JP2694163B2 - Method for producing high-purity silica - Google Patents

Method for producing high-purity silica

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Publication number
JP2694163B2
JP2694163B2 JP22504288A JP22504288A JP2694163B2 JP 2694163 B2 JP2694163 B2 JP 2694163B2 JP 22504288 A JP22504288 A JP 22504288A JP 22504288 A JP22504288 A JP 22504288A JP 2694163 B2 JP2694163 B2 JP 2694163B2
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Japan
Prior art keywords
silica
acid
purity
chelating agent
solution
Prior art date
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JP22504288A
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Japanese (ja)
Other versions
JPH0274515A (en
Inventor
孝司 坂口
和彦 矢口
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Fuji Silysia Chemical Ltd
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Fuji Silysia Chemical Ltd
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Description

【発明の詳細な説明】 [産業上の利用分野] 本発明は高純度シリカの製造法に関するものである。
詳しくは、クロマトグラフィー用充填剤、電子材料原
料、触媒担体、食品添加物、化粧品添加剤(ファンデー
ション)、光ファイバー用高純度ガラス及び光学ガラス
の原料、更には医療用材料等の用途に好適である各種不
純金属成分の少ない高純度シリカの製造法に関するもの
である。
TECHNICAL FIELD The present invention relates to a method for producing high-purity silica.
Specifically, it is suitable for use as a packing material for chromatography, electronic material raw material, catalyst carrier, food additive, cosmetic additive (foundation), raw material of high-purity glass for optical fiber and optical glass, and further medical material. The present invention relates to a method for producing high-purity silica containing various impure metal components.

[従来の技術] 近年、高純度化されたシリカは多くの用途において需
要が増加しているが、その純度は更に高いものが望まれ
ている。例えば、クロマトグラフィー用充填剤として利
用する場合、鉄などの微量金属不純物が混在するとシリ
カ表面の荷電が増加し、それに起因して極性物質のピー
クテーリングが生じたり、塩基性物質が吸着しやすくな
り、目的物質の回収率や純度が悪くなる。
[Prior Art] Demand for highly purified silica has increased in many applications in recent years, but higher purity is desired. For example, when used as a packing material for chromatography, when trace metal impurities such as iron are mixed, the charge on the silica surface increases, which causes peak tailing of polar substances and facilitates adsorption of basic substances. However, the recovery rate and purity of the target substance deteriorate.

また、シリカを半導体封止剤フィラーの原料として用
いる場合、Naなどのアルカリ金属の混入は配線の腐蝕を
起こし、また、U及びThなどの放射性元素の混入は、ソ
フトエラーの原因となる。従ってIC、LSIの分野におい
て、シリカフィラーの高純度化が要求される。
Further, when silica is used as a raw material for the semiconductor encapsulant filler, the incorporation of an alkali metal such as Na causes corrosion of the wiring, and the incorporation of radioactive elements such as U and Th causes a soft error. Therefore, high purification of silica filler is required in the field of IC and LSI.

他方、触媒担体として、シリカを利用する場合、各種
不純成分の混入による純度の低下は対象触媒反応の副反
応が起こりやすくなり、目的生成物の収率、純度に悪影
響を及ぼす。
On the other hand, when silica is used as the catalyst carrier, a decrease in purity due to the incorporation of various impure components easily causes a side reaction of the target catalytic reaction, which adversely affects the yield and purity of the target product.

このような各分野の需要に応ずるためには、各種の微
量金属不純物が少ない高純度のシリカが要求される。
In order to meet such demands in each field, high-purity silica containing various trace metal impurities is required.

従来、シリカの製造法としては一般的に、乾式法、湿
式法とに大別され、前者はハロゲン化ケイ素又はアルコ
キシシランなどの気相分解法であり、後者は、珪酸アル
カリ又はアルコキシシラン等の酸による加水分解であ
る。
Conventionally, silica production methods are generally roughly classified into a dry method and a wet method. The former is a vapor phase decomposition method such as a silicon halide or an alkoxysilane, and the latter is an alkali silicate or an alkoxysilane. Hydrolysis by acid.

乾式法による高純度シリカの製造法としては、例え
ば、下記のものが知られている。
As a method for producing high-purity silica by the dry method, for example, the following are known.

四塩化ケイ素に代表されるハロゲン化ケイ素を火災
と共に耐火性の標的上に吹きつけて、付着溶融成長さ
せ、粉砕することによる高純度シリカの製法。(特開昭
58−140,313号) ハロゲン化ケイ素の火炎中、気相加水分解によって
生成する高純度超微粒子状シリカを更に火炎中で溶融す
ることにより高純度シリカを製造する方法。(特開昭59
−152,215号) ところが、これら乾式法の場合、次のような問題点が
挙げられる。
A method for producing high-purity silica by spraying a silicon halide, typified by silicon tetrachloride, with a fire onto a refractory target, depositing, melting and growing, and crushing. (JP
No. 58-140,313) A method for producing high-purity silica by further melting high-purity ultrafine silica particles produced by gas phase hydrolysis in a flame of a silicon halide in a flame. (Japanese Patent Laid-Open No. 59
However, these dry methods have the following problems.

