがで
きる。また水熱反応に用いるスラリーに添加するリチウ
ムイオンとしては水酸化リチウムまたは水酸化リチウム
・１水和物が用いられる。リチウムイオンの添加割合は
前記一般式における０＜ｘ≦２であれば本発明は達成で
きるが、好ましくは０.４≦ｘ≦２の範囲にあるのがよ
い。反応に用いるナトリウムイオンとしては水酸化ナト
リウムが用いられる。 更にフッ素イオンは特に添加しな
くても目的とするケイ酸塩は得られるが、添加すること
によってケイ酸塩の特性を向上することができる。フッ
素イオンの添加割合は０≦ｙ≦４、好ましくは２≦ｙ≦
４の範囲である。フッ素イオンとしてはフッ化水素酸、
フッ化リチウム、フッ化ナトリウム、フッ化カリウム、
フッ化アンモニウム等が用いられる。By performing filtration and washing with water in this way, a purified and concentrated coprecipitate of silicic acid and magnesium is obtained, and a slurry obtained by adding water, lithium ions, monovalent cations and, if necessary, fluorine ions, to an autoclave. Preparation 10
The hydrothermal reaction is performed at a temperature of 0 ° C to 300 ° C. As the hydrothermal reaction conditions used in the present invention, the reaction temperature is 100 ° C.
To 300 ° C, particularly preferably 170 ° C to 250
° C, pressure is 0 to 100 kg / cm 2 (gauge pressure),
Particularly preferably, the reaction is carried out under a pressure of 6 to 40 kg / cm 2 (cage pressure), and a reaction time of 1 to 24 hours is sufficient. Among the starting materials used in the present invention, sodium metasilicate and water glass Nos. 1 to 4 can be used as sodium silicate, and sodium hydroxide, potassium hydroxide, ammonia, carbonate An aqueous solution such as sodium or lithium hydroxide can be used. As the magnesium salt, a mineral salt of magnesium such as magnesium chloride, magnesium nitrate, and magnesium sulfate can be used. Lithium ion to be added to the slurry used for the hydrothermal reaction is lithium hydroxide or lithium hydroxide.
-Monohydrate is used. The present invention can be achieved if the addition ratio of lithium ions is 0 <x ≦ 2 in the above general formula, but is preferably in the range of 0.4 ≦ x ≦ 2. Sodium hydroxide is used as the sodium ion used for the reaction . Further, although the desired silicate can be obtained without particularly adding fluorine ions, the characteristics of the silicate can be improved by adding it. The addition ratio of fluorine ions is 0 ≦ y ≦ 4, preferably 2 ≦ y ≦
4 range. Hydrofluoric acid as fluorine ion,
Lithium fluoride, sodium fluoride, potassium fluoride,
Ammonium fluoride or the like is used.
【００１２】水熱反応終了後、オートクレーブ内容物を
取り出し、乾燥・粉砕することにより最終製品である合
成膨潤性ケイ酸塩が得られる。本発明によって得られた
合成ケイ酸塩は３−八面体型スメクタイトであるヘクト
ライトに類似したＸ線回析パターンを持っている。また
大きな陽イオン交換容量を持っており、水中において優
れた膨潤性および分散性を示しほとんど着色しない水系
ゲルを生成する特徴があり、チクソトロピー的性質を有
している。そのため、増粘剤、チクソトロピー付与剤、
粘結剤、コロイド安定剤として水性塗料、インク、化粧
品、医薬品などに幅広く利用することができる。更に有
機物複合体とすることにより親油性粘土として用いるこ
ともできる。After completion of the hydrothermal reaction, the contents of the autoclave are taken out, dried and pulverized to obtain a synthetic swellable silicate as a final product. The synthetic silicate obtained according to the present invention has an X-ray diffraction pattern similar to hectorite, which is a 3-octahedral smectite. In addition, it has a large cation exchange capacity, is characterized by producing an aqueous gel that exhibits excellent swelling and dispersing properties in water and hardly discolors, and has thixotropic properties. Therefore, thickeners, thixotropic agents,
It can be widely used as a binder and a colloid stabilizer in aqueous paints, inks, cosmetics, pharmaceuticals and the like. Furthermore, it can be used as a lipophilic clay by forming an organic composite.
