JP2010195657A - Method for producing ultrafine particle tin oxide powder - Google Patents
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本発明は、超微細な酸化錫粉末の製造方法に関し、より詳しくは、比表面積１０ｍ2以上の超微細な酸化錫粉末を容易に製造する方法に関する。 The present invention relates to a method for producing ultrafine tin oxide powder, and more particularly to a method for easily producing ultrafine tin oxide powder having a specific surface area of 10 m 2 or more.
液晶表示装置などに透明導電材料のＩＴＯ等の薄膜が広く用いられている。近年、液晶表示装置などの高精細化や高透明化のために、ＩＴＯ薄膜を形成するターゲット（酸化Ｉｎ−酸化錫、酸化Ｇａ−酸化錫など）について、内部構造の均一化、および利用効率の向上のためノジュール発生低減化による高性能化が求められている。このため、副成分の酸化錫についても微細粉末が求められている。 Thin films of transparent conductive material such as ITO are widely used in liquid crystal display devices and the like. In recent years, targets for forming an ITO thin film (such as oxide In-tin oxide and oxide oxide Ga-tin oxide) for high definition and high transparency of liquid crystal display devices, etc. There is a need for higher performance by reducing the generation of nodules for improvement. For this reason, fine powders are also required for the subcomponent tin oxide.
従来、酸化錫粉末の製造方法として以下の方法が知られている。
（イ）塩化第二錫溶液をアンモニア等で中和し、メタ錫酸と水酸化錫の混合沈澱を生成させ、これを回収し、空気中で５００℃以上に強熱して酸化錫粉末を製造する方法。
（ロ）金属錫を硝酸溶解し、あるいは電解酸化してメタ錫酸を形成した後に、焼成酸化して酸化錫粉末を製造する方法（特許文献１：特許第３１７３４４０号公報）。
（ハ）塩化第二錫をアルコールに溶解した溶液と、アンモニア水とアルコールの混合溶液を徐々に混合して錫酸化物を生成させ、この錫酸化物を濾別し、回収した錫酸化物ケーキに水を加えて攪拌し、濾過する処理を数回繰り返して酸根を除去した後に、水を加えて錫酸化物ゾルを製造する方法（特許文献２：特開２００３−８９５２４号公報）。
Conventionally, the following methods are known as methods for producing tin oxide powder.
(B) The stannic chloride solution is neutralized with ammonia, etc., to produce a mixed precipitate of metastannic acid and tin hydroxide, which is recovered and ignited in air at 500 ° C. or higher to produce tin oxide powder. how to.
(B) A method of producing tin oxide powder by dissolving metal tin in nitric acid or electrolytically oxidizing it to form metastannic acid, followed by baking oxidation (Patent Document 1: Japanese Patent No. 3173440).
(C) A solution in which stannic chloride is dissolved in alcohol and a mixed solution of aqueous ammonia and alcohol are gradually mixed to produce tin oxide, and this tin oxide is filtered and recovered. A method of adding tin to water, stirring and filtering several times to remove acid radicals and then adding water to produce a tin oxide sol (Patent Document 2: JP 2003-89524 A).
上記(イ)(ロ)の方法によって製造される酸化錫粉末は比表面積１０ｍ2未満であり、これより微細な酸化錫粉末を得ることができない。また、これらの酸化錫粉末をビーズミルなどでひたすら粉砕しても、最大でも比表面積９ｍ2程度であり、これ以上に微粉化するのが難しい。一方、上記(ハ)の方法によれば粒径がサブミクロンの酸化錫微粒子が懸濁したゾルが形成される。しかし、有機溶媒中で塩化錫を加水分解する方法であるため処理に手間がかかり面倒である。また、この方法で得られるのは錫酸化物ゾル（酸化錫含有量６〜１２重量％）であり、通常の濾布では濾別することができないので、乾燥粉末化するのに手間がかかる。 The tin oxide powder produced by the above methods (a) and (b) has a specific surface area of less than 10 m 2 , and a finer tin oxide powder cannot be obtained. Moreover, even if these tin oxide powder was earnestly ground in bead mill, a specific surface area 9m 2 approximately at the maximum, it is difficult to finely divided further into. On the other hand, according to the method (c), a sol in which tin oxide fine particles having a particle size of submicron are suspended is formed. However, since it is a method of hydrolyzing tin chloride in an organic solvent, the process is troublesome and troublesome. Further, a tin oxide sol (tin oxide content: 6 to 12% by weight) obtained by this method cannot be separated by a normal filter cloth, so that it takes time and effort to form a dry powder.