ハロゲン化ケイ素等のシリカ原料が高価である。 Silica raw materials such as silicon halides are expensive.

ハロゲン化ケイ素としてクロロシラン系の原料を使
用した場合、製品にクロルが残留しやすく低クロル化が
困難である。
When a chlorosilane-based raw material is used as the silicon halide, chloro tends to remain in the product, and it is difficult to reduce chloro.

クロロシラン系の場合、腐蝕性及び可燃性である為、
取扱難い。
In the case of chlorosilane type, it is corrosive and flammable,
It is difficult to handle.

一方、湿式法による高純度シリカの製造法としては、
例えば、次のような沈澱法による製造法が知られてい
る。
On the other hand, as a method for producing high-purity silica by the wet method,
For example, the following precipitation method is known.

ケイ酸ソーダ水溶液をカチオン交換樹脂で処理して
得られた酸性シリカゾルを、アンモニアによりアルカリ
性シリカゾルとし、この溶液を硝酸アンモニウムと接触
させて凝集沈澱シリカゲルを製造し、酸処理、水洗、乾
燥、溶融を至て高純度シリカゲルを得る方法。(特開昭
60−180,911号)。
An acidic silica sol obtained by treating an aqueous solution of sodium silicate with a cation exchange resin is converted to an alkaline silica sol with ammonia, and this solution is brought into contact with ammonium nitrate to produce coagulated precipitated silica gel, which is acid treated, washed with water, dried and melted. To obtain high-purity silica gel. (JP
60-180,911).

硝酸水溶液にケイ酸ソーダ水溶液を徐々に、添加
し、沈澱シリカゲルを製造し、酸処理,水洗,乾燥,焼
成を至て高純度シリカを得る方法。(特開昭61−48,422
号) エチレンジアミン四酢酸又はシュウ酸などのキレー
ト剤と、過酸化水素の存在下でケイ酸ナトリウムと鉱酸
を反応させ沈澱シリカを製造し、酸処理,水洗,乾燥,
焼成を至て高純度シリカを得る方法。(特開昭61−178,
414号及び同62−12,608号) 鉱酸中にフッ素イオンを含有させるか、又はシリカ
ゾルにフッ素含有化合物を添加して沈澱シリカを製造
し、水洗、酸処理、水洗、乾燥、焼成を至て高純度シリ
カを得る方法。(特開昭63−21,213号及び同63−21,214
号) しかしながら、これらの方法では、いずれもケイ酸ア
ルカリを原料として用いるが、一般的に、ケイ酸アルカ
リ中には種々の金属不純物を含むため、最終的に得られ
るシリカ中にもこれら不純物が若干、含有され真に高純
度品を製造することは難しかった。例えば、上記の方
法では、Tiの除去には効果があるものの、鉱酸の濃度が
高いと過酸化水素が分解しやすく、その他の金属の除去
効果は低い。また、上記の方法では、Al、Feの除去効
果は高いものの、本発明者等の追試結果によると生成シ
リカ中にフッ素が残留し、その量は高いものでは200ppm
にも達し高純度シリカとは言い難い。更に、上記〜
の方法の場合、シリカの生成形体が沈澱性シリカであ
り、微細なものしか得られないため、製造し得る粒子径
範囲が狭く、また、脱水時の固液分離が良くないもので
あった。その上、これらの製品は比表面積が著しく小さ
いため、例えば、吸着剤用としての利用は非常に難しか
った。
A method in which a sodium silicate aqueous solution is gradually added to a nitric acid aqueous solution to produce precipitated silica gel, and acid treatment, water washing, drying and firing are performed to obtain high purity silica. (JP-A-61-48,422
No.) A chelating agent such as ethylenediaminetetraacetic acid or oxalic acid is reacted with sodium silicate and a mineral acid in the presence of hydrogen peroxide to produce precipitated silica, which is treated with acid, washed with water, dried,
A method of obtaining high-purity silica by firing. (JP-A-61-178,
No. 414 and No. 62-12,608) Fluorine ion is contained in mineral acid or fluorine-containing compound is added to silica sol to produce precipitated silica, which is washed with water, treated with acid, washed with water, dried and fired to achieve high Method for obtaining pure silica. (JP-A-63-21,213 and 63-21,214
However, in all of these methods, alkali silicate is used as a raw material, but in general, since alkali silicate contains various metal impurities, these impurities are also contained in finally obtained silica. To some extent, it was difficult to produce a truly high purity product containing it. For example, although the above method is effective in removing Ti, when the concentration of mineral acid is high, hydrogen peroxide is easily decomposed and the effect of removing other metals is low. Further, in the above method, Al, although the effect of removing Fe is high, according to the additional test results of the present inventors, fluorine remains in the produced silica, the amount is 200ppm in high.
It is hard to call it high purity silica. In addition,
In the case of the method (1), since the produced form of silica is a precipitating silica and only fine particles can be obtained, the range of particle sizes that can be produced is narrow, and solid-liquid separation during dehydration is not good. Moreover, since these products have a remarkably small specific surface area, it was very difficult to use them as an adsorbent, for example.