【００１３】[0013]
【実施例】以下実施例を掲げて本発明を詳述する。なお
実施例中、下記測定および試験はそれぞれ以下に説明す
る方法に従って行った。The present invention will be described in detail with reference to the following examples. In the examples, the following measurements and tests were performed according to the methods described below.
【００１４】（１）１％液透過率測定方法：試料１ｇを
純水９９ｇを入れた２００ｍｌ溶ビーカーに投入し、ホ
モミキサーで１０分間分散させた後、室温で２４時間放
置し、分光光度計を用いて波長５００ｎｍの光線透過率
を測定した。 （２）メチレンブルー吸着試験方法：ＪＢＡＳ−１０７
−７７に準じて測定した。 （３）流動学的性質測定方法：試料８ｇを純粋３９２ｇ
を入れた５００ｍｌ溶ビーカーに投入し、ホモミキサー
で１０分間分散させた後室温で２４時間放置し、ＪＢＡ
Ｓ−１０８−７７の２.４直読式回転粘土計による流動
性質の測定法に準じて測定した。粘度計はＦａｎｎ Ｖ
Ｇメーターを用いた。 （４）洗浄速度測定法：直径１１ｃｍの磁製ヌッチェに
Ｎｏ.５濾紙をセットし吸引ビンに取付け吸引圧５００
ｍｍＨｇで各反応沈澱物スラリーを濾過し、ケーキ形成
後純水１０００ｍｌを通水し、その速度を測定する。(1) Method for measuring 1% liquid transmittance: 1 g of a sample was put into a 200 ml melting beaker containing 99 g of pure water, dispersed for 10 minutes by a homomixer, and then left at room temperature for 24 hours to obtain a spectrophotometer. Was used to measure the light transmittance at a wavelength of 500 nm. (2) Methylene blue adsorption test method: JBAS-107
It measured according to -77. (3) Rheological property measuring method: 392 g of pure 8 g of sample
Into a 500 ml dissolving beaker, and disperse with a homomixer for 10 minutes, then stand at room temperature for 24 hours.
It was measured according to the method of measuring flow properties using a 2.4 direct-reading rotary clay meter of S-108-77. Viscometer is Fann V
A G meter was used. (4) Washing speed measuring method: No. 5 filter paper was set in a porcelain nutsche having a diameter of 11 cm, and was attached to a suction bottle, and suction pressure was 500
Each reaction precipitate slurry was filtered at mmHg, and after forming a cake, 1000 ml of pure water was passed through to measure the speed.
【００１５】実施例１ ２ｌのビーカーに水１,０００ｍｌを入れ、塩化マグネ
シウム六水和物一般試薬（純度９８％）５２ｇを溶解し
た。別の５００ｍｌのビーカーに３号水ガラス（ＳｉＯ
2 ２９％、Ｎａ2Ｏ ９.４％）７８.５ｇを入れ、水２０
０ｍｌを加えて希釈液とし、これに６ＮのＮａＯＨ液４
６ｍｌを加えて均一な溶液として、この液を上記塩化マ
グネシウム溶液に攪拌下、１０分間で注下した。Example 1 1,000 ml of water was placed in a 2 liter beaker, and 52 g of magnesium chloride hexahydrate general reagent (purity: 98%) was dissolved therein. In a separate 500 ml beaker, place the No. 3 water glass (SiO
2 29%, placed in a Na 2 O 9.4%) 78.5g, water 20
0 ml was added to make a diluent, to which 6N NaOH solution 4
6 ml was added to form a uniform solution, and this solution was poured into the magnesium chloride solution with stirring for 10 minutes.
