JP2001294420A - Purification method of alkali silicate solution - Google Patents
Purification method of alkali silicate solutionInfo
- Publication number
- JP2001294420A JP2001294420A JP2000110916A JP2000110916A JP2001294420A JP 2001294420 A JP2001294420 A JP 2001294420A JP 2000110916 A JP2000110916 A JP 2000110916A JP 2000110916 A JP2000110916 A JP 2000110916A JP 2001294420 A JP2001294420 A JP 2001294420A
- Authority
- JP
- Japan
- Prior art keywords
- aqueous solution
- alkali silicate
- silica
- solution
- particles
- 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.)
- Withdrawn
Links
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- Separation Using Semi-Permeable Membranes (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高純度シリカや高
純度コロイダルシリカ、高純度シリカゲルの原料に用い
得る珪酸アルカリ水溶液を、低コストで精製することの
できる精製方法に関するものである。本発明により精製
された珪酸アルカリ水溶液は、特に、半導体シリコンウ
エハの研磨加工時に用いられる研磨剤の製造原料などと
して好適に用いることができる。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying an aqueous alkali silicate solution which can be used as a raw material for high-purity silica, high-purity colloidal silica, and high-purity silica gel at low cost. The aqueous alkali silicate solution purified according to the present invention can be suitably used particularly as a raw material for producing an abrasive used for polishing a semiconductor silicon wafer.
【０００２】[0002]
【従来の技術】従来より珪酸アルカリ水溶液を原料とし
て製造されるコロイダルシリカは、ブラウン管製造にお
ける蛍光体の接着バインダー、電池中の電解液のゲル化
剤、揺変剤、飛散防止剤、半導体素子表面の金属配線お
よび絶縁膜の研磨剤などとして、様々な用途に用いられ
てきた。また、高純度のコロイダルシリカは、半導体封
止用樹脂のフィラー、シリコンウエハ研磨剤、化粧品
用、食品加工用などの様々な用途に用いられてきた。し
かしこれらのコロイダルシリカにおいて、原料の珪酸ア
ルカリ水溶液はＦｅ、Ｃｒ、Ｎｉ、Ｃｕを含有している
ので、それらの一部が金属性不純物として水酸化物のコ
ロイド状微粒子となっている。したがって、金属性不純
物やコロイド状不純物微粒子の混入を嫌う分野において
は、これらを実質的に含まない高純度な珪酸アルカリ水
溶液を必要としていた。特に半導体シリコンウエハの研
磨加工に用いられる研磨剤に存在する金属、特にＣｕは
研磨加工中にウエハ内部に深く拡散し、ウエハ品質を劣
化させ、該ウエハによって形成された半導体デバイスの
特性を著しく低下させるという事実が明らかとなった。2. Description of the Related Art Colloidal silica conventionally produced from an aqueous solution of alkali silicate is used as an adhesive binder for a phosphor in the production of a cathode ray tube, a gelling agent for an electrolytic solution in a battery, a thixotropic agent, an anti-scattering agent, and a semiconductor element surface. Has been used in various applications as a polishing agent for metal wiring and insulating films. In addition, high-purity colloidal silica has been used in various applications such as fillers for resin for semiconductor encapsulation, abrasives for silicon wafers, cosmetics, and food processing. However, in these colloidal silicas, the aqueous solution of alkali silicate as a raw material contains Fe, Cr, Ni, and Cu, and some of them are hydroxide colloidal fine particles as metallic impurities. Therefore, in a field in which metallic impurities and fine particles of colloidal impurities are not to be mixed, a high-purity alkali silicate aqueous solution substantially free of these has been required. In particular, metals, particularly Cu, present in the polishing agent used for polishing a semiconductor silicon wafer diffuse deeply into the wafer during the polishing process, thereby deteriorating the quality of the wafer and significantly deteriorating the characteristics of the semiconductor device formed by the wafer. The fact that it was made clear.