また、従来の上記製造方法(イ)(ロ)は、回収した殿物を空気中で焼成し酸化させてＳｎＯ2にするため、焼成時に融着しやすく、微細な酸化錫粉末を得るのが難しい。また、上記(ロ)の方法は、メタ錫酸の粒径が比較的大きいため、低温で長時間かけて焼成しても微細な酸化錫粉末を得られない。さらに、これらの酸化錫粉末をさらに機械粉砕する方法では微細化に限界があり、粉砕装置からの不純物の混入も問題になる。 In addition, since the conventional production methods (a) and (b) are fired and oxidized in the air to oxidize SnO 2 , it is easy to fuse during firing, and a fine tin oxide powder is obtained. difficult. In the method (b), since the particle diameter of metastannic acid is relatively large, fine tin oxide powder cannot be obtained even if it is fired for a long time at a low temperature. Furthermore, the method of further mechanically pulverizing these tin oxide powders has a limit in miniaturization, and mixing of impurities from the pulverizer becomes a problem.
本発明は、従来の製造方法における上記問題を解決したものであり、簡単な処理手段によって比表面積１０ｍ2以上の酸化錫微粉末を製造する方法を提供する。 The present invention solves the above-mentioned problems in the conventional production method, and provides a method for producing a tin oxide fine powder having a specific surface area of 10 m 2 or more by simple processing means.
本発明は、以下の構成によって上記問題を解決した酸化錫微粉末の製造方法に関する。
〔１〕塩化第一錫溶液を、過酸化水素の存在下、該溶液中の錫量に対して１５０グラム当量倍以上の加熱水に混合し、生成した酸化錫沈澱を濾別回収し、乾燥後、熱処理することによって比表面積１０ｍ2以上の酸化錫粉末を製造することを特徴とする酸化錫微粉末の製造方法。
〔２〕錫濃度１０ｇ/Ｌ以上の塩化第一錫溶液を、過酸化水素の存在下、該溶液中の錫量に対して１５０グラム当量倍以上の４５℃以上に加熱した純水に、攪拌下、少量づつ添加し、酸化錫沈澱を生成させる上記[１]の酸化錫微粉末の製造方法。
〔３〕塩化第一錫溶液を、該溶液中の錫量に対して１当量以上の過酸化水素を含み、該溶液中の錫量に対して１５０グラム当量倍以上の４５℃〜７５℃に加熱した純水に混合する上記[１]または上記[２]に記載する酸化錫微粉末の製造方法。
〔４〕塩化第一錫溶液に該溶液中の錫量に対して１当量以上の過酸化水素を加えてなる前駆体溶液を、該溶液中の錫量に対して１５０グラム当量倍以上の４５℃〜７５℃に加熱した純水に混合する上記[１]または上記[２]に記載する酸化錫微粉末の製造方法。
〔５〕塩化第一錫溶液を、該溶液中の錫量に対して１５０グラム当量倍以上の加熱水に、攪拌しながら、３０分以上の時間をかけて滴下する上記[１]〜上記[４]の何れかに記載する酸化錫微粉末の製造方法。
〔６〕回収した酸化錫沈澱を５０℃〜１５０℃に加熱乾燥し、純水を加えた後に２００℃〜７５０℃で仮焼する上記[１]〜上記[５]の何れかに記載する酸化錫微粉末の製造方法。
The present invention relates to a method for producing a tin oxide fine powder that solves the above problems by the following constitution.
[1] Stannous chloride solution is mixed with heated water at least 150 gram equivalent times the amount of tin in the presence of hydrogen peroxide, and the resulting tin oxide precipitate is collected by filtration and dried. Thereafter, a tin oxide powder having a specific surface area of 10 m 2 or more is produced by heat treatment.
[2] Stir a stannous chloride solution having a tin concentration of 10 g / L or more in pure water heated to 45 ° C. or more, which is 150 grams equivalent times or more the amount of tin in the solution in the presence of hydrogen peroxide. The method for producing a fine powder of tin oxide according to the above [1], wherein the fine powder is added little by little to produce a tin oxide precipitate.
[3] The stannous chloride solution contains 1 equivalent or more of hydrogen peroxide with respect to the amount of tin in the solution, and is 45 ° C. to 75 ° C., which is 150 grams equivalent or more with respect to the amount of tin in the solution. The method for producing a tin oxide fine powder according to the above [1] or [2], which is mixed with heated pure water.
