JP2740810B2 - Production method of silica gel with excellent alkali resistance - Google Patents
Production method of silica gel with excellent alkali resistanceInfo
- Publication number
- JP2740810B2 JP2740810B2 JP1006788A JP678889A JP2740810B2 JP 2740810 B2 JP2740810 B2 JP 2740810B2 JP 1006788 A JP1006788 A JP 1006788A JP 678889 A JP678889 A JP 678889A JP 2740810 B2 JP2740810 B2 JP 2740810B2
- Authority
- JP
- Japan
- Prior art keywords
- silica gel
- alkali resistance
- treatment
- alkali
- aqueous solution
- 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 - Lifetime
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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
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/157—After-treatment of gels
- C01B33/159—Coating or hydrophobisation
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (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） 本発明は耐アルカリ性に優れたシリカゲルの製法に関
するもので、詳しくは、強アルカリ水溶液と接触しても
侵蝕を受けることが少ないシリカゲルを得るための方法
である。Description: TECHNICAL FIELD The present invention relates to a method for producing silica gel having excellent alkali resistance. More specifically, the present invention relates to a method for obtaining a silica gel which is hardly corroded even when contacted with a strong alkaline aqueous solution. This is the method.
（従来技術とその問題点） シリカゲルは幅広い分野で利用されており、例えば、
吸湿乾燥剤、触媒、触媒担体、クロマト分離吸着剤、プ
ラスチック充填剤、アンチブロッキング充填剤、更に、
化粧品原料等に利用されている。(Prior art and its problems) Silica gel is used in a wide range of fields.
Hygroscopic desiccant, catalyst, catalyst carrier, chromatographic separation adsorbent, plastic filler, anti-blocking filler,
It is used as a raw material for cosmetics.
従来、シリカゲルの製法としては、いくつか知られて
いるが、一般的な方法として、例えば、ケイ酸アルカリ
水溶液と鉱酸水溶液とを混合してコロイド状シリカを生
成させ、次いで、ゲル化しヒドロゲルとした後、水洗し
て副生した水溶液の中和塩を除去し、更に、必要に応じ
て、熟成した後、乾燥することにより製造する方法が知
られている。（例えば、特公昭48−13834号参照） ところが、この製法により得られるシリカゲルはアル
カリ水溶液に弱く、特に、強アルカリ水溶液と接触する
と、シリカゲルの一部が溶解侵蝕を受けると言う欠点が
ある。この原因は下記反応式に示す通り、シリカの一部
がケイ酸ナトリウムとなり水溶化するためであるが、特
に、シリカゲル自体の比表面積が極めて大きい（約1000
m2/g以上のものもある）ため、アルカリ水溶液との接触
面積を増大しているのも、この傾向を増大している要因
である。Conventionally, several methods for producing silica gel are known, but as a general method, for example, an aqueous solution of an alkali silicate and an aqueous solution of a mineral acid are mixed to produce colloidal silica, which is then gelled to form a hydrogel. Then, a method is known in which the product is washed with water to remove a neutralized salt of the by-produced aqueous solution, and, if necessary, aged and then dried. (See, for example, Japanese Patent Publication No. 48-13834.) However, the silica gel obtained by this method has a disadvantage that it is susceptible to an aqueous alkali solution, and in particular, when it comes into contact with a strong aqueous alkali solution, a part of the silica gel is dissolved and eroded. This is because a part of silica becomes sodium silicate and becomes water-soluble as shown in the following reaction formula. In particular, the specific surface area of silica gel itself is extremely large (about 1000
m 2 / g or more), an increase in the contact area with the aqueous alkaline solution is also a factor that increases this tendency.