[発明の課題と解決手段] 本発明者等は上記実情に鑑み、ケイ酸化合物の溶液を
原料として高純度シリカを製造する場合、各種の金属不
純物を効率的に除去し、真に高純度のシリカを得るため
の方法につき鋭意検討を重ねた結果、前記溶液を特定の
キレート剤と接触させることにより各種の微量金属不純
物が極めて良好に除去され、結果的に高純度のシリカが
得られることを見い出し本発明を完成した。即ち、本発
明の要旨は、ケイ酸化合物の溶液、シリカゾル又はシリ
カヒドロゲルをフェノール性水酸基及びスルホン酸基を
配位子とするキレート剤と接触させ、次いで、これを原
料としてシリカを得ることを特徴とする高純度シリカの
製造法に関する。
[Problems and Solutions of the Invention] In view of the above situation, the present inventors efficiently remove various metal impurities when producing high-purity silica using a solution of a silicic acid compound as a raw material, and obtain a truly high-purity silica. As a result of extensive studies on a method for obtaining silica, it was found that various trace metal impurities were removed very well by bringing the solution into contact with a specific chelating agent, resulting in high-purity silica. Found and completed the present invention. That is, the gist of the present invention is that a solution of a silicic acid compound, a silica sol or a silica hydrogel is brought into contact with a chelating agent having a phenolic hydroxyl group and a sulfonic acid group as a ligand, and then silica is obtained using this as a raw material. And a method for producing high-purity silica.

以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.

本発明で原料となるケイ酸化合物としては、例えば、
ケイ酸アルカリ,シリカゾル,シリカヒドロゲルなどが
挙げられる。ケイ酸アルカリの場合を例にとり説明す
る。本発明で対象となるケイ酸アルカリとしては、ケイ
酸ナトリウム,ケイ酸カリウム,ケイ酸アンモニウムな
どであり、例えば、ケイ酸ナトリウムの場合、市販のケ
イ酸ナトリウム、JIS特1、1、2、3、4号及びオル
トケイ酸ナトリウム,メタケイ酸ナトリウムなどが挙げ
られる。これらのケイ酸アルカリ中には一般的にAlが数
100〜数1000ppm、 Feが数10〜数1000ppm、 Tiが数10〜数100ppm、そしてU及びThなどのα放射体よ
りなる不純物が 約数10〜数100ppb程度含まれている。
Examples of the silicic acid compound used as a raw material in the present invention include:
Examples thereof include alkali silicate, silica sol, silica hydrogel and the like. The case of alkali silicate will be described as an example. Examples of the alkali silicate to be used in the present invention include sodium silicate, potassium silicate, and ammonium silicate. For example, in the case of sodium silicate, commercially available sodium silicate, JIS features 1, 2, 3 No. 4, sodium orthosilicate, sodium metasilicate and the like. In these alkali silicates, Al is generally a few
100-several 1000 ppm, Fe several tens-several 1000 ppm, Ti several tens-several 100 ppm, and impurities such as U and Th, which are α emitters, are contained in the order of several tens-several 100 ppb.

また、ケイ酸アルカリ水溶液の濃度は、通常、SiO2
度として1〜20重量%、好ましくは2〜10重量%であ
る。この濃度があまり低い場合には、処理すべきケイ酸
アルカリ水溶液の容量が増え、精製操作が大変であり、
逆に、あまり高い場合には、ケイ酸アルカリ水溶液に酸
を加えてpH調整する際に溶液がゲル化するので好ましく
ない。この溶液のゲル化は酸の種類や使用量によって異
なるので、実際のケイ酸アルカリ水溶液の濃度はその処
理方法に応じて前記範囲より選択される。
The concentration of the alkaline silicate aqueous solution is usually 1 to 20% by weight, preferably 2 to 10% by weight, as the SiO 2 concentration. If this concentration is too low, the volume of the alkali silicate aqueous solution to be treated increases, and the refining operation is difficult.
On the other hand, if it is too high, the solution gels when the pH is adjusted by adding an acid to the alkali silicate aqueous solution, which is not preferable. The gelation of this solution depends on the type and amount of the acid used, so the actual concentration of the aqueous alkali silicate solution is selected from the above range depending on the treatment method.

本発明においては、上述の如きケイ酸化合物の溶液を
フェノール性水酸基及びスルホン酸基を配位子とするキ
レート剤と接触させることを必須の要件とするものであ
る。即ち、この本発明の処理により従来の精製法では十
分に除去できなかった各種の金属不純物を効果的に除去
できるのである。例えば、Tiの場合、酸洗浄の繰り返し
操作により10ppm程度までは除去可能であったが、それ
以上の精製は困難であった。本発明の場合には、再現性
よく極めて低レベルまで減少させることが可能である。
In the present invention, it is an essential requirement to bring the solution of the silicic acid compound as described above into contact with a chelating agent having a phenolic hydroxyl group and a sulfonic acid group as a ligand. That is, by the treatment of the present invention, various metal impurities that could not be sufficiently removed by the conventional purification method can be effectively removed. For example, in the case of Ti, it was possible to remove up to about 10 ppm by repeating the acid washing, but further purification was difficult. In the case of the present invention, it can be reproducibly reduced to an extremely low level.

