JP2005305336A - Silica adsorbent and preparation method therefor - Google Patents
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本発明は，シリカ吸着材及びその製造方法に関する。 The present invention relates to a silica adsorbent and a method for producing the same.
従来より、シリカゲルを代表に，多種多様のシリカ吸着材が市販されている。既存のシリカ吸着材としては、シリカ１次粒子の大きさにより比表面積，全細孔容積が変化するので，多種多様の吸着材が存在するが，大別するとＡ形シリカゲルとＢ形シリカゲルの２種類がある。Ａ形シリカゲルは小粒子径であるためマイクロ孔が多く存在し，高比表面積であるが，全細孔容積は小さい。逆にＢ形シリカゲルは，メソ孔やマクロ孔が多く存在し，全細孔容積が大きいが，低比表面積となる。また、各種吸着材の吸着特性を考慮し，異なる吸着材をブレンドすることにより，様々な吸着特性を得ることができる。 Conventionally, a wide variety of silica adsorbents, such as silica gel, are commercially available. As the existing silica adsorbent, the specific surface area and the total pore volume vary depending on the size of the silica primary particles, so there are a wide variety of adsorbents. There are types. Since A-type silica gel has a small particle size, there are many micropores and a high specific surface area, but the total pore volume is small. Conversely, B-type silica gel has many mesopores and macropores, and has a large total pore volume but a low specific surface area. In addition, in consideration of the adsorption characteristics of various adsorbents, various adsorbent characteristics can be obtained by blending different adsorbents.
シリカ吸着材の多くは，ケイ酸ソーダと硫酸を均一混合した後，脱塩／水洗，及び乾燥して製造されている。
シリカゲルの製造において、ケイ酸ソーダを酸で加水分解し，生成する初期のシリカ分子は一次粒子（primely particle）といわれている。この一次粒子の粒子径は、ｐH，温度，塩，シリカ濃度の影響を受けて変化する。一次粒子の粒子径の増大と共に、一次粒子が系から分離し沈殿を生じたり，均一なゲル状態を示したりする。シリカゲルはこの一次粒子が互いに連結した構造を持ち，粒子間の空隙が細孔となる。
Most silica adsorbents are manufactured by mixing sodium silicate and sulfuric acid uniformly, then desalting / washing with water, and drying.
In the production of silica gel, the initial silica molecules produced by hydrolyzing sodium silicate with an acid are said to be primary particles. The particle size of the primary particles changes under the influence of pH, temperature, salt, and silica concentration. As the particle size of the primary particles increases, the primary particles separate from the system and precipitate, or show a uniform gel state. Silica gel has a structure in which the primary particles are connected to each other, and voids between the particles become pores.
一次粒子の接点付近で，可溶性シリカ分子が析出し，狭い空隙を埋め，なめらかな表面となれば，微細な空隙は消失してしまうが、十分にこの接点が埋められず，ミクロポアとして存在するものがＡ形シリカゲルである。一方、微細接点の空隙が埋められ，ミクロポアとしての空隙は消失し，代わりに大きな空隙が生じたものがＢ形シリカゲルやＩＤ形シリカゲルである。 If soluble silica molecules are deposited near the primary particle contacts and fill the narrow voids, resulting in a smooth surface, the fine voids disappear, but the contacts are not sufficiently filled and exist as micropores. Is A-type silica gel. On the other hand, the voids of the fine contacts are filled, the voids as micropores disappear, and the B-type silica gel and ID-type silica gel in which large voids are generated instead.
Ａ型シリカゲルは、比表面積が大きいため、吸着対象物質の相対圧が低いときの吸着量は比較的大きいものの、全細孔容積が小さいため、吸着対象物質の相対圧が高いときの吸着量を多くできないという問題があった。 A type silica gel has a large specific surface area, so the adsorption amount when the relative pressure of the adsorption target substance is low is relatively large, but the total pore volume is small, so the adsorption amount when the relative pressure of the adsorption target substance is high is There was a problem of not being able to do much.
また、Ｂ型シリカゲルは、全細孔容積が大きいため、吸着対象物質の相対圧が高いときの吸着量は比較的大きいものの、ミクロポアが少ないため、吸着対象物質の相対圧が低いときには、十分に吸着することができないという問題があった。 In addition, since B type silica gel has a large total pore volume, the adsorption amount when the relative pressure of the adsorption target substance is high is relatively large, but there are few micropores. There was a problem that it could not be adsorbed.
更に、Ｂ型シリカゲルは、生じたメソポアやマクロポアの空隙がインクボトル型となり，吸脱着にヒステリシスが観察される。このヒステリシスは，調湿目的には不都合を生ずる場合があるので，このヒステリシスを示す圧力の範囲（中・高相対圧）では，湿度が変化しても調湿効果が十分に発揮されない。つまり、Ｂ型シリカゲルを調湿剤として使用した場合、一旦水を吸着すると、その後、室内の湿度が低下しても水を放出しにくく、調湿剤としての機能が不十分であるという問題があった。 Further, in the B type silica gel, the generated mesopores and macropores are in the ink bottle type, and hysteresis is observed in the adsorption / desorption. Since this hysteresis may cause inconveniences for humidity control purposes, the humidity control effect is not fully exhibited even if the humidity changes within the pressure range (medium / high relative pressure) that shows this hysteresis. In other words, when B-type silica gel is used as a humidity control agent, once water is adsorbed, it is difficult to release water even if the indoor humidity decreases, and the function as a humidity control agent is insufficient. there were.