（SiO2）ｎ＋2nNaOH→nNaSiO3＋nH2O そのため、上記製法で得たシリカゲルをアルカリ水溶
液と接触する必要のある用途に利用した場合には、アル
カリにより侵蝕を受け寿命が短かくなる問題点があっ
た。例えば、粒子状シリカゲルを各種蛋白質の分離精製
を目的としたゲル浸透、イオン交換、吸着クロマトグラ
フィー等のカラム充填剤として用いた場合、精製処理後
において、充填剤に吸着した不純蛋白などを脱着のため
強アルカリ水溶液で洗浄することがしばしばあるが、こ
の際に、充填剤である粒状シリカゲルが侵蝕され粒子が
微小化するとともに、充填層の有効容積が減少する問題
が生ずる。また、シリカゲルを固定化酵素の担体として
用いる場合も、基準と酵素の反応終了後、失活酵素の脱
着をアルカリ水溶液にて行なうことがあるが、この場合
も、固定相が同様に侵蝕される現象が発生する。(SiO 2 ) n + 2 nNaOH → nNaSiO 3 + nH 2 O Therefore, when the silica gel obtained by the above-mentioned production method is used for an application requiring contact with an alkaline aqueous solution, there is a problem that the silica is eroded by alkali and the life is shortened. Was. For example, when particulate silica gel is used as a column packing material for gel permeation, ion exchange, adsorption chromatography, etc. for the purpose of separating and purifying various proteins, after the purification treatment, it is possible to desorb impurity proteins and the like adsorbed on the packing material. For this reason, washing with a strong alkaline aqueous solution is often performed. At this time, however, there is a problem that the granular silica gel as the filler is eroded, the particles are miniaturized, and the effective volume of the packed bed is reduced. Also, when silica gel is used as a carrier for the immobilized enzyme, the deactivated enzyme may be desorbed with an alkaline aqueous solution after the reaction between the standard and the enzyme, but in this case, the stationary phase is similarly eroded. The phenomenon occurs.
（発明の課題と解決手段） 本発明者は上記実情に鑑み、ケイ酸アルカリと鉱酸と
から製造されたシリカゲルの耐アルカリ性を改善するこ
とを目的として種々検討した結果、従来法により得たシ
リカゲルに、ジルコニウム成分を担持させることによ
り、耐アルカリ性に優れたシリカゲルが回収できること
を見い出し、本発明を完成するに到った。(Problems and Solutions to the Invention) In view of the above-mentioned circumstances, the present inventors have conducted various studies with the aim of improving the alkali resistance of silica gel produced from an alkali silicate and a mineral acid. In addition, it was found that silica gel having excellent alkali resistance can be recovered by supporting a zirconium component, thereby completing the present invention.
以下、本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
本発明では、主として、ケイ酸アルカリと鉱酸とを主
原料として製造されたシリカゲルを対象とし、これを更
にジルコニル塩水溶液と接触処理することにより、ジル
コニウム成分を担持させるものであるが、原料のケイ酸
アルカリとしては、通常、ケイ酸ナトリウム、ケイ酸カ
リウム、ケイ酸リチウムなどのケイ酸アルカリ金属塩が
挙げられ、一方、鉱酸としては、通常、硫酸、塩酸、硝
酸などの無機酸、又は、酢酸、シュウ酸などの有機酸が
挙げられる。In the present invention, mainly, silica gel produced using an alkali silicate and a mineral acid as main raw materials, and further subjected to a contact treatment with a zirconyl salt aqueous solution to support a zirconium component. As the alkali silicate, usually, sodium silicate, potassium silicate, an alkali metal silicate such as lithium silicate, etc., as the mineral acid, usually, sulfuric acid, hydrochloric acid, inorganic acids such as nitric acid, or Acetic acid, oxalic acid and the like.