【０００３】一般的な珪酸アルカリ水溶液は、珪酸アル
カリガラスを高温高圧で水に溶かす方法や非晶質のシリ
カをアルカリ水溶液に溶解する方法で製造されている
が、製造工程で溶液になったばかりのものは、濁ってお
り濾過工程を経て製品となる。濾過工程としては、例え
ば特開平2-141416号公報や特開平9-110416号公報に記載
されている。前者はガラス溶解時にＡ型ゼオライトを添
加する方法で、後者は珪酸カルシウムアルカリを添加す
る方法で、いずれも数ミクロンのオーダーでの濾過を行
っている。これとは別に、高純度の珪酸アルカリ水溶液
を製造する方法は既にいくつか提案されている。特公昭
41-3369号公報には、アルカリ金属珪酸塩を純水で希釈
した後、Ｈ型陽イオン交換樹脂に接触させて脱カチオン
し、さらに酸を加えて強酸性とした後、再度Ｈ型陽イオ
ン交換樹脂およびＯＨ型陰イオン交換樹脂に接触させて
脱カチオン脱アニオンし、アルカリを加えて加熱してシ
リカをコロイド化し、濃縮した後ＫＯＨを加えて珪酸カ
リ水溶液を得る方法が記載されている。また、四塩化珪
素から製造されたヒュームドシリカや、酸洗いされたシ
リカゲルなどの高純度のシリカ源をアルカリに溶かして
高純度珪酸アルカリ水溶液を得る方法は公知の方法とな
っている。また、通常の珪酸アルカリ水溶液を用いてコ
ロイダルシリカやシリカゲルを製造する工程で不純物を
除去する方法は数多く提案されている。特開平5-97422
号公報には、高純度コロイダルシリカの製造方法とし
て、珪酸アルカリ水溶液を純水で希釈した後、Ｈ型強酸
性陽イオン交換樹脂に接触させて脱アルカリし活性珪酸
の水溶液を得、さらに酸を加えて強酸性とした後Ｈ型強
酸性陽イオン交換樹脂、ＯＨ型強塩基性陰イオン交換樹
脂に接触させ高純度の活性珪酸とした後、粒子成長させ
て高純度コロイダルシリカを製造する方法が記載されて
いる。特開平4-231319号公報には上記方法の酸と同時に
シュウ酸を加える方法の記載がある。特開昭61-158810
号公報には、珪酸アルカリ水溶液を純水で希釈した後、
Ｈ型強酸性陽イオン交換樹脂に接触させて脱アルカリし
（活性珪酸の作成）、さらに酸を加えて強酸性とした
後、限外ろ過膜を用いて不純物を除去して得られたオリ
ゴ珪酸溶液（高純度の活性珪酸）の一部に、アンモニア
またはアミンを加え加熱を行いヒールゾルを調製し、こ
れに残りのオリゴ珪酸溶液を徐々に滴下し高純度シリカ
ゾルを得る方法が記載されている。特開平4-2606号公報
には上記同様に酸処理した珪酸アルカリ水溶液を、Ｈ型
強酸性陽イオン交換樹脂、ＯＨ型強塩基性陰イオン交換
樹脂に接触させ、これにアルカリ金属水酸化物水溶液を
加え６０〜１５０℃に加熱することにより安定な水性ゾ
ル生成させ、さらに限外ろ過膜を介して水を除き、次い
でＨ型強酸性陽イオン交換樹脂、ＯＨ型強塩基性陰イオ
ン交換樹脂と接触させ、最後にアンモニアを加えてシリ
カ以外の多価金属酸化物を実質的に含まない安定な水性
シリカゾルを生成する方法が記載されている。 いずれの方法も酸性にした珪酸溶液をイオン交換樹脂に
接触させて不純物イオンを除去する手段が基本になって
いる。[0003] A common alkali silicate aqueous solution is produced by a method of dissolving an alkali silicate glass in water at high temperature and pressure or a method of dissolving amorphous silica in an alkaline aqueous solution. The product becomes cloudy and becomes a product after a filtration process. The filtration step is described in, for example, JP-A-2-141416 and JP-A-9-110416. The former is a method in which A-type zeolite is added at the time of glass melting, and the latter is a method in which calcium silicate is added. In both cases, filtration is performed on the order of several microns. Apart from this, several methods for producing a high-purity aqueous alkali silicate solution have already been proposed. Tokiko
No. 41-3369 discloses that after diluting an alkali metal silicate with pure water, contacting with an H-type cation exchange resin to decationize, further adding an acid to make it strongly acidic, and then re-forming the H-type cation. It describes a method of decationizing and decationizing by contacting an cation-exchange resin and an OH-type anion exchange resin, adding an alkali and heating to colloidal silica, concentrating the mixture, and adding KOH to obtain an aqueous solution of potassium silicate. In addition, a method of obtaining a high-purity aqueous alkali silicate solution by dissolving a high-purity silica source such as fumed silica manufactured from silicon tetrachloride or pickled silica gel in an alkali is known. Also, many methods have been proposed for removing impurities in the process of producing colloidal silica or silica gel using a normal alkali silicate aqueous solution. JP 5-97422