[4] A precursor solution obtained by adding one equivalent or more of hydrogen peroxide to the stannous chloride solution with respect to the amount of tin in the solution is 45 grams equivalent to 45 times or more of the amount of tin in the solution. The manufacturing method of the tin oxide fine powder as described in the above [1] or the above [2], which is mixed with pure water heated to from 75 ° C to 75 ° C.
[5] The above-mentioned [1] to [[] above, wherein the stannous chloride solution is added dropwise to heated water of 150 gram equivalent times or more with respect to the amount of tin in the solution over 30 minutes while stirring. 4] The method for producing a tin oxide fine powder according to any one of [4].
[6] The recovered tin oxide precipitate is heated and dried at 50 ° C to 150 ° C, pure water is added, and then calcined at 200 ° C to 750 ° C. The oxidation according to any one of [1] to [5] above Manufacturing method of tin fine powder.
本発明の方法によれば、塩化第一錫溶液から適度に微細な酸化錫粉末を容易に製造することができる。本発明の方法によって製造される酸化錫微粉末は比表面積が大きく、１０ｍ2以上であるので、高い活性を有し、ＩＴＯの酸化錫材料に用いたときに、高密度で焼結性のよいターゲットを得ることができる。 According to the method of the present invention, a moderately fine tin oxide powder can be easily produced from a stannous chloride solution. Since the tin oxide fine powder produced by the method of the present invention has a large specific surface area of 10 m 2 or more, it has a high activity and has a high density and good sinterability when used as an ITO tin oxide material. You can get a target.
本発明の製造方法では、塩化第一錫溶液を大量の加熱水に混合し、過酸化水素の存在下で生成した酸化錫沈澱は、市販されている通常の濾布によって濾過することができるので、酸化錫沈澱の回収が容易である。さらに、塩化第一錫溶液を大量の加熱水に混合することによって塩素含有量の少ない酸化錫粉末を得ることができる。 In the production method of the present invention, the stannous chloride solution produced by mixing the stannous chloride solution with a large amount of heated water and in the presence of hydrogen peroxide can be filtered through a commercially available ordinary filter cloth. Recovery of the tin oxide precipitate is easy. Furthermore, a tin oxide powder with a low chlorine content can be obtained by mixing the stannous chloride solution with a large amount of heated water.
また、本発明の製造方法では、回収した酸化錫沈澱を加熱乾燥した後に、純水を加えて仮焼することによって、仮焼しても焼結しない粉末状態の微細な酸化錫粉末を容易に得ることができる。本発明の製造方法は、加熱水の水中で酸化錫を直接生成させので、仮焼時には酸化反応せず、焼結し難いので微細な粉末が得られる。なお、結晶水を
Further, in the production method of the present invention, the recovered tin oxide precipitate is heated and dried, and then pure water is added and calcined to easily obtain fine tin oxide powder in a powder state that does not sinter even if calcined. Obtainable. According to the production method of the present invention, tin oxide is directly generated in heated water, so that it does not undergo oxidation reaction during calcination and is difficult to sinter, so that a fine powder can be obtained. In addition, crystal water
以下、本発明を実施形態に基づき具体的に説明する。
本発明の製造方法は、塩化第一錫溶液を、過酸化水素の存在下、該溶液中の錫量に対して１５０グラム当量倍以上の加熱水に混合し、生成した酸化錫沈澱を濾別回収し、乾燥後、熱処理することによって比表面積１０ｍ2以上の酸化錫粉末を製造することを特徴とする酸化錫微粉末の製造方法である。
Hereinafter, the present invention will be specifically described based on embodiments.
In the production method of the present invention, a stannous chloride solution is mixed with heated water at least 150 gram equivalent times the amount of tin in the solution in the presence of hydrogen peroxide, and the resulting tin oxide precipitate is filtered off. A method for producing a fine tin oxide powder comprising producing a tin oxide powder having a specific surface area of 10 m 2 or more by collecting, drying and heat-treating.
