JPH0755818B2 - Method for producing high-purity silica - Google Patents
Method for producing high-purity silicaInfo
- Publication number
- JPH0755818B2 JPH0755818B2 JP28577888A JP28577888A JPH0755818B2 JP H0755818 B2 JPH0755818 B2 JP H0755818B2 JP 28577888 A JP28577888 A JP 28577888A JP 28577888 A JP28577888 A JP 28577888A JP H0755818 B2 JPH0755818 B2 JP H0755818B2
- Authority
- JP
- Japan
- Prior art keywords
- silica
- aqueous solution
- acid
- purity silica
- producing high
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/126—Preparation of silica of undetermined type
- C01B33/128—Preparation of silica of undetermined type by acidic treatment of aqueous silicate solutions
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Silicon Compounds (AREA)
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方法に関する。詳しく
は、アルカリけい酸塩水溶液から、アルカリ金属、塩
素、ウランなど放射性を有する不純物のほか、特にチタ
ンの含有率が極めて低い高純度シリカを製造する方法に
関する。TECHNICAL FIELD The present invention relates to a method for producing high-purity silica. More specifically, it relates to a method for producing high-purity silica having an extremely low content of titanium in addition to radioactive impurities such as alkali metals, chlorine and uranium from an aqueous solution of alkali silicate.
本発明の方法により得られる高純度シリカは、電子部品
封止用樹脂組成物の充填剤、分散剤などとして、また、
特殊セラミックスの原料として好適に用いられるほか、
透明石英ガラスの原料としての用途が期待される。High-purity silica obtained by the method of the present invention is used as a filler, a dispersant, etc. for a resin composition for sealing electronic parts,
Suitable for use as a raw material for special ceramics,
It is expected to be used as a raw material for transparent quartz glass.
従来より、透明石英ガラスの原料としては天然水晶が用
いられている。しかし、半導体分野において電子部品素
子の集積度が高まるのに伴って、使用する原材料に対す
る高純度化の要求が厳しくなるのに対して、良好の天然
水晶は枯渇しつつある。そのため、天然水晶の合成高純
度シリカで代替しようとする検討が行われている。Conventionally, natural quartz has been used as a raw material for transparent quartz glass. However, in the field of semiconductors, as the degree of integration of electronic component devices increases, demands for high purity of raw materials used become strict, while good natural quartz is being depleted. Therefore, studies are being made to replace natural quartz with synthetic high-purity silica.
本発明は、このような要望に対応できる高純度シリカを
製造する方法を提供することを目的とするものである。An object of the present invention is to provide a method for producing high-purity silica that can meet such demands.
天然水晶に代わる合成高純度シリカを得る方法の一つと
して、アルカリけい酸塩水溶液を原料とする高純度シリ
カの製法としては； １）けい酸アルカリ水溶液を酸で処理することによって
精製する方法： （特開昭59-54632号，特開昭60-191016号など）． ２）上記の処理に際して、H2O2の存在下で行う方法（特
開昭61-286212号など）． などが提案されている。As one of the methods for obtaining synthetic high-purity silica as an alternative to natural quartz, a method for producing high-purity silica using an alkali silicate aqueous solution as a raw material is: 1) A method for purifying an alkali silicate aqueous solution by treating with an acid: (JP-A-59-54632, JP-A-60-191016, etc.). 2) A method of performing the above treatment in the presence of H 2 O 2 (JP-A-61-286212, etc.). Have been proposed.
これらの方法によって、純度のかなり高いシリカを製造
することはできる。しかし、１）の方法には、Tiの除去
が困難であるという難点がある。By these methods, it is possible to produce silica of considerably high purity. However, the method 1) has a drawback that it is difficult to remove Ti.
Tiは、石英ガラスの紫外部における透過率を低下させる
ので、石英ガラスの原料からは除去しなければならない
不純物の代表的なものである。Ti reduces the transmittance of the quartz glass in the ultraviolet region, and is therefore a typical impurity that must be removed from the raw material of the quartz glass.
一般に、Tiの鉱酸への溶解度は小さいので原料中に含ま
れるTiを所要の濃度レベルまで抽出除去するには多段階
の酸洗浄処理を要し、コスト高になる。実際面で、けい
酸アルカリ水溶液を原料として、Ti含有率が5ppmを下回
るシリカを得ることは困難であった。In general, since the solubility of Ti in mineral acids is low, a multi-step acid cleaning treatment is required to extract and remove Ti contained in the raw material to a required concentration level, resulting in high cost. Practically, it was difficult to obtain silica having a Ti content of less than 5 ppm by using an alkali silicate aqueous solution as a raw material.