【００１６】得られた反応沈澱物を直ちに濾過および１
ｌの純粋で洗浄し、内容積１ｌのステンレス製オートク
レーブに移し、水酸化リチウム−水和物［ＬｉＯＨ・Ｈ
2Ｏ］１.４ｇを溶解した水溶液５０ｍｌおよび水酸化ナ
トリウム １.３ｇを溶解した水溶液５０ｍｌを加えてス
ラリー状し、１７０℃、８ｋｇ／ｃｍ2ゲージ圧で１２
時間反応させた。反応終了後、冷却し反応物を取り出
し、８０℃で乾燥した後ラボミルにて粉砕した。オート
クレーブ処理前の反応沈澱物の洗浄速度を下記表１に示
した。本実施例で得た物質の粉末回析Ｘ線パターンはヘ
クトライトにほぼ一致した。一方、本物質のメチレンブ
ルー吸着量（ＪＢＡＳ−１０７−７７）および蒸留水を
用いて２％の懸濁液となした分散液の流動学的性質を回
転粘土計の一種であるＦａｎｎ ＶＧメーターで測定し
た結果を下記表２に示した。The reaction precipitate obtained is immediately filtered and
of pure water, transferred to a stainless steel autoclave having an internal volume of 1 l, and lithium hydroxide-hydrate [LiOH.H
[2 O] 50 ml of an aqueous solution in which 1.4 g of sodium hydroxide was dissolved and 50 ml of an aqueous solution in which 1.3 g of sodium hydroxide were dissolved, and slurried at 170 ° C. and 8 kg / cm 2 gauge pressure.
Allowed to react for hours. After completion of the reaction, the reaction mixture was cooled, the reaction product was taken out, dried at 80 ° C., and then pulverized by a lab mill. The washing speed of the reaction precipitate before the autoclave treatment is shown in Table 1 below. The powder diffraction X-ray pattern of the substance obtained in this example almost coincided with hectorite. On the other hand, the amount of methylene blue adsorbed on this substance (JBAS-107-77) and the rheological properties of a 2% suspension using distilled water were measured with a Fann VG meter, a kind of rotary clay meter. The results obtained are shown in Table 2 below.
【００１７】実施例２ 実施例１と同様にして得られた反応沈澱物の水洗物を１
ｌ内容積のオートクレーブに移し、水酸化リチウム・１
水和物［ＬｉＯＨ・Ｈ2Ｏ］１.４ｇを溶解した水溶液５
０ｍｌおよび４６％フッ化水素酸６.２ｇを水５０ｍｌ
に希釈した液を加えてスラリー状とし、１５０℃、５ｋ
ｇ／ｃｍ2ゲージ圧で１０時間反応させた。反応終了後
冷却し、反応物を取り出し、８０℃で乾燥した後、ラボ
ミルにて粉砕した。Example 2 A washed product of the reaction precipitate obtained in the same manner as in Example 1 was washed with 1
1 Transfer to an autoclave of internal volume and add lithium hydroxide
Aqueous solution 5 in which 1.4 g of hydrate [LiOH.H 2 O] is dissolved
0 ml and 6.2 g of 46% hydrofluoric acid in 50 ml of water
Into a slurry by adding the diluted solution to
The reaction was performed at g / cm 2 gauge pressure for 10 hours. After completion of the reaction, the reaction mixture was cooled, the reaction product was taken out, dried at 80 ° C., and pulverized by a lab mill.
【００１８】得られた物質の粉末回析Ｘ線パターンはヘ
クトライトにほぼ一致し、一方メチレンブルー吸着量
（ＪＢＡＳ−１０７−７７）および蒸留水を用いて２％
懸濁液となした分散液の流動学的性質を表２に示した。The powder diffraction X-ray pattern of the obtained substance almost coincides with that of hectorite, while the amount of adsorbed methylene blue (JBAS-107-77) and 2%
The rheological properties of the suspension dispersion are shown in Table 2.