本発明の製造方法に用いる塩化第一錫溶液（SnCl2・２H2O）は、金属錫を塩酸で加熱溶解して調製した塩化第一錫塩酸溶液を用いることができる。あるいは、塩化第一錫を水または希塩酸水（十分に精製された塩化第一錫を用いる場合には塩酸を用いなくてもよい）に溶解して調製した塩化第一錫溶液を用いることができる。塩化第一錫溶液は液中の錫濃度が１０ｇ/Ｌ以上の高濃度溶液が好ましい。溶液中の錫濃度がこれより低いと、生成物が微細になり、濾過が難しくなる。実操業では錫濃度４０〜１１０ｇ/Ｌの塩化第一錫溶液が適当である。塩化第一錫溶液は余剰な塩酸を含むものでもよい。なお、塩化第二錫溶液（SnCl4・５H2O）を用いてもよいが、一般に塩化第二錫は高価であるので、コストの点で不利になる。 As the stannous chloride solution (SnCl 2 .2H 2 O) used in the production method of the present invention, a stannous chloride hydrochloric acid solution prepared by heating and dissolving metallic tin with hydrochloric acid can be used. Alternatively, a stannous chloride solution prepared by dissolving stannous chloride in water or dilute hydrochloric acid water (in the case of using sufficiently purified stannous chloride, hydrochloric acid may not be used) can be used. . The stannous chloride solution is preferably a high concentration solution having a tin concentration of 10 g / L or more. If the tin concentration in the solution is lower than this, the product becomes fine and filtration becomes difficult. In actual operation, a stannous chloride solution having a tin concentration of 40 to 110 g / L is suitable. The stannous chloride solution may contain excess hydrochloric acid. Although a stannic chloride solution (SnCl 4 .5H 2 O) may be used, since stannic chloride is generally expensive, it is disadvantageous in terms of cost.
過酸化水素（H2O2）は、塩化第一錫溶液に添加した前駆体溶液として用いてもよく、あるいは加熱水に添加してもよい。過酸化水素の添加量は上記塩化第一錫溶液中の錫量に対して１当量以上が好ましい。この量が１当量より少ないと、過酸化水素を添加したときに茶色い沈澱になり、濾過性のよい酸化錫沈澱が得られず、歩留まりが低下する。 Hydrogen peroxide (H 2 O 2 ) may be used as a precursor solution added to the stannous chloride solution, or may be added to heated water. The amount of hydrogen peroxide added is preferably 1 equivalent or more with respect to the amount of tin in the stannous chloride solution. When this amount is less than 1 equivalent, a brown precipitate is formed when hydrogen peroxide is added, and a tin oxide precipitate with good filterability cannot be obtained, resulting in a decrease in yield.
塩化第一錫溶液を混合する加熱水は、上記溶液中の錫量に対して１５０グラム当量倍以上の水量が用いられる。塩化第一錫溶液を大量の加熱水に混合することによって塩素含有量の少ない酸化錫粉末を得ることができる。加熱水の水量がこれより少ないと、生成物の歩留まりが低下し、また生成物中の塩素含有量が高くなる。加熱水の温度は４５℃以上が適当であり、４５℃〜７５℃が好ましい。加熱水の温度が４５℃より低いと濾過性のよい酸化錫沈澱が得られず、７５℃より高いと装置上の問題が生じると共にエネルギーが無駄になる。 As the heating water for mixing the stannous chloride solution, an amount of water that is 150 grams equivalent times or more the amount of tin in the solution is used. By mixing the stannous chloride solution with a large amount of heated water, a tin oxide powder having a low chlorine content can be obtained. If the amount of heated water is less than this, the yield of the product will decrease, and the chlorine content in the product will increase. The temperature of the heated water is suitably 45 ° C or higher, preferably 45 ° C to 75 ° C. If the temperature of the heated water is lower than 45 ° C., a tin oxide precipitate having good filterability cannot be obtained, and if it is higher than 75 ° C., problems on the apparatus occur and energy is wasted.
塩化第一錫溶液を、過酸化水素の存在下で、加熱水に混合するには、塩化第一錫溶液を少量づつ攪拌した加熱水に添加する。例えば、塩化第一錫溶液を３０分以上の時間をかけて滴下するのが好ましい。 To mix the stannous chloride solution with heated water in the presence of hydrogen peroxide, the stannous chloride solution is added in small portions to the stirred heated water. For example, it is preferable to drop the stannous chloride solution over 30 minutes or more.