また、２）の方法は、H2O2を用いてTiを鉱酸への溶解度
の大きい錯体に変換することによって抽出除去を容易に
しようとするものである。微量のTiを抽出除去するのに
H2O2を用いることは有効であるが、H2O2は熱分解によっ
て猛毒性を有するオゾンを生成するという難点を有し、
また、Tiの抽出処理の際に発泡するなど実用面において
取扱いの点で問題がある。Further, the method 2) is intended to facilitate extraction and removal by converting Ti into a complex having high solubility in mineral acid using H 2 O 2 . For extracting and removing a small amount of Ti
Although it is effective to use H 2 O 2 , H 2 O 2 has a drawback that it produces ozone which is highly toxic by thermal decomposition.
In addition, there is a problem in terms of handling in practical use, such as foaming during the Ti extraction process.
本発明者らは、従来の方法における前記の問題点を改善
するための研究を行い、アルカリけい酸塩水溶液を原料
として、微量のTiを除去する際の抽出助剤として過硫酸
アンモニウム（以下、APSという）が好適であることを
見出し、本発明を完成した。The present inventors conducted research to improve the above-mentioned problems in the conventional method, using an aqueous solution of alkali silicate as a raw material, ammonium persulfate (hereinafter, referred to as APS) as an extraction aid when removing a trace amount of Ti. The present invention has been completed.
すなわち本発明は、「一般式：M2O・nSiO2（ただし、Ｍ
はアルカリ金属元素、ｎはSiO2のモル数で0.5〜５を示
す）で表されるアルカリけい酸塩の水溶液を鉱酸と反応
させ、得られたシリカを鉱酸で処理して不純物を抽出除
去し高純度シリカを製造する方法において、前記の反応
および／または不純物抽出を過硫酸アンモニウムの存在
下で行うことを特徴とする高純度シリカの製造方法」を
要旨とする。That is, the present invention provides the following general formula: M 2 O · nSiO 2 (where M
Is an alkali metal element, and n is the number of moles of SiO 2 and represents 0.5 to 5), and an aqueous solution of an alkali silicate represented by the formula (3) is reacted with a mineral acid, and the obtained silica is treated with the mineral acid to extract impurities. In the method for producing high-purity silica by removing it, the above-mentioned reaction and / or impurity extraction are carried out in the presence of ammonium persulfate.
本発明の方法で原料のアルカリけい酸塩水溶液として
は、けい酸のナトリウム塩，カリウム塩，リチウム塩な
どの水溶液を用いることができる。In the method of the present invention, an aqueous solution of sodium silicate, potassium salt, lithium salt or the like of silicic acid can be used as the raw material alkali silicate aqueous solution.
また、反応および不純物抽出の各工程で用いられる鉱酸
としては、硫酸，硝酸，塩酸などが挙げられ、実用上、
硫酸を用いるのが好ましい。In addition, examples of the mineral acid used in each step of reaction and impurity extraction include sulfuric acid, nitric acid, hydrochloric acid, etc.
Preference is given to using sulfuric acid.
Ti抽出助剤としてのAPSの添加方法は、前記鉱酸の水溶
液にAPSを溶解させてもよいし、また、予め調製されたA
PS水溶液を前記鉱酸と混合してもよい。The method of adding APS as a Ti extraction aid, APS may be dissolved in an aqueous solution of the mineral acid, or A prepared in advance.
The PS aqueous solution may be mixed with the mineral acid.
APSの使用量は、存在するTiに対して等モル以上、好ま
しくは10〜100倍モルに相当する量とするのがよい。The amount of APS used should be an equimolar amount or more, preferably 10 to 100 times the molar amount of Ti present.
Ti抽出処理は、温度20℃以上、好ましくは50〜140℃の
範囲で行うのがよい。The Ti extraction treatment may be performed at a temperature of 20 ° C or higher, preferably 50 to 140 ° C.
常圧における処理液の沸点よりも高い温度で加圧下で処
理すると、Ti抽出処理の所要時間を短縮することができ
る。加圧抽出の際の温度は、高い程好ましいが酸による
装置の腐食やエネルギーコストを考慮すると、110〜140
℃の範囲が実用的である。When the treatment is performed under pressure at a temperature higher than the boiling point of the treatment liquid at normal pressure, the time required for the Ti extraction treatment can be shortened. The temperature during pressure extraction is preferably as high as possible, but considering the corrosion of the equipment due to acid and the energy cost, 110-140
The range of ℃ is practical.
Ti抽出処理の時間は、回分式の場合には５分から５時間
程度、また、連続式の場合には30秒から30分程度、好ま
しくは１〜10分程度である。The time for the Ti extraction treatment is about 5 minutes to 5 hours in the case of the batch method, and about 30 seconds to 30 minutes in the case of the continuous method, preferably about 1 to 10 minutes.