【００１９】実施例３ １ｌのビーカーに水３００ｍｌと３号水ガラス（ＳｉＯ
2 ２９％、Ｎａ2Ｏ ９.４％）７８.５ｇおよび１２Ｎ
ＮＨ4ＯＨ １７９ｍｌを投入した。別に硫酸マグネシウ
ム７水塩（純度９８％）６８.５ｇを２００ｍｌに溶解
した。この液を上記水ガラス・アンモニア水混液中に５
分間で滴下した。得られた反応沈澱物を直ちに濾過、洗
浄し、内容積１ｌのステンレス製オートクレーブに移
し、水酸化リチウム１水和物（ＬｉＯＨ・Ｈ2Ｏ）１.４
ｇを溶解した水溶液５０ｍｌおよび水酸化ナトリウム
１.８ｇを溶解した水溶液５０ｍｌを加えてスラリー状
とし、２００℃、２４ｋｇ／ｃｍ2ゲージ圧で５時間反
応させた。反応終了後、冷却し反応物を取り出し、８０
℃で乾燥した後、ラボミルにて粉砕した。オートクレー
ブ処理前の反応沈澱物の洗浄速度を表１に示した。得ら
れた物質の粉末回析Ｘ線パターンはヘクトライトにほぼ
一致した。一方、メチレンブルー吸着量および２％分散
液の流動学的性質を表２に示した。EXAMPLE 3 300 ml of water and No. 3 water glass (SiO
2 29%, Na 2 O 9.4%) 78.5 g and 12N
179 ml of NH 4 OH were introduced. Separately, 68.5 g of magnesium sulfate heptahydrate (98% purity) was dissolved in 200 ml. Put this solution in the above water glass / ammonia water mixture.
In minutes. The resulting reaction precipitate was immediately filtered and washed, transferred to a stainless steel autoclave having an internal volume of 1 liter, and lithium hydroxide monohydrate (LiOH.H 2 O) 1.4.
g of an aqueous solution containing 50 g of sodium hydroxide and sodium hydroxide
A slurry was prepared by adding 50 ml of an aqueous solution in which 1.8 g was dissolved, and reacted at 200 ° C. and 24 kg / cm 2 gauge pressure for 5 hours. After completion of the reaction, the reaction product was cooled and taken out.
After drying at ℃, it was pulverized in a laboratory mill. The washing speed of the reaction precipitate before the autoclave treatment is shown in Table 1. The powder diffraction X-ray pattern of the obtained substance almost coincided with hectorite. Table 2 shows the methylene blue adsorption amount and the rheological properties of the 2% dispersion.
【００２０】実施例４ ３号水ガラス７８.５ｇを水３００ｍｌに加えて希釈液
とした（原料−１）。別に塩化マグネシウム６水和物、
１級試薬（純度９８％）５２ｇを水 ２００ｍｌに溶解
した（原料−２）。更に別に１Ｎ ＮａＯＨ２７６ｍｌ
を調製した（原料−３）。２ｌのビーカーに水５００ｍ
ｌを投入し攪拌下で上記３種類の原料を同時に１０分間
で注加した。得られた反応沈澱物を直ちに濾過・洗浄し
内容積１ｌのステンレス製オートクレーブに移し、水酸
化リチウム１水和物（ＬｉＯＨ・Ｈ2Ｏ）１.４ｇを溶解
した水溶液５０ｍｌおよび水酸化ナトリウム１.８ｇを
溶解した水溶液５０ｍｌを加えてスラリー状とし２５０
℃、４２ｋｇ／ｃｍ2ゲージ圧で２時間反応させた。反
応終了後冷却し、反応物を取り出し８０℃で乾燥した
後、ラボミルにて粉砕した。オートクレーブ処理前の反
応沈澱物の洗浄速度を表１に示した。得られた物質の粉
末回析Ｘ線パターンはヘクトライトにほぼ一致した。メ
チレンブルー吸着量および２％分散液の流動学的性質を
表２に示した。Example 4 78.5 g of No. 3 water glass was added to 300 ml of water to prepare a diluent (raw material-1). Separately magnesium chloride hexahydrate,
52 g of a primary reagent (98% purity) was dissolved in 200 ml of water (raw material-2). 276 ml of 1N NaOH
Was prepared (raw material-3). 500m water in 2l beaker
and the above three kinds of raw materials were simultaneously poured in 10 minutes under stirring. The resulting reaction precipitate was immediately filtered and washed, transferred to a stainless steel autoclave having an internal volume of 1 l, and 50 ml of an aqueous solution in which 1.4 g of lithium hydroxide monohydrate (LiOH.H 2 O) was dissolved, and 1.0 ml of sodium hydroxide. 50 g of an aqueous solution in which 8 g are dissolved to form a slurry,
The reaction was performed at 42 ° C. and a pressure of 42 kg / cm 2 gauge for 2 hours. After completion of the reaction, the reaction mixture was cooled, the reaction product was taken out, dried at 80 ° C., and pulverized by a lab mill. The washing speed of the reaction precipitate before the autoclave treatment is shown in Table 1. The powder diffraction X-ray pattern of the obtained substance almost coincided with hectorite. Table 2 shows the amount of methylene blue adsorbed and the rheological properties of the 2% dispersion.