また本発明ではケイ酸化合物の代りにシリカゾル又は
シリカヒドロゲルを用いることもできる。シリカゾル及
びシリカヒドロゲルは通常の方法で得られたものが使用
できる。
Further, in the present invention, silica sol or silica hydrogel can be used instead of the silicic acid compound. As the silica sol and silica hydrogel, those obtained by a usual method can be used.

本発明で特定するキレート剤の具体例としては、通
常、クロモトロープ酸、タイロン、5−スルホサリチル
酸、オキシン−5−スルホン酸など及びそれらの可溶性
塩(ナトリウム塩など)が挙げられる。これら化合物は
2種以上併用してもよい。このキレート剤の添加量は原
料のケイ酸化合物、シリカゾル又はシリカヒドロゲル中
の金属不純物の含有量及び目標とするシリカの純度など
により適宜、選定されるが、通常、ケイ酸アルカリを用
いる場合、ケイ酸アルカリに対して0.1〜20重量%の範
囲から選ばれる。
Specific examples of the chelating agent specified in the present invention generally include chromotropic acid, tyrone, 5-sulfosalicylic acid, oxine-5-sulfonic acid and the like and soluble salts thereof (sodium salt and the like). You may use together 2 or more types of these compounds. The amount of the chelating agent added is appropriately selected depending on the raw material silicic acid compound, the content of metal impurities in the silica sol or silica hydrogel and the target purity of silica, etc. It is selected from the range of 0.1 to 20% by weight with respect to the acid and alkali.

更に、本発明では上記キレート剤とともに、エチレン
ジアミン四酢酸、チオリンゴ酸、シュウ酸、クエン酸、
サリチル酸及びこれらの可溶性塩(ナトリウム塩、カル
シウム塩など)などのキレート剤を併用して用いても効
果がある。このキレート剤の使用量も一概には言えない
が、通常、クロモトロープ酸、タイロン、5−スルホサ
リチル酸、オキシン−5−スルホン酸及びそれらの可溶
性塩(ナトリウム塩など)などのキレート剤に対して0.
2〜2重量倍好ましくは0.3〜1重量倍程度である。
Furthermore, in the present invention, together with the chelating agent, ethylenediaminetetraacetic acid, thiomalic acid, oxalic acid, citric acid,
It is also effective to use a chelating agent such as salicylic acid and a soluble salt thereof (sodium salt, calcium salt, etc.) in combination. The amount of this chelating agent used cannot be generally stated, but it is usually relative to chelating agents such as chromotropic acid, tyrone, 5-sulfosalicylic acid, oxine-5-sulfonic acid and their soluble salts (such as sodium salts). 0.
It is about 2 to 2 times by weight, preferably about 0.3 to 1 times by weight.

ケイ酸化合物の溶液と上記キレート剤の接触処理は、
通常、該溶液中に所定量のキレート剤を添加し撹拌保持
するが、キレート剤は水に溶解し徐々に(例えば、30分
以上かけて)添加した方が精製効果が大きいので好まし
い。
The contact treatment between the solution of the silicic acid compound and the chelating agent is
Usually, a predetermined amount of the chelating agent is added to the solution and kept under stirring, but it is preferable that the chelating agent is dissolved in water and gradually added (for example, over 30 minutes) because the purification effect is large.

本発明では上述の接触処理を終えた原料からシリカを
製造するが、この方法は特に限定されるものではなく、
公知の方法に従って種々の方法を採用することができ
る。要するに、本発明の最大のポイントは、原料をキレ
ート剤と接触処理させるところにあるもので、その後の
工程には特段の特徴はない。したがって、ケイ酸アルカ
リ水溶液の場合には、常法通り、鉱酸と混合しヒドロゲ
ルを生成させ、次いで、これを洗浄、乾燥することによ
り高純度シリカを得ることができる。この際のケイ酸ア
ルカリ水溶液と鉱酸との混合方法は、通常、ケイ酸アル
カリ水溶液を鉱酸中に添加し酸性領域で反応させるか、
又は、両者を混合物が酸性領域となるように同時に混合
する方法が望ましい。このときのpHは通常2〜6、好ま
しくは3〜5である。
In the present invention, silica is produced from the raw material that has been subjected to the above contact treatment, but this method is not particularly limited,
Various methods can be adopted according to known methods. In short, the most important point of the present invention is to bring the raw material into contact with the chelating agent, and there is no particular feature in the subsequent steps. Therefore, in the case of an aqueous alkali silicate solution, a high purity silica can be obtained by mixing with a mineral acid to form a hydrogel and then washing and drying the same in a conventional manner. At this time, the method of mixing the alkaline silicate aqueous solution and the mineral acid is usually added with the alkaline silicate aqueous solution in the mineral acid and reacted in an acidic region,
Alternatively, a method in which both are simultaneously mixed so that the mixture is in the acidic region is desirable. The pH at this time is usually 2 to 6, preferably 3 to 5.