上記添加方法とは逆に、塩化第一錫溶液に加熱水を少量づつ添加すると沈澱物粒子が過小になり、濾過性のよい酸化錫沈澱は得られない。また、上記沈澱生成工程において、従来の製造方法で使用されている加水分解剤のアンモニア等を用いる必要はない。塩化第一錫溶液を過酸化水素の存在下で加熱水に滴下することによって、アンモニア等を用いずに、実用的なフィルター濾過が可能な濾過性の良い超微細な酸化錫沈澱を形成することができる。 Contrary to the above addition method, when heating water is added to the stannous chloride solution little by little, the precipitate particles become too small, and a tin oxide precipitate with good filterability cannot be obtained. Moreover, it is not necessary to use ammonia of the hydrolyzing agent currently used by the conventional manufacturing method in the said precipitation production | generation process. By dropping the stannous chloride solution into heated water in the presence of hydrogen peroxide to form ultrafine tin oxide precipitates with good filterability that can be practically filtered without using ammonia, etc. Can do.
塩化第一錫（SnCl2・２H2O）は、過酸化水素によって酸化されて、過酸化な錫の前駆体溶液になり、これを加熱水に混合することによって、加熱によって次式[１]〜[３]の反応が進み、酸化錫（SnO2）の沈澱が直接生じる。この沈澱物を濾過して回収し、加熱乾燥した後に、純水を加えて仮焼する。 Stannous chloride (SnCl 2 · 2H 2 O) is oxidized by hydrogen peroxide to become a peroxidized tin precursor solution, which is mixed with heated water and heated to the following formula [1] The reaction of [3] proceeds, and precipitation of tin oxide (SnO 2 ) occurs directly. This precipitate is collected by filtration, dried by heating, and then calcined with pure water.
SnCl2＋H2O2 → SnO2↓＋２HCl 〔１〕
SnCl2＋２HCl＋H2O2 → SnCl4＋２H2Ｏ 〔２〕
SnCl4＋２H2Ｏ → SnO2↓＋４HCl 〔３〕
SnCl 2 + H 2 O 2 → SnO 2 ↓ + 2HCl [1]
SnCl 2 + 2HCl + H 2 O 2 → SnCl 4 + 2H 2 O [2]
SnCl 4 + 2H 2 O → SnO 2 ↓ + 4HCl [3]
回収した沈殿物を５０℃〜１５０℃に加熱して乾燥し、純水を加えると水が弾けて沈澱物を粉状態にすることができる。これを２００℃〜７５０℃で仮焼しても焼結し難いので、比表面積１０ｍ2以上の微細な酸化錫粉末を容易に得ることができる。また、沈殿物を加熱乾燥した後に純水を添加することによって、ゲル状の硬く固結した状態の生成物が粉末化し、また沈殿物に残留する塩素も除去することができる。回収沈澱に加える純水の水量は沈澱１ｇに対して１ｇ以上が好ましく、余剰な水分は濾過して除去すればよい。 The collected precipitate is heated to 50 ° C. to 150 ° C. and dried, and when pure water is added, the water is repelled and the precipitate can be made into a powder state. Since it is difficult to sinter even if calcined at 200 ° C. to 750 ° C., fine tin oxide powder having a specific surface area of 10 m 2 or more can be easily obtained. Further, by adding pure water after the precipitate is heated and dried, the gel-like hard and consolidated product is pulverized, and chlorine remaining in the precipitate can be removed. The amount of pure water added to the recovered precipitate is preferably 1 g or more with respect to 1 g of the precipitate, and excess water may be removed by filtration.
さらに、仮焼することによって残留塩素が揮発して除去される。沈澱物に残留する塩化第二錫は沸点が低い（約１１４℃）ので、２００℃以上に仮焼することによって除去することができる。仮焼後に粒度調整のために微粉砕あるいは解砕しても良い。仮焼温度は２００℃〜７５０℃が適当である。２００℃より低いと残留塩素の除去が不十分になり、７５０℃を上回ると酸化錫が焼結しやすくなり、比表面積が急激に低下する。なお、結晶水を除きたい場合には高温で仮焼するほどよい。 Furthermore, residual chlorine volatilizes and is removed by calcination. Since stannic chloride remaining in the precipitate has a low boiling point (about 114 ° C.), it can be removed by calcination at 200 ° C. or higher. After calcination, fine pulverization or pulverization may be performed for particle size adjustment. The calcining temperature is suitably 200 ° C to 750 ° C. When the temperature is lower than 200 ° C., residual chlorine is not sufficiently removed. When the temperature is higher than 750 ° C., tin oxide is easily sintered and the specific surface area is rapidly decreased. In addition, when it is desired to remove crystal water, it is better to calcine at high temperature.