In the publication, as a method for producing high-purity colloidal silica, an aqueous solution of an active silicic acid was obtained by diluting an aqueous solution of an alkali silicate with pure water, and then contacting it with an H-type strongly acidic cation exchange resin to obtain an aqueous solution of active silicic acid. In addition, a method of producing high-purity colloidal silica by contacting an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin to obtain high-purity active silicic acid, and then growing the particles by making the particles highly acidic. Has been described. Japanese Patent Application Laid-Open No. Hei 4-213319 describes a method of adding oxalic acid simultaneously with the acid of the above method. JP-A-61-158810
In the official gazette, after diluting an alkali silicate aqueous solution with pure water,
Oligosilicate obtained by contacting with H-type strongly acidic cation exchange resin for dealkalization (preparation of activated silicic acid), adding acid to make it strongly acidic, and removing impurities using ultrafiltration membrane A method is described in which ammonia or an amine is added to a part of a solution (high-purity active silicic acid), heating is performed to prepare a heel sol, and the remaining oligosilicic acid solution is gradually added dropwise to obtain a high-purity silica sol. JP-A-4-2606 discloses that an aqueous alkali silicate solution treated in the same manner as above is brought into contact with an H-type strongly acidic cation exchange resin and an OH-type strongly basic anion exchange resin, and an alkali metal hydroxide aqueous solution is added thereto. And heated to 60 to 150 ° C. to form a stable aqueous sol, and further remove water through an ultrafiltration membrane. Then, an H-type strongly acidic cation exchange resin, an OH type strongly basic anion exchange resin, It describes a method of contacting and finally adding ammonia to produce a stable aqueous silica sol substantially free of multivalent metal oxides other than silica. Both methods are basically based on means for removing an impurity ion by bringing an acidified silicic acid solution into contact with an ion exchange resin.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、特公昭
41-3369号公報、特開平5-97422号公報、特開平4-231319
号公報、特開昭61-158810号公報、特開平4-2606号に記
載の方法では工程が煩雑に長いばかりでなく、希薄な珪
酸液を強酸性にするために大量の酸を使用しなくてはな
らず、その酸を後工程で除去しなくてはなず、そのアニ
オン交換法による除去では樹脂の再生にまた数倍のアル
カリを必要とし、コスト的に問題がある。また、いった
ん活性ゾルを作成してから精製する方法では、活性ゾル
は分画分子量20000程度の限外濾過膜を通過しないので
（1〜3nmくらいの大きさの微粒子になっている）、そこ
に含まれる酸不溶性の不純物微粒子を除去することは出
来なくなってしまう。要するに、後工程でいかなる精製
方法を行うにせよ、予め微粒子除去を行った珪酸アルカ
リ水溶液を原料に使用しなくては根本的な解決法は得ら
れない。また、四塩化珪素から製造されたヒュームドシ
リカや珪酸エステルから得られたシリカ、酸洗いされた
シリカゲルなどの高純度のシリカ源をアルカリに溶かし
て高純度珪酸アルカリ水溶液を得る公知方法は、シリカ
原料のコストが高すぎて、そのような珪酸アルカリ水溶
液は限られた用途にしか使用できない。また、特開平2-1
41416号公報や特開平9-110416号公報に記載の方法で
は、サブミクロンの微粒子は除去できず、汎用の珪酸ア
ルカリ水溶液にしか使用できない。したがって本発明の
目的は、高純度シリカや高純度コロイダルシリカ、高純
度シリカゲルの原料に用い得る珪酸アルカリ水溶液を、
低コストで精製することのできる精製方法を提供するこ
とにある。[Problems to be solved by the invention]
No. 41-3369, JP-A-5-97422, JP-A-4-313319