酸処理を施して得られたシリカは、次いで任意の温度の
水を用いて洗滌し、必要によりろ過操作を組み合せて脱
酸脱水処理する。The silica obtained by the acid treatment is then washed with water at an arbitrary temperature and, if necessary, a deoxidation dehydration treatment is carried out by combining a filtering operation.
なお、本発明で使用する酸は精製または電子グレードと
称される高純度品を、また原料や使用する酸の希釈また
はシリカの洗滌などに用いる水は不純物の少ない純水を
用いることが好ましい。The acid used in the present invention is preferably a high-purity product called refined or electronic grade, and the water used for diluting the raw material or the acid used or washing the silica is preferably pure water containing few impurities.
なお、アルカリ金属の過硫酸塩もTi抽出助剤としての機
能を有するが、本発明で目的とするシリカはアルカリ金
属についてもその含有率が低いことが望ましいので、本
発明の方法において用いられるTi抽出助剤としての過硫
酸塩化合物はアンモニウム塩であることが好ましい。Although the alkali metal persulfate also has a function as a Ti extraction aid, it is preferable that the target silica of the present invention has a low content rate of alkali metal, so that it is used in the method of the present invention. The persulfate compound as the extraction aid is preferably an ammonium salt.
本発明の方法によれば、アルカリけい酸塩水溶液を原料
として、不純物含有率としてアルカリ金属:10ppm以下、
塩素:3ppm以下、ウランなど放射性元素:3ppb以下、更
に、チタン:5ppm以下である、不純物含有率が極めて低
い高純度のシリカ粒子を得ることができる。According to the method of the present invention, as an alkali silicate aqueous solution as a raw material, alkali metal as an impurity content rate: 10 ppm or less,
It is possible to obtain high-purity silica particles having an extremely low impurity content, in which chlorine is 3 ppm or less, radioactive elements such as uranium are 3 ppb or less, and titanium is 5 ppm or less.
本発明の方法で用いられるAPSは、入手が容易であり、
安全性が高く取扱いやすいのでシリカの製造工程で問題
なく使用することができる。APS used in the method of the present invention is easily available,
Since it is safe and easy to handle, it can be used without problems in the silica manufacturing process.
本発明の方法で得られたシリカ粒子は従来技術による場
合に比較して、不純物含有率が極めて低いので、特に高
集積回路封止用樹脂組成物の充填剤として用いられ、ま
た、透明石英ガラスや特殊セラミックスなどの原料とし
ての用途が期待される。Since the silica particles obtained by the method of the present invention have an extremely low impurity content as compared with the case of the prior art, they are used as a filler for a resin composition for encapsulating highly integrated circuits, and are also transparent quartz glass. It is expected to be used as a raw material for materials such as and special ceramics.
以下、本発明の方法を実施例および比較例により具体的
に説明する。Hereinafter, the method of the present invention will be specifically described with reference to Examples and Comparative Examples.
実施例−1. けい酸ソーダ＃３号（JIS K1408,3号相当品，SiO2:28
％，Na2O:9％,Ti:60ppm）6kgを減圧下で50℃に加温して
脱水濃縮し、SiO2:32％の繊維化用原液を得た。本原液
の粘度は30℃で約100ポイズであり、曳糸性も良好であ
った。Example-1. Sodium silicate # 3 (JIS K1408, No. 3 equivalent, SiO 2 : 28
%, Na 2 O: 9%, Ti: 60 ppm) 6 kg was heated to 50 ° C. under reduced pressure and dehydrated and concentrated to obtain a fiberizing stock solution of SiO 2 : 32%. The viscosity of this stock solution was about 100 poise at 30 ° C, and the spinnability was also good.
この原液をろ過後、押し出し機を用い孔径0.2mmφ，孔
数200個の金−白金合金製ノズルを通して6m/分の速度
で、50℃に保持した反応浴−予めAPS:17.1gを溶解させ
た、硫酸13重量％水溶液20l中へ押し出した。After filtering this undiluted solution, a reaction bath kept at 50 ° C. at a speed of 6 m / min through a gold-platinum alloy nozzle having a hole diameter of 0.2 mmφ and 200 holes using an extruder was used to dissolve APS: 17.1 g in advance. , And extruded into 20 l of a 13% by weight aqueous solution of sulfuric acid.
押し出された原液はNa2Oが酸と反応し中和されて凝固
し、透明な繊維状ゲルに変化した。The extruded stock solution was converted into a transparent fibrous gel by Na 2 O reacting with an acid to be neutralized and coagulated.
反応浴からの繊維状ゲルの取り出しは、ベルトコンベア
ーにより、コンベアーの速度は1m/分で、繊維状ゲルの
反応浴での浸漬時間は約１分であった。The fibrous gel was taken out of the reaction bath by a belt conveyor at a conveyor speed of 1 m / min, and the dipping time of the fibrous gel in the reaction bath was about 1 minute.