ゲル化後、場合によって、鉱酸溶液で浸漬処理し洗浄
するのが好ましく、この処理によりキレート除去できな
かった金属不純物が更に溶出除去される。次いで、イオ
ン交換水で水洗浄するが、この際にキレート剤を含むイ
オン交換水を用いると特に洗浄効果が大きく望ましい。
なお、これらの洗浄操作は必要に応じて2回以上繰り返
し行なうことができる。
After gelation, in some cases, it is preferable to carry out a dipping treatment with a mineral acid solution for washing, and this treatment further elutes and removes metal impurities that could not be removed by chelation. Next, it is washed with ion-exchanged water. At this time, if ion-exchanged water containing a chelating agent is used, the washing effect is particularly large and desirable.
Note that these washing operations can be repeated twice or more as necessary.

また別途にシリカゾル及びシリカヒドロゲルにキレー
ト剤を接触処理させることによっても高純度シリカが得
られる。
High-purity silica can also be obtained by separately treating the silica sol and silica hydrogel with a chelating agent.

このようにして得られたシリカは乾燥して高純度シリ
カとして回収される。
The silica thus obtained is dried and recovered as high-purity silica.

[発明の効果] 本発明によれば、ケイ酸化合物の溶液、シリカゲル又
はシリカヒドロゲルを特定のキレート剤と接触させるこ
とにより、結果的に、各種の金属不純物含有量の極めて
低い高純度シリカを得ることができる。そのため、本発
明で得られるシリカはクロマトグラフィー用充填剤、電
子材料原料、触媒担体、食品添加物、化粧品添加剤、光
ファイバー用高純度ガラス及び光学ガラスの原料、医療
用材料として幅広く利用することができる。また本発明
では多孔性のシリカゲルも製造可能であるので、更に、
各種用途に利用できる。
EFFECTS OF THE INVENTION According to the present invention, a solution of a silicic acid compound, silica gel or silica hydrogel is brought into contact with a specific chelating agent, and as a result, highly pure silica having extremely low content of various metal impurities is obtained. be able to. Therefore, the silica obtained in the present invention can be widely used as a packing material for chromatography, an electronic material raw material, a catalyst carrier, a food additive, a cosmetic additive, a high-purity glass for optical fiber and a raw material of an optical glass, and a medical material. it can. Further, since porous silica gel can be produced in the present invention, further,
It can be used for various purposes.

[実施例] 次に、本発明を更に具体的に説明するが、本発明はそ
の要旨を超えない限り以下の実施例の記述に限定される
ものではない。
[Examples] Next, the present invention will be described more specifically, but the present invention is not limited to the description of the following examples unless it exceeds the gist.

実施例1 市販の珪酸ナトリウム水溶液(SiO2濃度27.0重量%、
Na2O濃度8.2%)30mlとり、撹拌した。
Example 1 Commercially available sodium silicate aqueous solution (SiO 2 concentration 27.0% by weight,
Na 2 O concentration 8.2%) 30 ml was taken and stirred.

これとは別にETA(エチレンジアミン四酢酸ニナトリ
ウム、関東化学特級)0.5588gとクロモトロープ酸二ナ
トリウム(メルク特級)0.6005gをイオン交換水90.5ml
に分散させて珪酸ナトリウム水溶液中に30分かけて徐々
に添加した。撹拌は約5時間行ない赤かっ色の色に変化
した。
Separately, 0.5588 g of ETA (disodium ethylenediaminetetraacetate, Kanto Chemical Special Grade) and 0.6005 g of disodium chromotropic acid (Merck Special Grade) are ion-exchanged water 90.5 ml.
And was gradually added to the sodium silicate aqueous solution over 30 minutes. The stirring was continued for about 5 hours and the color changed to reddish brown.

この溶液を(1+9)硫酸水溶液29.5ml中に加え、NH
4OH水溶液でpHを3.0に調整した後pH4.0まで上げた。よ
く撹拌後この水溶液を80℃で1時間保持しゲル化させ
た。
This solution was added to 29.5 ml of (1 + 9) sulfuric acid aqueous solution, and NH
The pH was adjusted to 3.0 with a 4 OH aqueous solution and then raised to pH 4.0. After stirring well, this aqueous solution was kept at 80 ° C. for 1 hour for gelation.

このシリカヒドロゲルを細かく粉砕した後、イオン交
換水約5で、洗浄した後 5N HCl200ml中に入れ約2
時間80℃に保ち常温で8時間撹拌した。1mMのシュウ酸
が含まれるイオン交換水約25で洗浄した後イオン交換
水約25で洗浄し、オーブン乾燥機にて乾燥した。
This silica hydrogel was finely crushed, washed with about 5 parts of ion-exchanged water, and then put into 200 ml of 5N HCl for about 2 parts.
The temperature was kept at 80 ° C. and the mixture was stirred at room temperature for 8 hours. After washing with about 25 ion-exchanged water containing 1 mM oxalic acid, it was washed with about 25 ion-exchanged water and dried in an oven dryer.

シリカ中の不純物含有量を後記表−1に示す。 The content of impurities in silica is shown in Table 1 below.