In the method described in JP-A-61-158810, JP-A-4-2606, the process is not only complicated and long, but also a large amount of acid is not used to make a dilute silicate solution strongly acidic. In addition, the acid must be removed in a subsequent step, and the removal by the anion exchange method requires several times as much alkali to regenerate the resin, which is costly. In addition, in the method in which the active sol is once prepared and then purified, the active sol does not pass through an ultrafiltration membrane having a molecular weight cutoff of about 20,000 (it is in the form of fine particles of about 1 to 3 nm). The acid-insoluble impurity fine particles contained therein cannot be removed. In short, no matter what purification method is performed in the subsequent step, a fundamental solution cannot be obtained unless an alkali silicate aqueous solution from which fine particles have been removed is used as a raw material. Further, a known method of dissolving a high-purity silica source such as fumed silica or silica obtained from silicon tetrachloride, silica obtained from a silicate ester, and an acid-washed silica gel in an alkali to obtain a high-purity alkali silicate aqueous solution is known as silica. The raw material costs are too high and such an aqueous alkali silicate solution can only be used for limited applications. In addition, JP-A-2-1
The methods described in JP 41416 and JP-A-9-110416 cannot remove submicron fine particles and can be used only for a general-purpose alkali silicate aqueous solution. Therefore, an object of the present invention is a high-purity silica or a high-purity colloidal silica, an alkali silicate aqueous solution that can be used as a raw material for a high-purity silica gel,
An object of the present invention is to provide a purification method that can be purified at low cost.
【０００５】[0005]
【課題を解決するための手段】本発明者らは鋭意研究を
重ねた結果、上記のような従来の課題を解決することを
得た。すなわち本発明は、珪酸アルカリ水溶液の粘度を
予め1〜50mPa・sに調節し、これを分画分子量15000以下
の限外濾過膜を通過させて、シリカ当たりのＣｕの含有
率が200ppb以下であり、かつ1nm以上の大きさの粒子が
実質的に存在しない珪酸アルカリ水溶液にすることを特
徴とする珪酸アルカリ水溶液の精製方法を提供するもの
である。また本発明は、分画分子量3000〜15000の限外
濾過膜を使用する前記の方法を提供するものである。ま
た本発明は、前記の方法により得られた、シリカ当たり
のＣｕの含有率が200ppb以下であり、かつ1nm以上の大
きさの粒子が実質的に存在しない珪酸アルカリ水溶液を
提供するものである。Means for Solving the Problems As a result of intensive studies, the present inventors have solved the above-mentioned conventional problems. That is, the present invention adjusts the viscosity of the aqueous alkali silicate solution to 1 to 50 mPas in advance, passes this through an ultrafiltration membrane having a cut-off molecular weight of 15,000 or less, and the Cu content per silica is 200 ppb or less. It is intended to provide a method for purifying an aqueous solution of an alkali silicate, characterized in that the solution is an aqueous solution of an alkali silicate substantially free of particles having a size of 1 nm or more. The present invention also provides the above-mentioned method using an ultrafiltration membrane having a molecular weight cutoff of 3,000 to 15,000. The present invention also provides an alkali silicate aqueous solution obtained by the above method, having a Cu content of not more than 200 ppb per silica and substantially no particles having a size of 1 nm or more.