本発明の実施例を以下に示す。結果を表１に示す。
〔比表面積〕酸化錫粉末の比表面積はＱＵＡＮＴＡＣＨＲＯＭＥ社製ＡＵＴＯＳＯＲＢ−１ＭＰ機を用い、ＢＥＴ３点法に従ってＢＥＴ比表面積を測定した。
Examples of the present invention are shown below. The results are shown in Table 1.
[Specific surface area] The BET specific surface area of the tin oxide powder was measured according to the BET three-point method using an AUTOSORB-1MP machine manufactured by QUANTACHROME.
〔実施例１〕
塩化第一錫５００ｇを純水２.８リットルおよび塩酸１５０ccに溶解して原料液を調製した。一方、純水５リットルと過酸化水素３９０ccを混合し、６０℃に加熱した加熱水を調製した。加熱水を攪拌しながら上記原料液を加熱水に９０分かけて滴下した。生成した沈澱５６０ｇを濾過して回収し、６０℃に加熱して乾燥し、２リットルの純水を加え後に濾過し、５００℃で仮焼し、酸化錫粉末３３０ｇを得た。この酸化錫粉末の比表面積および塩素濃度を表１に示した。
[Example 1]
A raw material solution was prepared by dissolving 500 g of stannous chloride in 2.8 liters of pure water and 150 cc of hydrochloric acid. Meanwhile, 5 liters of pure water and 390 cc of hydrogen peroxide were mixed and heated water heated to 60 ° C. was prepared. The raw material liquid was added dropwise to the heated water over 90 minutes while stirring the heated water. 560 g of the generated precipitate was collected by filtration, heated to 60 ° C. and dried, filtered after adding 2 liters of pure water, and calcined at 500 ° C. to obtain 330 g of tin oxide powder. The specific surface area and chlorine concentration of this tin oxide powder are shown in Table 1.
〔実施例２〕
塩化第一錫５００ｇ、純水２.８リットル、塩酸２５０cc、および過酸化水素２５０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水５０リットルを５０℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に６０分かけて滴下した。生成した沈澱５６０ｇを濾過して回収し、１２０℃に加熱して乾燥し、０.２リットルの純水を加えて６００℃で仮焼することによって、酸化錫粉末３３１ｇを得た。この酸化錫粉末のＢＥＴ比表面積および塩素濃度を表１に示した。
[Example 2]
A precursor raw material solution was prepared by mixing 500 g of stannous chloride, 2.8 liters of pure water, 250 cc of hydrochloric acid, and 250 cc of hydrogen peroxide while cooling. Meanwhile, 50 liters of pure water was heated to 50 ° C. The precursor raw material liquid was added dropwise to the heated water over 60 minutes while stirring the heated water. 560 g of the generated precipitate was collected by filtration, heated to 120 ° C. and dried, and then added with 0.2 liters of pure water and calcined at 600 ° C. to obtain 331 g of tin oxide powder. Table 1 shows the BET specific surface area and chlorine concentration of the tin oxide powder.
〔実施例３〕
塩化第一錫５００ｇ、純水６.１リットル、および過酸化水素３９０ccを混合した前駆体原料液（塩酸なし）を調製した。一方、純水８リットルを６５℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に９０分かけて滴下した。生成した沈澱５２０ｇを濾過して回収し、１２０℃に加熱して乾燥し、０.５リットルの純水を加えて４５０℃で仮焼することによって、酸化錫粉末３０７ｇを得た。この酸化錫粉末のＢＥＴ比表面積および塩素濃度を表１に示した。
Example 3
A precursor raw material liquid (without hydrochloric acid) in which 500 g of stannous chloride, 6.1 liters of pure water, and 390 cc of hydrogen peroxide were mixed was prepared. Meanwhile, 8 liters of pure water was heated to 65 ° C. The precursor raw material liquid was dropped into the heated water over 90 minutes while stirring the heated water. The produced precipitate 520 g was collected by filtration, heated to 120 ° C., dried, added with 0.5 liters of pure water and calcined at 450 ° C. to obtain 307 g of tin oxide powder. Table 1 shows the BET specific surface area and chlorine concentration of the tin oxide powder.