得られた繊維状ゲルの40gを、予めAPS0.41gを溶解させ
た、硫酸13重量％硫酸水溶液:500ml中に浸漬し、撹拌し
ながら100℃で30分間処理した。繊維状ゲルはこまかく
開裂し、長さ２〜5mmの短繊維状シリカとなった。40 g of the obtained fibrous gel was immersed in 500 ml of a 13 wt% sulfuric acid aqueous solution in which 0.41 g of APS was dissolved in advance, and the mixture was treated at 100 ° C. for 30 minutes while stirring. The fibrous gel was finely cleaved into short fibrous silica with a length of 2-5 mm.
次いで、得られた短繊維状シリカを脱イオン水500mlの
中に入れて10分間撹拌した後、ヌッチェを用いて脱水し
た。Then, the obtained short fiber silica was put in 500 ml of deionized water, stirred for 10 minutes, and then dehydrated using a Nutsche.
この酸による抽出処理−水洗の操作を３回繰り返し、更
に水による洗滌を５回繰り返した後のシリカ中の硫酸根
濃度は1ppm以下であった。The acid extraction-washing operation was repeated 3 times, and the washing with water was repeated 5 times, and the concentration of sulfate group in the silica was 1 ppm or less.
得られたシリカを150℃で１夜乾燥後、1200℃で１時間
加熱処理した。The obtained silica was dried at 150 ° C. overnight and then heat-treated at 1200 ° C. for 1 hour.
得られたシリカ中の不純物含有率は、表−１に示される
ように、いづれも1ppm以下であった。The content of impurities in the obtained silica was 1 ppm or less in each case as shown in Table 1.
実施例−2. APS使用量を表−２に示すように変えたほかは、実施例
−１と同様の方法によって処理し、シリカを得た。得ら
れたシリカ中の不純物含有率は表−１に併記した通り
で、Ti含有率はいづれも5ppm未満であった。Example-2. Silica was obtained by treating in the same manner as in Example-1, except that the amount of APS used was changed as shown in Table-2. The content of impurities in the obtained silica is as shown in Table 1 together, and the content of Ti was less than 5 ppm in each case.
比較例−1. APSを使用しないほかは、実施例−１と同様の方法によ
って処理し、シリカを得た。Comparative Example-1 Silica was obtained by treating in the same manner as in Example-1, except that APS was not used.
得られたシリカ中の不純物含有率は、表−１に併記した
通りで、Tiは5.0ppmであった。The content of impurities in the obtained silica is as shown in Table 1 together, and Ti was 5.0 ppm.
Claims (1)
リ金属元素、ｎはSiO2のモル数で0.5〜５を示す）で表
されるアルカリけい酸塩の水溶液を鉱酸と反応させ、得
られたシリカを鉱酸で処理して不純物を抽出除去し高純
度シリカを製造する方法において、前記の反応および／
または不純物抽出を過硫酸アンモニウムの存在下で行う
ことを特徴とする高純度シリカの製造方法。1. An aqueous solution of an alkali silicate represented by the general formula: M 2 O.nSiO 2 (where M is an alkali metal element and n is 0.5 to 5 in terms of the number of moles of SiO 2 ), and an aqueous solution of an alkali silicate is used as a mineral acid. And treating the resulting silica with a mineral acid to extract and remove impurities to produce high-purity silica.
Alternatively, a method for producing high-purity silica, which comprises extracting impurities in the presence of ammonium persulfate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28577888A JPH0755818B2 (en) | 1988-11-14 | 1988-11-14 | Method for producing high-purity silica |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28577888A JPH0755818B2 (en) | 1988-11-14 | 1988-11-14 | Method for producing high-purity silica |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02133311A JPH02133311A (en) | 1990-05-22 |
| JPH0755818B2 true JPH0755818B2 (en) | 1995-06-14 |
Family
ID=17695945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28577888A Expired - Fee Related JPH0755818B2 (en) | 1988-11-14 | 1988-11-14 | Method for producing high-purity silica |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0755818B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6791769B2 (en) * | 2017-01-24 | 2020-11-25 | 太平洋セメント株式会社 | Method for manufacturing purified silica |
| JP6804315B2 (en) * | 2017-01-24 | 2020-12-23 | 太平洋セメント株式会社 | Method for manufacturing purified silica |
| JP7089421B2 (en) * | 2018-07-02 | 2022-06-22 | 株式会社アドマテックス | Slurry composition containing fibrous filler and method for producing the same |
-
1988
- 1988-11-14 JP JP28577888A patent/JPH0755818B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02133311A (en) | 1990-05-22 |
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