【０００６】従来、珪酸ソーダ、珪酸カリに代表される
珪酸アルカリ水溶液はその製造工程で最終製品になる前
に濾過が行われるが、この濾過は１ミクロン程度の粒子
を除去し目視で透明となる程度の精製であって、サブミ
クロンの粒子が除去されていない。珪酸アルカリ水溶液
製品を長時間静置すると澱が発生したり、濁りが生じる
現象はよく知られているが、本発明者らの検討によれ
ば、この現象はサブミクロンの粒子が沈降したり、サブ
ミクロンの粒子を核としてシリカが析出して起こる現象
であることが分かった。本発明者らはこのサブミクロン
の粒子を去することにより、不純物特に重金属の少ない
珪酸アルカリ水溶液を得ることができ、この珪酸アルカ
リ水溶液を用いれば、２次製品の品質を改良することが
できる。Conventionally, an aqueous solution of an alkali silicate represented by sodium silicate and potassium silicate is subjected to filtration before it becomes a final product in the production process. This filtration removes particles of about 1 micron and becomes visually transparent. With only a degree of purification, submicron particles have not been removed. It is well known that the alkali silicate aqueous solution forms sediment or turbidity when left for a long time, but according to the study of the present inventors, the phenomenon is that submicron particles settle, It was found that this phenomenon was caused by precipitation of silica with submicron particles as nuclei. By removing the submicron particles, the present inventors can obtain an aqueous solution of an alkali silicate containing a small amount of impurities, in particular, heavy metals. Using this aqueous solution of an alkali silicate can improve the quality of a secondary product.
【０００７】[0007]
【発明の実施の形態】以下、本発明をさらに説明する。
まず、使用する限外濾過膜について説明する。限外濾過
膜が適用される分離は対象粒子が1nmから数ミクロンで
あるが、溶解した高分子物質をも対象とするため、ナノ
メータ域では濾過精度を分画分子量で表現している。 ミ
クロン付近の濾過はマイクロ濾過とも呼ばれ、この範囲
の濾過では本発明の目的は達成できない。本発明では、
分画分子量15000以下の限外濾過膜を使用する。この範
囲の膜を使用すると1nm以上の粒子を分離することがで
きる。更に好ましくは分画分子量3000〜15000の限外濾
過膜を使用するのがよい。3000未満の膜では濾過抵抗が
大きすぎて処理時間が長くなり不経済であり、15000を
超えると、精製度が低くなり目的を達成できない。限外
濾過膜の材質はとくに制限されないが、例えばポリスル
ホン、ポリアクリルニトリル、燒結金属、セラミック、
カーボンなどが挙げられるが、耐熱性や濾過速度などか
らポリスルホン製が好ましい。限外濾過膜の形状は、ス
パイラル型、チューブラー型、中空糸型などあり、どれ
でも使用できるが、中空糸型がコンパクトで使用しやす
い。BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be further described.
First, the ultrafiltration membrane used will be described. The separation to which the ultrafiltration membrane is applied has a target particle size of 1 nm to several microns. However, since it is intended for a dissolved high molecular substance, the filtration accuracy is expressed in terms of the molecular weight cutoff in the nanometer range. Filtration near the micron is also called microfiltration, and the filtration in this range cannot achieve the object of the present invention. In the present invention,
Use an ultrafiltration membrane with a cut-off molecular weight of 15,000 or less. Use of a membrane in this range can separate particles of 1 nm or more. It is more preferable to use an ultrafiltration membrane having a molecular weight cutoff of 3000 to 15000. If the membrane is less than 3000, the filtration resistance is too large, and the treatment time is prolonged, which is uneconomic. If it exceeds 15,000, the purification degree is lowered and the object cannot be achieved. Although the material of the ultrafiltration membrane is not particularly limited, for example, polysulfone, polyacrylonitrile, sintered metal, ceramic,
Although carbon etc. are mentioned, polysulfone is preferable from heat resistance and filtration speed. The shape of the ultrafiltration membrane includes a spiral type, a tubular type and a hollow fiber type, and any type can be used. The hollow fiber type is compact and easy to use.
【０００８】用いる珪酸アルカリ水溶液としては、通常
水ガラス（水ガラス１号〜４号等）と呼ばれる珪酸ナト
リウム水溶液が好適に用いられる。このものは比較的安
価であり、容易に手に入れることができる。また、Ｎａ
イオンを嫌う半導体用途の２次製品を考慮すると珪酸カ
リウム水溶液は高純度化の対象にふさわしい。As the aqueous solution of alkali silicate to be used, an aqueous solution of sodium silicate usually called water glass (water glass Nos. 1 to 4) is preferably used. It is relatively inexpensive and can be easily obtained. Na
Considering secondary products for semiconductors that dislike ions, an aqueous solution of potassium silicate is suitable for high purification.