〔実施例４〕
塩化第一錫５００ｇ、純水１.９リットル、塩酸２１０cc、および過酸化水素３９０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水２２リットルを７５℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に３０分かけて滴下した。生成した沈澱５５５ｇを濾過して回収し、６０℃に加熱して乾燥し、５リットルの純水を加えて濾過し、７５０℃で仮焼することによって、酸化錫粉末３２５ｇを得た。この酸化錫粉末のＢＥＴ比表面積および塩素濃度を表１に示した。
Example 4
A precursor raw material liquid was prepared by mixing 500 g of stannous chloride, 1.9 liters of pure water, 210 cc of hydrochloric acid, and 390 cc of hydrogen peroxide while cooling. On the other hand, 22 liters of pure water was heated to 75 ° C. The precursor raw material liquid was dropped into the heated water over 30 minutes while stirring the heated water. 555 g of the generated precipitate was collected by filtration, heated to 60 ° C. and dried, filtered by adding 5 liters of pure water, and calcined at 750 ° C. to obtain 325 g of tin oxide powder. Table 1 shows the BET specific surface area and chlorine concentration of the tin oxide powder.
〔実施例５〕
金属錫２６５ｇを塩酸６００ccに加熱して溶解させ、これに純水１６.５リットルを加えた後に、過酸化水素２９０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水６リットルを６０℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に９０分かけて滴下した。生成した沈澱５１０ｇを濾過して回収し、１００℃に加熱して乾燥し、２リットルの純水を加えて濾過し、３５０℃で仮焼することによって、酸化錫粉末３００ｇを得た。この酸化錫粉末のＢＥＴ比表面積および塩素濃度を表１に示した。
Example 5
265 g of metallic tin was dissolved in 600 cc of hydrochloric acid by heating, 16.5 liters of pure water was added thereto, and then 290 cc of hydrogen peroxide was mixed while cooling to prepare a precursor raw material solution. Meanwhile, 6 liters of pure water was heated to 60 ° C. The precursor raw material liquid was dropped into the heated water over 90 minutes while stirring the heated water. The produced precipitate 510 g was collected by filtration, heated to 100 ° C. and dried, filtered by adding 2 liters of pure water, and calcined at 350 ° C. to obtain 300 g of tin oxide powder. Table 1 shows the BET specific surface area and chlorine concentration of the tin oxide powder.
〔比較例１〕
塩化第一錫５００ｇ、純水２.８リットル、塩酸１５０cc、および過酸化水素３９０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水３リットルを６０℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に６０分かけて滴下した。生成した沈澱４５０ｇを濾過して回収し、１２０℃に加熱して乾燥し、０.２リットルの純水を加えて濾過し、６００℃で仮焼することによって、酸化錫粉末２６５ｇを得た。この酸化錫粉末のＢＥＴ比表面積は３０ｍ2/ｇであり、塩素濃度は８５ppmに上昇した。
[Comparative Example 1]
A precursor raw material solution was prepared by mixing 500 g of stannous chloride, 2.8 liters of pure water, 150 cc of hydrochloric acid, and 390 cc of hydrogen peroxide while cooling. Meanwhile, 3 liters of pure water was heated to 60 ° C. The precursor raw material liquid was added dropwise to the heated water over 60 minutes while stirring the heated water. 450 g of the produced precipitate was collected by filtration, heated to 120 ° C., dried, filtered by adding 0.2 liter of pure water, and calcined at 600 ° C. to obtain 265 g of tin oxide powder. The tin oxide powder had a BET specific surface area of 30 m 2 / g and a chlorine concentration increased to 85 ppm.
〔比較例２〕
塩化第一錫５００ｇ、純水２.８リットル、塩酸１５０cc、および過酸化水素３９０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水２５リットルを４０℃に加熱した。この加熱水を攪拌しながら、上記前駆体原料液をこの加熱水に６０分かけて滴下した。生成した沈澱は２０ｇであった。
[Comparative Example 2]
A precursor raw material solution was prepared by mixing 500 g of stannous chloride, 2.8 liters of pure water, 150 cc of hydrochloric acid, and 390 cc of hydrogen peroxide while cooling. Meanwhile, 25 liters of pure water was heated to 40 ° C. The precursor raw material liquid was added dropwise to the heated water over 60 minutes while stirring the heated water. The produced precipitate was 20 g.
〔比較例３〕
塩化第一錫５００ｇ、純水１.９リットル、塩酸２１０cc、および過酸化水素３９０ccを冷却しながら混合して前駆体原料液を調製した。一方、純水２５リットルを上記前駆体溶液に加えて混合し、６５℃まで加熱し攪拌した。生成した沈殿物を濾過したところ、回収できた沈殿物は５ｇであった。
[Comparative Example 3]
A precursor raw material liquid was prepared by mixing 500 g of stannous chloride, 1.9 liters of pure water, 210 cc of hydrochloric acid, and 390 cc of hydrogen peroxide while cooling. On the other hand, 25 liters of pure water was added to the precursor solution, mixed, heated to 65 ° C. and stirred. The produced precipitate was filtered, and the recovered precipitate was 5 g.