ケイ酸アルカリと鉱酸とからシリカゲルを製造する方
法としては、本発明では特に限定されず、種々の公知法
に従って製造することができる。例えば、両者の水溶液
を混合しコロイド状シリカとし、次いで、ゲル化しヒド
ロゲル化した後、水洗、乾燥する方法が採用し得る。そ
して、これらの各工程の条件も、従来の公知法の範囲か
ら選定することができる。本発明で用いるシリカゲルの
タイプは通常、RD型、Ａ型、Ｂ型又はID型のいずれのも
のでもよい。シリカゲルの比表面積は例えば、600m2/g
以上のものが望ましく、特に、本発明の場合、比表面積
の大きいシリカゲルの方が耐アルカリ性の向上効果が大
きい。このようなシリカゲルは市販もされており、例え
ば、富士デヴィソン化学（株）製のシリカゲルなどを用
いるのが望ましい。なお、本発明の処理に供するシリカ
ゲルは、通常、50〜300メッシュ程度の粒径のものが望
ましい。また、本発明ではシリカゲルを予め、150〜200
℃の温度で加熱処理し賦活しておいてもよい。The method for producing silica gel from an alkali silicate and a mineral acid is not particularly limited in the present invention, and it can be produced according to various known methods. For example, a method of mixing both aqueous solutions to form colloidal silica, then gelling and hydrogelling, washing with water, and drying may be employed. The conditions for each of these steps can also be selected from the range of conventional known methods. The type of silica gel used in the present invention may be any of RD type, A type, B type and ID type. The specific surface area of silica gel is, for example, 600 m 2 / g
The above-mentioned ones are desirable, and in the case of the present invention, silica gel having a large specific surface area has a greater effect of improving alkali resistance. Such silica gel is commercially available. For example, silica gel manufactured by Fuji Devison Chemical Co., Ltd. is preferably used. The silica gel to be subjected to the treatment of the present invention preferably has a particle size of about 50 to 300 mesh. Further, in the present invention, silica gel in advance, 150-200
It may be activated by heating at a temperature of ° C.
本発明においては、上述のようなシリカゲルにジルコ
ニウム成分を担持させることを必須の要件とするもので
ある。要するに、このジルコニウム成分を担持させるこ
とにより、シリカゲルの耐アルカリ性を著しく向上させ
ることができるのである。In the present invention, it is essential that a zirconium component is supported on the above-mentioned silica gel. In short, by supporting the zirconium component, the alkali resistance of the silica gel can be significantly improved.
シリカゲルにジルコニウム成分を担持させる方法とし
ては、通常、シリカゲルをジルコニル塩水溶液と接触処
理する方法が代表的である。ジルコニル塩としては、通
常、硝酸、塩酸、硫酸、リン酸などの無機酸又は酢酸、
プロピオン酸、ナフテン酸などの有機酸のジルコニル塩
が挙げられ、なかでも、硝酸ジルコニルが好ましい。ジ
ルコニル塩水溶液の濃度はシリカゲルとの接触方式及び
処理条件などにより異なるが、一般的には、シリカゲル
1g当りに対して0.1〜50重量％、好ましくは0.4〜25重量
％である。As a method of supporting a zirconium component on silica gel, typically, a method of treating silica gel with an aqueous solution of zirconyl salt is typical. As the zirconyl salt, usually, an inorganic acid such as nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid,
Examples include zirconyl salts of organic acids such as propionic acid and naphthenic acid, and among them, zirconyl nitrate is preferable. The concentration of the aqueous zirconyl salt solution varies depending on the method of contact with silica gel and the processing conditions.
It is 0.1 to 50% by weight, preferably 0.4 to 25% by weight, based on 1 g.
ジルコニル塩水溶液とシリカゲルとの接触処理の方法
は、通常、ジルコニウム塩水溶液中にシリカゲルを混
合し、必要に応じて、減圧脱泡した後、例えば、0.5〜2
0時間、常温〜60℃で浸漬処理を行なう方法、シリカ
ゲルを充填したカラムにジルコニル塩水溶液を通液処理
する方法、シリカゲルに対してジルコニル塩水溶液を
均一に散布し均一混合した後、例えば、0.5〜20時間、
常温で保持する方法などが挙げられる。また、接触処理
の温度は例えば、10〜80℃程度の温度でよいが、通常は
室温でよい。この接触処理により、シリカゲルにジルコ
ニウム成分を担持させることができる。ジルコニウム成
分の担持量としては、通常、シリカゲルのシラノール基
の濃度に対して、Zrとして0.01〜0.2倍である。ジルコ
ニウム成分の担持量があまり少ない場合には、本発明で
期待する耐アルカリ性の向上効果は減退する。The method of contact treatment between the aqueous solution of zirconyl salt and silica gel is usually performed by mixing silica gel in an aqueous solution of zirconium salt and, if necessary, defoaming under reduced pressure, for example, 0.5 to 2
0 hours, a method of performing immersion treatment at room temperature to 60 ° C., a method of passing a zirconyl salt aqueous solution through a column filled with silica gel, and uniformly spraying and uniformly mixing the zirconyl salt aqueous solution with respect to silica gel, for example, 0.5 ~ 20 hours,
For example, a method of holding at room temperature may be used. Further, the temperature of the contact treatment may be, for example, a temperature of about 10 to 80 ° C., but is usually room temperature. The zirconium component can be supported on the silica gel by this contact treatment. The loading amount of the zirconium component is usually 0.01 to 0.2 times as Zr with respect to the concentration of the silanol group of the silica gel. If the amount of the supported zirconium component is too small, the effect of improving alkali resistance expected in the present invention is reduced.