表−1より明らかなように、シリカ中の各不純物元素
は総て25ppm以下でありU.Thもそれぞれ0.1ppb以下の低
放射性高純度シリカが得られた。
As is clear from Table 1, each impurity element in silica was 25 ppm or less in total, and U.Th was 0.1 ppb or less, and low-radioactive high-purity silica was obtained.

また、この試料をB.E.T.測定による細孔分布を調べた
ところ、第1図のように多孔性シリカゲルであった。な
お図中SAはシリカ1g当りの比表面積(m2/g)、PVはシリ
カ1g当りの細孔容積(ml/g)である。
When the pore distribution of this sample was examined by BET measurement, it was porous silica gel as shown in FIG. In the figure, SA is the specific surface area per 1 g of silica (m 2 / g), and PV is the pore volume per 1 g of silica (ml / g).

実施例2 市販の珪酸ナトリウム水溶液(SiO2濃度27.0重量%、
Na2O濃度8.2重量%)30mlとり、撹拌した。
Example 2 Commercially available sodium silicate aqueous solution (SiO 2 concentration 27.0% by weight,
Na 2 O concentration 8.2 wt%) 30 ml was taken and stirred.

これとは別にエチレンジアミン四酢酸カルシウム二ナ
トリウム(和光純薬製)0.6149gとクロモトロープ酸二
ナトリウム(メルク特級)0.6012gをイオン交換水90.5m
lに分散させて、珪酸ナトリウム水溶液中に30分かけて
徐々に添加した。撹拌は5時間行ない赤かっ色の色に変
化した。
Separately, 0.6149 g of calcium disodium ethylenediaminetetraacetate (manufactured by Wako Pure Chemical Industries, Ltd.) and 0.6012 g of disodium chromotropic acid (Merck special grade) are added to ion-exchanged water 90.5 m.
It was dispersed in 1 l and gradually added to an aqueous sodium silicate solution over 30 minutes. After stirring for 5 hours, the color changed to reddish brown.

この溶液を(1+9)硫酸水溶液29.5ml中に加えNH4O
H水溶液でpHを3.0に調整した後pH4.0まで上げた。よく
撹拌後この水溶液を80℃で1時間保持しゲル化させた。
This solution was added to 29.5 ml of (1 + 9) sulfuric acid aqueous solution and NH 4 O was added.
The pH was adjusted to 3.0 with an aqueous H solution and then raised to pH 4.0. After stirring well, this aqueous solution was kept at 80 ° C. for 1 hour for gelation.

このシリカヒドロゲルを細かく粉砕した後、イオン交
換水約5で洗浄した後5N HCl200ml中に入れ常温で一
夜浸漬した。その後、イオン交換水約40で洗浄し、オ
ーブン乾燥機で乾燥した。
The silica hydrogel was finely pulverized, washed with about 5 of ion-exchanged water, and then placed in 200 ml of 5N HCl and immersed at room temperature overnight. Then, it was washed with about 40 ion-exchanged water and dried in an oven dryer.

シリカ中の不純物含有量を後記表−1に示す。 The content of impurities in silica is shown in Table 1 below.

実施例3 市販の珪酸ナトリウム水溶液(SiO2濃度27.0重量%、
Na2O濃度8.2重量%)30mlとり、撹拌した。
Example 3 Commercially available sodium silicate aqueous solution (SiO 2 concentration 27.0% by weight,
Na 2 O concentration 8.2 wt%) 30 ml was taken and stirred.

これとは別にクロモトロープ酸二ナトリウム(メルク
特級)0.6005gをイオン交換水90.5mlに分散させて、珪
酸ナトリウム水溶液中に30分かけて徐々に添加した。撹
拌は約5時間行ない赤かっ色の色に変化した。
Separately, 0.6005 g of disodium chromotropic acid (Merck special grade) was dispersed in 90.5 ml of ion-exchanged water and gradually added to the sodium silicate aqueous solution over 30 minutes. The stirring was continued for about 5 hours and the color changed to reddish brown.

この溶液を(1+9)硫酸水溶液29.5ml中に加えNH4O
H水溶液でpHを3.0に調整した後pH4.0まで上げた。よく
撹拌後この水溶液を80℃で1時間保持しゲル化させた。
This solution was added to 29.5 ml of (1 + 9) sulfuric acid aqueous solution and NH 4 O was added.
The pH was adjusted to 3.0 with an aqueous H solution and then raised to pH 4.0. After stirring well, this aqueous solution was kept at 80 ° C. for 1 hour for gelation.

このシリカヒドロゲルを細かく粉砕した後、イオン交
換水約5で洗浄した後5N HCl200ml中に入れ常温で一
夜浸漬した。その後、イオン交換水約40で洗浄し、オ
ーブン乾燥機で乾燥した。
The silica hydrogel was finely pulverized, washed with about 5 of ion-exchanged water, and then placed in 200 ml of 5N HCl and immersed at room temperature overnight. Then, it was washed with about 40 ion-exchanged water and dried in an oven dryer.

シリカ中の不純物含有量を後記表−1に示す。 The content of impurities in silica is shown in Table 1 below.