〔比較例４〕
実施例１において製造した乾燥物に純水を加えずに５００℃で仮焼したところ、堅い固形物になり、粉末を得るには粉砕する必要があった。また、粉末には粉砕機からの不純物が混入し、鉄およびニッケルの量が高くなり、塩素含有量も５０ppmと高かった。
[Comparative Example 4]
When the dried product produced in Example 1 was calcined at 500 ° C. without adding pure water, it became a hard solid and needed to be pulverized to obtain a powder. Further, impurities from the pulverizer were mixed in the powder, the amount of iron and nickel was high, and the chlorine content was as high as 50 ppm.
〔比較例５〕
電解酸化法、硝酸溶解法で製造した酸化錫粉末は、例えば、５００℃で焼成した粉末のBET比表面積は何れも７ｍ2/ｇ程度である。
[Comparative Example 5]
In the tin oxide powder produced by the electrolytic oxidation method or nitric acid dissolution method, for example, the BET specific surface area of the powder fired at 500 ° C. is about 7 m 2 / g.
Claims (6)
The stannous chloride solution is mixed with heated water in an amount of 150 gram equivalents or more with respect to the amount of tin in the solution in the presence of hydrogen peroxide, and the resulting tin oxide precipitate is collected by filtration, dried, and heat treated. To produce a tin oxide powder having a specific surface area of 10 m 2 or more.
A small amount of a stannous chloride solution having a tin concentration of 10 g / L or more in pure water heated to 45 ° C. or more that is 150 grams equivalent times or more the amount of tin in the solution in the presence of hydrogen peroxide with stirring. The method for producing a fine powder of tin oxide according to claim 1, wherein the fine powder is added step by step to form a tin oxide precipitate.
A stannous chloride solution containing 1 equivalent or more hydrogen peroxide with respect to the amount of tin in the solution and heated to 45 ° C. to 75 ° C., which is 150 grams equivalent times or more with respect to the amount of tin in the solution The manufacturing method of the tin oxide fine powder of Claim 1 or Claim 2 mixed with water.
A precursor solution obtained by adding one equivalent or more of hydrogen peroxide to the stannous chloride solution with respect to the amount of tin in the solution is 45 ° C to 75 times 150 grams equivalent or more with respect to the amount of tin in the solution. The manufacturing method of the tin oxide fine powder of Claim 1 or Claim 2 mixed with the pure water heated at degreeC.
The stannous chloride solution is dropped into heated water of 150 gram equivalent times or more with respect to the amount of tin in the solution over 30 minutes while stirring. The manufacturing method of the tin oxide fine powder described in 2.
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| CN102229439A (en) * | 2011-04-22 | 2011-11-02 | 浙江大学 | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6046924A (en) * | 1983-08-25 | 1985-03-14 | Mitsubishi Metal Corp | Production of fine powder of tin oxide having low electrical resistance |
| JPS63112421A (en) * | 1986-10-29 | 1988-05-17 | Mitsubishi Metal Corp | Production of antiomony-doped tin oxide powder |
| JPH11310415A (en) * | 1998-04-27 | 1999-11-09 | Mitsubishi Materials Corp | Highly pure tin oxide and its production |
| JP2008222540A (en) * | 2007-03-09 | 2008-09-25 | Daiichi Kigensokagaku Kogyo Co Ltd | Method for producing tin oxide sol, and method for controlling average grain diameter of tin oxide sol |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6046924A (en) * | 1983-08-25 | 1985-03-14 | Mitsubishi Metal Corp | Production of fine powder of tin oxide having low electrical resistance |
| JPS63112421A (en) * | 1986-10-29 | 1988-05-17 | Mitsubishi Metal Corp | Production of antiomony-doped tin oxide powder |
| JPH11310415A (en) * | 1998-04-27 | 1999-11-09 | Mitsubishi Materials Corp | Highly pure tin oxide and its production |
| JP2008222540A (en) * | 2007-03-09 | 2008-09-25 | Daiichi Kigensokagaku Kogyo Co Ltd | Method for producing tin oxide sol, and method for controlling average grain diameter of tin oxide sol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102229439A (en) * | 2011-04-22 | 2011-11-02 | 浙江大学 | Low-temperature preparation method of nanocrystalline tin dioxide lithium ion battery negative electrode material |
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