【０００９】前記とは別に、固体状のメタ珪酸アルカリ
を水に溶かして精製前の珪酸アルカリ水溶液を調製する
こともできる。メタ珪酸アルカリは晶析工程を経て製造
されるため、不純物の少ないものがある。Apart from the above, it is also possible to prepare an aqueous solution of alkali silicate before purification by dissolving solid alkali metasilicate in water. Alkali metasilicate is produced through a crystallization step, and therefore has a small amount of impurities.
【００１０】このような珪酸アルカリ水溶液は、精製前
に予め粘度を1〜50mPa・s、好ましくは５〜３０mPa・sに
調節しておくのがよい。粘度の調節方法としては、水希
釈、加熱、表面張力低下剤の添加などがあり、それらを
組み合わせて経済的に最適な条件にすればよい。The viscosity of such an aqueous alkali silicate solution is preferably adjusted to 1 to 50 mPa · s, preferably 5 to 30 mPa · s before purification. Examples of the method of adjusting the viscosity include dilution with water, heating, and addition of a surface tension reducing agent, and these may be combined to obtain economically optimal conditions.
【００１１】前記の本発明の方法により得られた珪酸ア
ルカリ水溶液は、シリカ当たりのＣｕの含有率が200ppb
以下であり、1nm以上の大きさの粒子が実質的に存在し
ない水溶液となる。The aqueous alkali silicate solution obtained by the method of the present invention has a Cu content per silica of 200 ppb.
Or less, and an aqueous solution substantially free of particles having a size of 1 nm or more.
【００１２】[0012]
【実施例】以下、実施例および比較例を示し、本発明を
さらに詳細に説明する。 （実施例１）ＪＩＳ３号珪酸ソーダ（ＳｉＯ2：28.8重
量％、Ｎａ2Ｏ：9.7重量％、Ｈ2Ｏ：61.5重量％）40kｇ
に脱イオン水17.6kｇを加えて均一に混合しＳｉＯ2：20
重量％の希釈珪酸ソーダを作成した。この希釈珪酸ソー
ダは、シリカ当たりのＣｕの含有率が280ppbであり、僅
かに黒ずんでおり、25℃の粘度が9mPa・sであった。この
希釈珪酸ソーダに対し、分画分子量10000の中空糸型限
外濾過膜（旭化成(株)製マイクローザＵＦモジュールＳ
ＬＰ−３０５３）を用いてポンプ循環送液による加圧濾
過を行い、精製濾液約30kｇと不純物の濃縮された循環
液約17kｇに分離した。精製濾液はシリカ当たりのＣｕ
の含有率が150ppbであり、無色透明でありコロイド粒子
の除去が確認された。一方循環液は黒ずんで僅かに不透
明であった。また、1nm以上の大きさの粒子が実質的に
存在しないことが確認された。The present invention will be described below in more detail with reference to Examples and Comparative Examples. (Example 1) 40 kg of JIS No. 3 sodium silicate (SiO 2 : 28.8% by weight, Na 2 O: 9.7% by weight, H 2 O: 61.5% by weight)
Mixed with deionized water 17.6kg uniformly on to SiO 2: 20
A weight percent diluted sodium silicate was made. This diluted sodium silicate had a Cu content of 280 ppb per silica, was slightly dark, and had a viscosity at 25 ° C. of 9 mPa · s. A hollow fiber type ultrafiltration membrane having a molecular weight cut off of 10,000 (Microza UF module S manufactured by Asahi Kasei Corp.)
LP-3053) was used to perform pressure filtration by pump circulation and separated into about 30 kg of a purified filtrate and about 17 kg of a circulating liquid in which impurities were concentrated. The purified filtrate is Cu per silica
Was 150 ppb, it was colorless and transparent, and removal of colloid particles was confirmed. On the other hand, the circulating fluid was dark and slightly opaque. It was also confirmed that particles having a size of 1 nm or more were not substantially present.