【００２１】比較例１ １ｌのビーカーに水３００ｍｌを入れ、３号ガラス（Ｓ
ｉＯ2 ２９％、Ｎａ2Ｏ ９.４％）７８.５ｇを溶解し１
２規定の塩酸２０ｍｌを攪拌しながら一度に加えてケイ
酸溶液を得た。次に水１００ｍｌに塩化マグネシウム６
水和物、試薬１級（純度９８％）５２ｇを溶解した溶液
を加えてケイ酸−マグネシウム塩均質溶液を得た。この
ケイ酸−マグネシウム塩均質溶液を２規定の水酸化ナト
リウム溶液２６０ｍｌ中に攪拌しながら５分間で滴下し
た。得られた反応沈澱物を直ちに濾過洗浄し内容積１ｌ
のステンレス製オートクレーブに移し、水酸化リチウム
水和物（ＬｉＯＨ・Ｈ2Ｏ）１.４ｇを溶解した水溶液５
０ｍｌおよび水酸化ナトリウム１.３ｇを溶解した水溶
液５０ｍｌを加えてスラリー状とし、２００℃、１６ｋ
ｇ／ｃｍ2で３時間反応させた。冷却後、反応物を取り
出し、８０℃で乾燥した後ラボミルにて粉砕した。オー
トクレーブ処理前の反応沈澱物の洗浄速度を表１に示し
た。一方、本比較例で得られた物質の粉末回析Ｘ線パタ
ーンはヘクトライトにほぼ一致した。メチレンブルー吸
着量および蒸留水を用いて２％懸濁液とした分散液の流
動学的性質を表２に示した。Comparative Example 1 300 ml of water was placed in a 1 liter beaker, and glass No. 3 (S
dissolve 78.5 g of iO 2 29%, Na 2 O 9.4%)
20 ml of 2N hydrochloric acid was added all at once with stirring to obtain a silicic acid solution. Then magnesium chloride 6 in 100 ml of water
A solution in which 52 g of the hydrate and reagent first grade (purity 98%) were dissolved was added to obtain a homogeneous solution of silicic acid-magnesium salt. The homogeneous solution of the silicate-magnesium salt was added dropwise to 260 ml of a 2N sodium hydroxide solution over 5 minutes with stirring. The resulting reaction precipitate was immediately washed by filtration and the internal volume was 1 l.
Aqueous solution in which 1.4 g of lithium hydroxide hydrate (LiOH.H 2 O) was dissolved.
0 ml and 50 ml of an aqueous solution in which 1.3 g of sodium hydroxide are dissolved to form a slurry.
The reaction was performed at g / cm 2 for 3 hours. After cooling, the reaction product was taken out, dried at 80 ° C., and pulverized by a lab mill. The washing speed of the reaction precipitate before the autoclave treatment is shown in Table 1. On the other hand, the powder diffraction X-ray pattern of the substance obtained in this comparative example almost coincided with hectorite. Table 2 shows the amount of methylene blue adsorbed and the rheological properties of the dispersion prepared as a 2% suspension using distilled water.