ジルコニル塩水溶液との接触処理を終えたシリカゲル
は、通常、引き続き水洗処理すると、シリカゲルの耐ア
ルカリ性が一層向上するので望ましい。水洗処理は通
常、シリカゲルをカラムに充填し、カラム中に水を連続
的に通水する方法、又は、水中にシリカゲルを懸濁さ
せ、次いで、傾斜あるいは濾過により水を除去する方法
などが採用される。後者の場合、例えば、２〜10回程
度、繰り返し実施してもよい。水洗処理の温度は通常、
常温で差し支えない。The silica gel which has been subjected to the contact treatment with the aqueous solution of zirconyl salt is usually desirably subjected to a subsequent washing treatment, since the alkali resistance of the silica gel is further improved. The washing process is usually carried out by packing silica gel into a column and continuously passing water through the column, or suspending silica gel in water and then removing the water by slanting or filtration. You. In the latter case, for example, it may be repeatedly performed about 2 to 10 times. The temperature of the washing process is usually
No problem at room temperature.
次いで、シリカゲルは乾燥した後、製品化されるが、
更に、本発明では、ジルコニウムを担持したシリカゲル
を焼成処理することにより、一段と耐アルカリ性に優れ
た高品質の製品にすることができる。この焼成処理は通
常、200〜600℃の温度で、0.5〜24時間である。そし
て、焼成処理は通常、大気中で実施され、その加熱方法
は直接加熱又は間接加熱のいずれでもよい。焼成装置と
しては、例えば、電気高温マッフル炉、管状炉、連続ロ
ータリーキルン、連続コンベアー式電気炉、タンマン
炉、チューブ炉、坩堝炉、流気式電気炉、ポット炉など
が使用される。Next, the silica gel is dried and then commercialized,
Further, in the present invention, by baking the silica gel supporting zirconium, it is possible to obtain a high-quality product having more excellent alkali resistance. This baking treatment is usually performed at a temperature of 200 to 600 ° C. for 0.5 to 24 hours. The firing treatment is usually performed in the atmosphere, and the heating method may be either direct heating or indirect heating. As the firing apparatus, for example, an electric high-temperature muffle furnace, a tubular furnace, a continuous rotary kiln, a continuous conveyor-type electric furnace, a Tamman furnace, a tube furnace, a crucible furnace, a flow-type electric furnace, a pot furnace, and the like are used.
このようにして得られた、ジルコニウム成分が担持さ
れたシリカゲルは強アルカリとの接触によっても、その
重量が殆ど減少することもなく、耐アルカリ性が非常に
優れたものである。The thus-obtained silica gel carrying a zirconium component has a very high alkali resistance, with almost no decrease in weight even by contact with a strong alkali.
（実施例） 次に、本発明を実施例により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
記述に制約されるものではない。EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.
＜耐アルカリ性（重量減少率）測定方法＞ シリカゲルの試料を内径3mm、長さ23cmのステンレス
製パイプに充填し、これを蒸留水中で減圧脱泡した後、
pH9の水酸化ナトリウム水溶液を45℃の温度において6g/
minの流速で90分間、上向流により通液し、次いで、試
料を回収し170℃の温度で１時間乾燥した後、処理前後
のシリカゲルの重量減少率を次式（１）により求めた。<Method of measuring alkali resistance (weight loss ratio)> A silica gel sample was filled into a stainless steel pipe having an inner diameter of 3 mm and a length of 23 cm, and this was defoamed in distilled water under reduced pressure.
pH 9 sodium hydroxide aqueous solution at a temperature of 45 ℃ 6g /
The liquid was passed through an upward flow at a flow rate of min for 90 minutes, then the sample was recovered and dried at a temperature of 170 ° C. for 1 hour, and the weight loss rate of the silica gel before and after the treatment was determined by the following equation (1).