【００１３】（比較例１）日本化学工業(株)製の珪酸カ
リウム水溶液（ＳｉＯ2：26.4重量％、Ｋ2Ｏ：13.5重量
％、Ｈ2Ｏ：60.1重量％）4000ｇを20℃で分画分子量600
0の中空糸型限外濾過膜（旭化成(株)製マイクローザＵ
ＦモジュールＳＩＰ−１０１３）を用いてポンプ循環送
液による加圧濾過を試みた。20℃の珪酸カリウム水溶液
の粘度は97mPa・sであり、10分間で1gの濾液しか回収で
きなかった。Comparative Example 1 4000 g of an aqueous solution of potassium silicate (SiO 2 : 26.4% by weight, K 2 O: 13.5% by weight, H 2 O: 60.1% by weight) manufactured by Nippon Chemical Industrial Co., Ltd. was fractionated at 20 ° C. Molecular weight 600
0 hollow fiber ultrafiltration membrane (Microza U manufactured by Asahi Kasei Corporation)
Pressure filtration was attempted by pump circulation using F module SIP-1013). The viscosity of the aqueous solution of potassium silicate at 20 ° C. was 97 mPa · s, and only 1 g of the filtrate could be collected in 10 minutes.
【００１４】（実施例２）日本化学工業(株)製の珪酸カ
リウム水溶液（ＳｉＯ2：26.4重量％、Ｋ2Ｏ：13.5重量
％、Ｈ2Ｏ：60.1重量％）4000ｇを50℃で分画分子量600
0の中空糸型限外濾過膜（旭化成(株)製マイクローザＵ
ＦモジュールＳＩＰ−１０１３）を用いてポンプ循環送
液による加圧濾過を試みた。50℃の珪酸カリウム水溶液
の粘度は15mPa・sであり、30分間で2000gの精製濾液を回
収した。精製前の珪酸カリウム水溶液のシリカ当たりの
Ｃｕの含有率は250ppbであり、僅かに赤く着色して濁っ
ており、精製濾液のシリカ当たりのＣｕの含有率は190p
pbであり、無色透明でありコロイド粒子の除去が確認さ
れた。また、1nm以上の大きさの粒子が実質的に存在し
ないことが確認された。Example 2 4000 g of an aqueous solution of potassium silicate (SiO 2 : 26.4% by weight, K 2 O: 13.5% by weight, H 2 O: 60.1% by weight) manufactured by Nippon Chemical Industrial Co., Ltd. was fractionated at 50 ° C. Molecular weight 600
0 hollow fiber ultrafiltration membrane (Microza U manufactured by Asahi Kasei Corporation)
Pressure filtration was attempted by pump circulation using F module SIP-1013). The viscosity of the aqueous potassium silicate solution at 50 ° C. was 15 mPa · s, and 2000 g of the purified filtrate was recovered in 30 minutes. The content of Cu per silica in the aqueous solution of potassium silicate before purification was 250 ppb, the color was slightly reddish and cloudy, and the content of Cu per silica in the purified filtrate was 190 pb.
pb, it was colorless and transparent, and removal of colloid particles was confirmed. It was also confirmed that particles having a size of 1 nm or more were not substantially present.