【００２２】[0022]
【表１】 [Table 1]
【００２３】実施例５ 実施例１と同様にして得られた反応沈澱物の水洗物を１
ｌ内容積のオートクレーブに移し、水酸化リチウム１水
和物（ＬｉＯＨ・Ｈ2Ｏ）１.４ｇを溶解した水溶液５０
ｍｌおよび水酸化ナトリウム１.３ｇを溶解した水溶液
５０ｍｌを加えてスラリー状とし、２００℃、１６ｋｇ
／ｃｍ2ゲージ圧で１０時間反応させた。反応終了後冷
却し、反応物を３ｌのビーカーに移し、水を加えて全量
を１,５００ｍｌとした。別に１ｌのビーカーに８０℃
の熱水７００ｍｌを入れ、第四級アンモニウム塩（ジメ
チル・ジアルキルアンモニウムクロライド、アルキル基
の炭素数１６〜１８個）３２.５ｇを溶解した。この第
４級アンモニウム塩水溶液を上記反応物スラリーに加熱
攪拌しながら１０分間で滴下し、滴下終了後９０℃に加
熱して１時間保持した。生成物を濾過し熱水で充分水洗
し、８０℃で乾燥後、ラボミルにて粉砕した。Example 5 The washed product of the reaction precipitate obtained in the same manner as in Example 1 was washed with 1
The solution was transferred to an autoclave having an internal volume of 1 l, and an aqueous solution 50 dissolved with 1.4 g of lithium hydroxide monohydrate (LiOH.H 2 O).
and 50 g of an aqueous solution in which 1.3 g of sodium hydroxide are dissolved to form a slurry.
The reaction was carried out at a pressure of / cm 2 gauge for 10 hours. After completion of the reaction, the mixture was cooled, and the reaction product was transferred to a 3 liter beaker, and water was added to make the total volume 1,500 ml. Separately into a 1L beaker at 80 ° C
Of hot water (700 ml) was dissolved to dissolve 32.5 g of a quaternary ammonium salt (dimethyl dialkylammonium chloride, having 16 to 18 carbon atoms in the alkyl group). This quaternary ammonium salt aqueous solution was added dropwise to the reaction slurry with heating and stirring over 10 minutes, and after completion of the addition, the mixture was heated to 90 ° C. and maintained for 1 hour. The product was filtered, sufficiently washed with hot water, dried at 80 ° C., and pulverized by a lab mill.
【００２４】上記の操作で得られた物質は、炭素数１６
〜１８のアルキル基を有するジメチルジアルキルアンモ
ニウムとの有機複合体で親油性を示し、トルエン、キシ
レン、ベンゼン、四塩化炭素、クロロホルムなど各種有
機溶媒中で膨潤・分散した。その例としてトルエン系溶
媒へ４％分散させた時の流動学的性質（Ｆａｎｎ ＶＧ
メーターによる測定結果）を表３に示した。The substance obtained by the above operation has 16 carbon atoms.
An organic complex with dimethyldialkylammonium having an alkyl group of from 18 to 18 showed lipophilicity and swelled and dispersed in various organic solvents such as toluene, xylene, benzene, carbon tetrachloride and chloroform. As an example, rheological properties when dispersed in a toluene-based solvent at 4% (Fann VG
Table 3 shows the results of measurement with a meter.
【００２５】[0025]
【表２】 [Table 2]
【００２６】表２に明らかなように実施例１、２、３お
よび４で得られた本発明による製品の水系分散液は、比
較例１で得られた物および市販の純モンモリロナイトで
あるクニピアＦの水系分散液に比較して極めて高い粘
性、降伏値およびゲル強度を有し、水系溶媒に対するゲ
ル化剤として優れた性能を有するのがわかる。As is evident from Table 2, the aqueous dispersions of the products according to the invention obtained in Examples 1, 2, 3 and 4 are those obtained in Comparative Example 1 and the commercially available pure montmorillonite Kunipia F It has an extremely high viscosity, yield value and gel strength as compared with the aqueous dispersion of No. 5, and has excellent performance as a gelling agent for aqueous solvents.
【００２７】[0027]
【表３】 [Table 3]
【００２８】本発明の有機複合体は表３に明らかなよう
に有機溶媒中で膨潤、分散するので各種有機溶媒におけ
るゲル化剤、懸濁安定剤、チクソトロピィー付与剤など
として有用であることがわかる。As is clear from Table 3, the organic complex of the present invention swells and disperses in an organic solvent, and thus is useful as a gelling agent, a suspension stabilizer, a thixotropic agent and the like in various organic solvents. .