ここでアルカリ処理前重量とは170℃２時間焼成後デ
ジケーター内で常温に冷却し測定したシリカゲルの重量
であり、アルカリ処理後重量とは水酸化ナトリウムで調
製したpH9.0の水溶液を90分間6g/minの流量で接触させ
た後デジケーター中で常温に冷却し測定たシリカゲルの
重量である。 Here, the weight before alkali treatment is the weight of silica gel measured at 170 ° C. for 2 hours and then cooled to room temperature in a digitizer, and the weight after alkali treatment is 6 g of an aqueous solution of pH 9.0 prepared with sodium hydroxide for 90 minutes. The weight of silica gel measured after contacting at a flow rate of / min and cooling to room temperature in a digitizer.
実施例１ シリカゲル（富士デヴィソン化学（株）製）（比表面
積656m2/g）を粉砕し粒度80〜100メッシュのものを分級
し、これを予め、170℃の温度で２時間、加熱し賦活し
たシリカゲルを得た。Example 1 Silica gel (manufactured by Fuji Devison Chemical Co., Ltd.) (specific surface area: 656 m 2 / g) was pulverized and classified into particles having a particle size of 80 to 100 mesh, which were previously heated at 170 ° C. for 2 hours to activate. Silica gel was obtained.
このシリカゲル30gを硝酸ジルコニル（和光純薬
（株）製）17.8gを蒸溜水150mlに溶解した溶液中に浸漬
し、減圧脱泡を１時間、行なった後、常温で12時間、撹
拌処理を行なった。30 g of this silica gel was immersed in a solution of 17.8 g of zirconyl nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) in 150 ml of distilled water, degassed under reduced pressure for 1 hour, and then stirred at room temperature for 12 hours. Was.
次いで、混合物中のシリカゲルを濾過した後、170℃
の温度で２時間、乾燥することにより、ジルコニウム成
分を担持したシリカゲルを得た。Next, after filtering the silica gel in the mixture, 170 ° C.
At a temperature of 2 hours to obtain a silica gel supporting a zirconium component.
このシルカゲルについて、耐アルカリ性テストを行な
い、シリカゲルの重量減少率を求めたところ、4.42wt％
であり、原料シリカゲルの場合の重量減少率5.75wt％に
比べて、耐アルカリ性に優れたものであった。This silica gel was subjected to an alkali resistance test to determine the weight loss rate of silica gel.
It was excellent in alkali resistance as compared with the weight loss rate of the raw material silica gel of 5.75 wt%.
実施例２ 実施例１の方法において、硝酸ジルコニルとの接触処
理をシリカゲル10gに対し、硝酸ジルコニル8.26gを蒸溜
水50mlに溶解した溶液4.18mlを加え、よく振とうした
後、常温で12時間、密閉状態で保持することにより行な
った以外は、実施例１と同様な処理を行なったところ、
第１表に示す結果であった。Example 2 In the method of Example 1, the contact treatment with zirconyl nitrate was carried out by adding 4.18 ml of a solution of 8.26 g of zirconyl nitrate in 50 ml of distilled water to 10 g of silica gel, and shaking well. The same treatment as in Example 1 was carried out except that the treatment was carried out in a closed state.
The results are shown in Table 1.
実施例３ 実施例１の方法において、硝酸ジルコニル溶液との接
触処理を終えたシリカゲル10gについて、蒸溜水100mlに
懸濁させ撹拌後、10分間、放置し、次いで、上澄を捨て
再び蒸溜水100mlを加え懸濁させる洗浄処理を10回、繰
り返し行なった後、実施例１と同様な乾燥を行なった場
合の結果を第１表に示す。Example 3 In the method of Example 1, 10 g of silica gel which had been subjected to the contact treatment with the zirconyl nitrate solution was suspended in 100 ml of distilled water, stirred, left to stand for 10 minutes, and then the supernatant was discarded and 100 ml of distilled water was discarded again. Table 1 shows the results in the case where the washing treatment for adding and suspending was repeated 10 times and then the same drying as in Example 1 was performed.