実施例4〜5 実施例1の方法において、本発明のキレート剤を同量
のタイロン又は5−スルホサリチル酸に変更し、その他
は全く同様の方法でシリカを製造した場合のシリカ中の
不純物含有量を後記表−1に示す。
Examples 4 to 5 In the method of Example 1, the chelating agent of the present invention was changed to the same amount of Tyrone or 5-sulfosalicylic acid, and otherwise the content of impurities in silica when the silica was produced by exactly the same method. Is shown in Table 1 below.

比較例 市販の珪酸ナトリウム水溶液(SiO2濃度27.0重量%、
Na2O濃度8.2重量%)30mlとり、撹拌した。
Comparative Example Commercially available sodium silicate aqueous solution (SiO 2 concentration 27.0% by weight,
Na 2 O concentration 8.2 wt%) 30 ml was taken and stirred.

イオン交換水90.5mlを珪酸ナトリウム水溶液中に30分
かけて徐々に添加した。撹拌は約5時間行なった。
90.5 ml of ion-exchanged water was gradually added to the sodium silicate aqueous solution over 30 minutes. The stirring was performed for about 5 hours.

この溶液を(1+9)硫酸水溶液29.5ml中に加えNH4O
H水溶液でpHを3.0に調整した後pH4.0まで上げた。よく
撹拌後この水溶液を80℃で1時間保持しゲル化させた。
This solution was added to 29.5 ml of (1 + 9) sulfuric acid aqueous solution and NH 4 O was added.
The pH was adjusted to 3.0 with an aqueous H solution and then raised to pH 4.0. After stirring well, this aqueous solution was kept at 80 ° C. for 1 hour for gelation.

このシリカヒドロゲルを細かく粉砕した後、イオン交
換水約5で洗浄した後5N HCl200ml中に入れ常温で一
夜浸漬した。その後、イオン交換水約40で洗浄し、オ
ーブン乾燥機で乾燥した。
The silica hydrogel was finely pulverized, washed with about 5 of ion-exchanged water, and then placed in 200 ml of 5N HCl and immersed at room temperature overnight. Then, it was washed with about 40 ion-exchanged water and dried in an oven dryer.

シリカ中の不純物含有量その他を後記表−1に示す。 The content of impurities in silica and others are shown in Table 1 below.

表−1より明らかなようにシリカ中のTi53ppm、Al56p
pmなどが残存していた。
As is clear from Table-1, Ti53ppm, Al56p in silica
pm etc remained.

実施例6 pH1.2のシリカゾル(SiO2として5.0重量%)1000mlを
撹拌し、アンモニア水を加えてpH2.0にした。
Example 6 1000 ml of pH 1.2 silica sol (5.0% by weight as SiO 2 ) was stirred and aqueous ammonia was added to adjust the pH to 2.0.

よく撹拌後、この水溶液を80℃2時間保持しゲル化さ
せた。
After stirring well, this aqueous solution was kept at 80 ° C. for 2 hours for gelation.

その後の操作は、実施例1と全く同様の方法でシリカ
を製造した。
Subsequent operations were the same as in Example 1 to produce silica.

この時のシリカ中の不純物は Al 12ppm Ca 0.49p
pm Cr 0.081ppm Fe 2.3ppm Mg 0.16ppm Na 0.6
8ppm Ti 40ppm V 0.47ppm Zr 2.3ppm だった
が、pH1.2のシリカゾル(SiO2として5.0重量%)1000ml
を硫酸でpH1.2にした溶液50mlにクロモトロープ酸二ナ
トリウム4,0011gを加えて同様の処理をしたところ、Al
10ppm Ca 0.43ppm Cr 0.065ppm Fe 1.9ppm Mg
0.086ppm Na 0.62ppm Ti 22ppm V 0.27ppm Z
r 2.0ppmに減少した。
Impurities in the silica at this time were Al 12ppm Ca 0.49p
pm Cr 0.081ppm Fe 2.3ppm Mg 0.16ppm Na 0.6
8ppm Ti 40ppm V 0.47ppm Zr 2.3ppm, but silica sol with pH 1.2 (5.0wt% as SiO 2 ) 1000ml
Was added to 50 ml of a solution of sulfuric acid adjusted to pH 1.2 with 4,0011 g of disodium chromotropic acid salt and treated in the same manner.
10ppm Ca 0.43ppm Cr 0.065ppm Fe 1.9ppm Mg
0.086ppm Na 0.62ppm Ti 22ppm V 0.27ppm Z
r Reduced to 2.0 ppm.

実施例7 シリカヒドロゲル200ml(SiO2として5.0重量%)をイ
オン交換水約40で水洗し、180℃で乾燥したところ、A
l 13ppm Ca 1.2ppm Cr 0.092ppm Fe 1.9ppm Mg
1.9ppm Na 2.2ppm Ti 6.0ppm V 0.076ppm Zr
0.50ppmだった。
Example 7 200 ml of silica hydrogel (5.0 wt% as SiO 2 ) was washed with about 40 ion-exchanged water and dried at 180 ° C.
l 13ppm Ca 1.2ppm Cr 0.092ppm Fe 1.9ppm Mg
1.9ppm Na 2.2ppm Ti 6.0ppm V 0.076ppm Zr
It was 0.50 ppm.