【００１５】（実施例３）2640gの純水に600ｇの日本ア
エロジル(株)製のヒュームドシリカＡＥＲＯＳＩＬ−１
３０を加え、更に2760ｇの水酸化テトラメチルアンモニ
ウム20％水溶液を加えて、攪拌下70℃で溶解した。溶解
液は20℃の粘度は10mPa・sであり、僅かに白色半透明で
ありコロイド粒子の存在が確認された。これを分画分子
量6000の中空糸型限外濾過膜（旭化成(株)製マイクロー
ザＵＦモジュールＳＩＰ−１０１３）を用いてポンプ循
環送液による加圧濾過を行った。２0℃の珪酸アンモニ
ウム水溶液の粘度は8mPa・sであり、60分間で4000gの精
製濾液を回収した。精製前の珪酸アンモニウム水溶液の
シリカ当たりのＣｕの含有率は250ppbであり、僅かに白
色半透明であり、精製濾液のシリカ当たりのＣｕの含有
率は190ppbであり、無色透明でありコロイド粒子の除去
が確認された。また、1nm以上の大きさの粒子が実質的
に存在しないことが確認された。Example 3 600 g of fumed silica AEROSIL-1 manufactured by Nippon Aerosil Co., Ltd. in 2640 g of pure water
Then, 2760 g of a 20% aqueous solution of tetramethylammonium hydroxide was added, and the mixture was dissolved at 70 ° C. with stirring. The solution at 20 ° C. had a viscosity of 10 mPa · s, was slightly translucent in white, and the presence of colloid particles was confirmed. This was subjected to pressure filtration by pump circulation using a hollow fiber type ultrafiltration membrane having a molecular weight cutoff of 6000 (Microza UF module SIP-1013 manufactured by Asahi Kasei Corporation). The viscosity of the aqueous solution of ammonium silicate at 20 ° C. was 8 mPa · s, and 4000 g of the purified filtrate was recovered in 60 minutes. The content of Cu per silica in the aqueous solution of ammonium silicate before purification was 250 ppb, slightly translucent, the content of Cu in the purified filtrate was 190 ppb per silica, colorless and transparent, and removal of colloid particles Was confirmed. It was also confirmed that particles having a size of 1 nm or more were not substantially present.
【００１６】[0016]
【発明の効果】本発明によれば、高純度シリカや高純度
コロイダルシリカ、高純度シリカゲルの原料に用い得る
珪酸アルカリ水溶液を、低コストで精製することのでき
る精製方法が提供される。According to the present invention, there is provided a method for purifying an alkali silicate aqueous solution which can be used as a raw material for high-purity silica, high-purity colloidal silica, and high-purity silica gel at low cost.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4D006 GA06 HA01 HA21 HA61 KE11Q KE11R KE16Q KE16R KE30Q KE30R MA01 MB05 MC03 MC05 MC62 PB20 4G073 AA06 BA01 BD30 CB03 CB09 FA30 FD18 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA06 HA01 HA21 HA61 KE11Q KE11R KE16Q KE16R KE30Q KE30R MA01 MB05 MC03 MC05 MC62 PB20 4G073 AA06 BA01 BD30 CB03 CB09 FA30 FD18
Claims (3)
Pa・sに調節し、これを分画分子量15000以下の限外濾過
膜を通過させて、シリカ当たりのＣｕの含有率が200ppb
以下であり、かつ1nm以上の大きさの粒子が実質的に存
在しない珪酸アルカリ水溶液にすることを特徴とする珪
酸アルカリ水溶液の精製方法。1. The viscosity of an alkali silicate aqueous solution is previously set to 1 to 50 m
It was adjusted to Pas, and passed through an ultrafiltration membrane having a molecular weight cutoff of 15,000 or less, and the content of Cu per silica was 200 ppb.
A method for purifying an aqueous solution of an alkali silicate, wherein the method is an aqueous solution of an alkali silicate, wherein the aqueous solution is the following and substantially no particles having a size of 1 nm or more are present.
使用する請求項１に記載の方法。2. The method according to claim 1, wherein an ultrafiltration membrane having a molecular weight cutoff of 3,000 to 15,000 is used.
られた、シリカ当たりのＣｕの含有率が200ppb以下であ
り、かつ1nm以上の大きさの粒子が実質的に存在しない
珪酸アルカリ水溶液。3. An aqueous alkali silicate solution obtained by the method according to claim 1 or 2, having a Cu content of not more than 200 ppb per silica and having substantially no particles having a size of 1 nm or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000110916A JP2001294420A (en) | 2000-04-12 | 2000-04-12 | Purification method of alkali silicate solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000110916A JP2001294420A (en) | 2000-04-12 | 2000-04-12 | Purification method of alkali silicate solution |
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| Publication Number | Publication Date |
|---|---|
| JP2001294420A true JP2001294420A (en) | 2001-10-23 |
Family
ID=18623346
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|---|---|---|---|
| JP2000110916A Withdrawn JP2001294420A (en) | 2000-04-12 | 2000-04-12 | Purification method of alkali silicate solution |
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| Country | Link |
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2000
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