実施例４ 実施例１の方法において、硝酸ジルコニル溶液との接
触処理を終えたシリカゲル1gをステンレス製パイプ（内
径3mm、長さ23cm）に充填し、これに蒸溜水を通液し減
圧脱泡した後、45℃の温度で6g/minの流速で50分間、上
向流により通液する洗浄処理を施した後、実施例１と同
様な乾燥を行なった場合の結果を第１表に示す。Example 4 In the method of Example 1, 1 g of silica gel which had been subjected to the contact treatment with the zirconyl nitrate solution was filled in a stainless steel pipe (inner diameter 3 mm, length 23 cm), distilled water was passed through the pipe, and degassing was performed under reduced pressure. Then, after performing a washing treatment in which the solution is passed by an upward flow at a temperature of 45 ° C. and a flow rate of 6 g / min for 50 minutes, the same drying as in Example 1 is performed, and the results are shown in Table 1.
実施例５ 実施例２の方法において、硝酸ジルコニル溶液との接
触処理を終えたシリカゲル1gを実施例４に記載した洗浄
処理を施した後、実施例２と同様な処理を行なった場合
の結果を第１表に示す。Example 5 In the method of Example 2, the results obtained when 1 g of silica gel that had been subjected to the contact treatment with the zirconyl nitrate solution was subjected to the washing treatment described in Example 4 and then subjected to the same treatment as in Example 2 were performed. It is shown in Table 1.
実施例６ 実施例３の方法において、水による洗浄処理を終えた
シリカゲルを300℃の温度で２時間、焼成処理した場合
の結果を第１表に示す。Example 6 Table 1 shows the results obtained when the silica gel which had been washed with water in the method of Example 3 was calcined at a temperature of 300 ° C. for 2 hours.
実施例７ 実施例２の方法において、原料シリカゲルとして比表
面積730m2/gのものを粉砕して得た80〜100メッシュのも
のを用い、全く同様な処理を行い、シリカゲルの重量減
少率を求めたところ、2.7wt％であり、原料シリカゲル
の場合の重量減少率8.0wt％に比べて、大幅に耐アルカ
リ性が向上していた。Example 7 In the method of Example 2, a material having a specific surface area of 730 m 2 / g was used as a raw material silica gel, and 80 to 100 mesh obtained by pulverization was used. As a result, it was 2.7 wt%, and the alkali resistance was greatly improved as compared with the weight reduction rate of 8.0 wt% in the case of the raw material silica gel.
（効果） 以上のように、本発明によれば、シリカゲルをジルコ
ニル塩水溶液と接触処理することにより、シリカゲルに
ジルコニウム成分を担持させることにより耐アルカリ性
が大幅に向上した高品質のシリカゲルを得ることができ
る。したがって、本発明で得たシリカゲルを例えば、各
種カラム充填剤として用いても、アルカリ洗浄時にシリ
カゲル粒子が浸蝕されることもなく、充填剤としての寿
命を長くすることができる。 (Effects) As described above, according to the present invention, by contacting silica gel with an aqueous zirconyl salt solution, it is possible to obtain a high-quality silica gel having alkali resistance greatly improved by supporting the zirconium component on the silica gel. it can. Therefore, even when the silica gel obtained in the present invention is used as, for example, various column fillers, the silica gel particles are not eroded during alkali washing, and the life of the filler can be extended.
Claims (1)
せることを特徴とする耐アルカリ性に優れたシリカゲル
の製法。1. A method for producing silica gel having excellent alkali resistance, wherein a silica gel carries a zirconium component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006788A JP2740810B2 (en) | 1989-01-13 | 1989-01-13 | Production method of silica gel with excellent alkali resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1006788A JP2740810B2 (en) | 1989-01-13 | 1989-01-13 | Production method of silica gel with excellent alkali resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02188420A JPH02188420A (en) | 1990-07-24 |
| JP2740810B2 true JP2740810B2 (en) | 1998-04-15 |
Family
ID=11647918
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1006788A Expired - Lifetime JP2740810B2 (en) | 1989-01-13 | 1989-01-13 | Production method of silica gel with excellent alkali resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2740810B2 (en) |
-
1989
- 1989-01-13 JP JP1006788A patent/JP2740810B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH02188420A (en) | 1990-07-24 |
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