同じシリカヒドロゲル200ml(SiO2として5.0重量%)
をクロモトロープ酸二ナトリウムとエチレンジアミン四
酢酸カルシウム二ナトリウムとが溶解されているイオン
交換水約25に各10mM溶解し、接触させた。その後イオ
ン交換水15で水洗し、180℃で乾燥したら、 Al 8.7ppm Ca 1.0ppm Cr 0.090ppm Fe 1.9ppm Mg 0.27ppm Na 1.9ppm Ti 4.0ppm V 0.052ppm Zr 0.33ppmにまで減少した。
200 ml of the same silica hydrogel (5.0 wt% as SiO 2 )
10 mM of each was dissolved in about 25 ion-exchanged water in which disodium chromotropate and disodium calcium ethylenediaminetetraacetate were dissolved and brought into contact with each other. Then, it was washed with ion-exchanged water 15 and dried at 180 ° C., and then it was reduced to Al 8.7 ppm Ca 1.0 ppm Cr 0.090 ppm Fe 1.9 ppm Mg 0.27 ppm Na 1.9 ppm Ti 4.0 ppm V 0.052 ppm Zr 0.33 ppm.

【図面の簡単な説明】[Brief description of the drawings]

第1図は本発明の実施例1で得られたシリカの細孔分布
を示すグラフである。
FIG. 1 is a graph showing the pore size distribution of silica obtained in Example 1 of the present invention.

Claims (3)

(57)【特許請求の範囲】(57) [Claims] 【請求項1】ケイ酸化合物の溶液をフェノール性水酸基
及びスルホン酸基を配位子とするキレート剤と接触さ
せ、次いで、これを原料としてシリカを得ることを特徴
とする高純度シリカの製造法。
1. A method for producing high-purity silica, which comprises bringing a solution of a silicic acid compound into contact with a chelating agent having a phenolic hydroxyl group and a sulfonic acid group as a ligand, and then using this as a raw material to obtain silica. .
【請求項2】シリカゾル又はシリカヒドロゲルをフェノ
ール性水酸基及びスルホン酸基を配位子とするキレート
剤と接触させ、次いで、これを原料としてシリカを得る
ことを特徴とする高純度シリカの製造法。
2. A method for producing high-purity silica, which comprises contacting silica sol or silica hydrogel with a chelating agent having a phenolic hydroxyl group and a sulfonic acid group as a ligand, and then using this as a raw material to obtain silica.
【請求項3】前記キレート剤をエチレンジアミン四酢酸
ナトリウムもしくはエチレンジアミン四酢酸カルシウ
ム、チオリンゴ酸、シュウ酸、クエン酸及びサリチル酸
などから選ばれた少なくとも一種のキレート剤と併用し
て用いることを特徴とする特許請求の範囲第1項又は第
2項記載の高純度シリカの製造法。
3. A chelating agent which is used in combination with at least one chelating agent selected from sodium ethylenediaminetetraacetate or calcium ethylenediaminetetraacetate, thiomalic acid, oxalic acid, citric acid and salicylic acid. The method for producing high-purity silica according to claim 1 or 2.
JP22504288A 1988-09-08 1988-09-08 Method for producing high-purity silica Expired - Fee Related JP2694163B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP22504288A JP2694163B2 (en) 1988-09-08 1988-09-08 Method for producing high-purity silica

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP22504288A JP2694163B2 (en) 1988-09-08 1988-09-08 Method for producing high-purity silica

Publications (2)

Publication Number Publication Date
JPH0274515A JPH0274515A (en) 1990-03-14
JP2694163B2 true JP2694163B2 (en) 1997-12-24

Family

ID=16823131

Family Applications (1)

Application Number Title Priority Date Filing Date
JP22504288A Expired - Fee Related JP2694163B2 (en) 1988-09-08 1988-09-08 Method for producing high-purity silica

Country Status (1)

Country Link
JP (1) JP2694163B2 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080131717A1 (en) * 2006-12-05 2008-06-05 Obanda Diana N Protecting Wood With Stabilized Boron Complexes

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW530029B (en) * 1999-11-17 2003-05-01 Akzo Nobel Nv A method for manufacturing of silica sols
KR100477676B1 (en) * 1999-11-17 2005-03-18 악조 노벨 엔.브이. A method for manufacturing of silica sols
CN106111097A (en) * 2016-06-27 2016-11-16 中国海洋石油总公司 A kind of preparation method of high-purity column chromatography silica gel
JP6791769B2 (en) * 2017-01-24 2020-11-25 太平洋セメント株式会社 Method for manufacturing purified silica

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080131717A1 (en) * 2006-12-05 2008-06-05 Obanda Diana N Protecting Wood With Stabilized Boron Complexes
US9414598B2 (en) * 2006-12-05 2016-08-16 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Protecting wood with stabilized boron complexes

Also Published As

Publication number Publication date
JPH0274515A (en) 1990-03-14

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