【００２９】[0029]
【発明の効果】ケイ酸塩、アルカリおよびマグネシウム
塩を主原料として膨潤性ケイ酸塩を製造する場合、中間
生成物であるケイ酸・マグネシウム共沈物からの溶解質
の水洗除去が最終製品である該ケイ酸塩の品質に大きく
影響を与えるが、本発明の製造方法によれば、この共沈
物の水洗除去が短時間で容易に達成できるため、ゲル形
成能に優れ、分散水溶液の透明性にも優れた高性能のケ
イ酸塩を能率良く生産できる。また、濾過速度が速いた
め特殊な濾過・水洗装置を使用する必要はなく、従来の
装置で通常の条件下で実施できる。またケイ酸塩溶液は
そのままで反応に用いるため鉱酸類は不必要で且つその
分必要なアルカリ量も少なくてよいので経済的である。According to the present invention, when a swellable silicate is produced using silicate, alkali and magnesium salts as main raw materials, the final product is to wash and remove solutes from an intermediate product, a silicate-magnesium coprecipitate, with water. Although this greatly affects the quality of a certain silicate, according to the production method of the present invention, the coprecipitate can be easily washed off with water in a short time, so that it has excellent gel-forming ability and clearness of the dispersed aqueous solution. A high-performance silicate with excellent properties can be produced efficiently. In addition, since the filtration speed is high, it is not necessary to use a special filtration / washing device, and it can be carried out with a conventional device under ordinary conditions. In addition, since the silicate solution is used as it is in the reaction, mineral acids are unnecessary, and the amount of alkali required is less, which is economical.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭48−96499（ＪＰ，Ａ) 特開 昭61−86414（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01B 33/22 - 33/24 ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-48-96499 (JP, A) JP-A-61-86414 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C01B 33/22-33/24
Claims (1)
リ性水性媒体中で反応させてケイ酸・マグネシウム共沈
物を沈澱させる工程、 （２）該沈澱物を濾過および水洗して副生溶解質を除去
する工程、 （３）かくして得られた沈澱物に水酸化リチウムおよび
／または水酸化ナトリウムを添加し、さらに必要により
フッ素イオンを添加し１００℃〜３００℃の温度で水熱
反応せしめる工程および （４）得られた反応生成物を乾燥する工程、 よりなることを特徴とする下記一般式 【数１】 ［式中、ｘおよびｙは、０≦ｘ≦２、０≦ｙ≦４、Ｍ+
は１価の陽イオンを示す］ で表わされるヘクトライト型粘土鉱物に類似した構造を
有する膨潤性ケイ酸塩の製造方法。1. The following steps: (1) a step of reacting a sodium silicate and a magnesium salt in an alkaline aqueous medium to precipitate a silicate-magnesium coprecipitate; and (2) filtering and washing the precipitate. (3) Lithium hydroxide and / or sodium hydroxide are added to the precipitate thus obtained, and if necessary, fluorine ions are added, and hydrothermal treatment is performed at a temperature of 100 ° C to 300 ° C. A step of reacting; and (4) a step of drying the obtained reaction product. Wherein x and y are 0 ≦ x ≦ 2, 0 ≦ y ≦ 4, M +
Represents a monovalent cation.] A method for producing a swellable silicate having a structure similar to a hectorite-type clay mineral represented by the formula:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18615094A JP3314184B2 (en) | 1994-08-08 | 1994-08-08 | Method for producing swellable silicate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18615094A JP3314184B2 (en) | 1994-08-08 | 1994-08-08 | Method for producing swellable silicate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0848516A JPH0848516A (en) | 1996-02-20 |
| JP3314184B2 true JP3314184B2 (en) | 2002-08-12 |
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ID=16183263
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| JP18615094A Expired - Fee Related JP3314184B2 (en) | 1994-08-08 | 1994-08-08 | Method for producing swellable silicate |
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| JP4925040B2 (en) * | 2006-09-06 | 2012-04-25 | 独立行政法人物質・材料研究機構 | Method for producing metal ion-containing synthetic layered silicate |
| KR100748211B1 (en) * | 2006-10-25 | 2007-08-09 | 한국지질자원연구원 | Manufacturing method of hectorite from water glass |
| JP5405998B2 (en) * | 2009-12-08 | 2014-02-05 | クニミネ工業株式会社 | Protein crystal formation control agent |
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