また、Ａ形シリカゲルとＢ形シリカゲルのブレンド品では，ブレンドが均一に行われない時や、ブレンドされたシリカからの採取が不均一であると、希望する吸着特性を得ることができず、更に、Ａ型シリカゲルとＢ型シリカゲルそれぞれの短所はある程度補えるものの、それぞれの長所が薄められてしまうという問題があった。 In addition, in the blended product of A-type silica gel and B-type silica gel, when the blending is not performed uniformly or when the sampling from the blended silica is not uniform, the desired adsorption characteristics cannot be obtained. Although the disadvantages of the A-type silica gel and the B-type silica gel can be compensated to some extent, there is a problem that the respective advantages are diminished.
本発明は以上の点に鑑み成されたものであり、吸着対象物質の相対圧が低いときから高いときまで吸着性能が高く、吸着特性におけるヒステリシスが小さいシリカ吸着材及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above points, and provides a silica adsorbent having high adsorption performance and low hysteresis in adsorption characteristics from the time when the relative pressure of the substance to be adsorbed is low to high, and a method for producing the same. With the goal.
（１）請求項１の発明は、
窒素ガス吸着法による全細孔容積が０．５から０．９ｃｍ３／ｇであり、且つ，窒素ガス吸着法による比表面積が５００から８５０（好ましくは７２０から８５０）ｍ２／ｇであることを特徴とするシリカ吸着材を要旨とする。
(1) The invention of claim 1
The total pore volume by nitrogen gas adsorption method is 0.5 to 0.9 cm 3 / g, and the specific surface area by nitrogen gas adsorption method is 500 to 850 (preferably 720 to 850) m 2 / g. The summary is a silica adsorbent characterized by the following.
本発明のシリカ吸着材は、全細孔容積及び比表面積が上記範囲にあることにより、吸着対象物質が低相対圧であるときから高相対圧であるときまで、吸着性能が高い。つまり、本発明のシリカ吸着材は、比表面積が大きいことにより、吸着対象物質が低相対圧であるときでも吸着性能が高く、また、全細孔容積が大きいことにより、吸着対象物質が高相対圧であるときの吸着性能も高い。 The silica adsorbent of the present invention has high adsorption performance from when the adsorption target substance is at a low relative pressure to when it is at a high relative pressure because the total pore volume and specific surface area are in the above ranges. That is, the silica adsorbent of the present invention has a high specific surface area, so that the adsorption performance is high even when the adsorption target substance is at a low relative pressure. Adsorption performance when pressure is high.
また、本発明のシリカ吸着材は、吸着特性におけるヒステリシスが小さい。ヒステリシスが小さいと、吸着対象物質の相対圧の変化に伴い速やかに吸着／脱着が行われることになる。しかも低相対圧ではＡ型シリカゲルの性能を上回り、中・高相対圧ではＢ型シリカゲルの性能を上回り、ヒステリシスを示さないことは、調湿剤としての有効性が高い。つまり、本発明のシリカ吸着材は、水を吸着しても、湿度が低下したときには、直ちに、吸着していた水を放出するので、室内における湿度を一定に保つ作用を奏する。 Further, the silica adsorbent of the present invention has a small hysteresis in the adsorption characteristics. If the hysteresis is small, the adsorption / desorption is promptly performed with the change in the relative pressure of the substance to be adsorbed. In addition, the low relative pressure exceeds the performance of the A type silica gel, and the medium and high relative pressures exceed the performance of the B type silica gel. That is, even if the silica adsorbent of the present invention adsorbs water, when the humidity decreases, the adsorbed water is immediately released, so that the humidity in the room is kept constant.
また、本発明のシリカ吸着材は、脱着分子の脱着に抵抗が少ないので、触媒担体として優れている。
・前記全細孔容積は、図１に示すような窒素脱着等温線に基づき、ＢＥＴ法（ＤＨプロット）を用いて算出した値である。
Further, the silica adsorbent of the present invention is excellent as a catalyst carrier because it has little resistance to desorption of desorption molecules.
The total pore volume is a value calculated using a BET method (DH plot) based on a nitrogen desorption isotherm as shown in FIG.
・前記比表面積は、図１に示すような窒素脱着等温線に基づき、ＢＥＴ法を用いて算出した値である。
（２）請求項２の発明は、
１ｇあたりの窒素吸着能が，相対圧０．２では１８０から２５０（好ましくは２００から２４０）ｍＬ，相対圧０．５では２５０から３５０（好ましくは２８０から３１０）ｍＬ，相対圧０．９では４００から５５０（好ましくは４２０から５１０）ｍＬであることを特徴とする請求項１記載のシリカ吸着材を要旨とする。
The specific surface area is a value calculated using the BET method based on a nitrogen desorption isotherm as shown in FIG.
(2) The invention of claim 2
Nitrogen adsorption capacity per gram is 180 to 250 (preferably 200 to 240) mL at a relative pressure of 0.2, 250 to 350 (preferably 280 to 310) mL at a relative pressure of 0.5, and a relative pressure of 0.9. The gist of the silica adsorbent according to claim 1, characterized in that it is 400 to 550 mL (preferably 420 to 510) mL.
本発明のシリカ吸着材は、上記のように、低相対圧での吸着能がＡ形シリカゲルと同様に高く，高相対圧においてもＢ形シリカゲルと同様に吸着能が高いので，オールマイティーな吸着材であると言える。 As described above, the silica adsorbent of the present invention has a high adsorptive capacity at a low relative pressure as in the case of A-type silica gel, and an adsorbing capacity as high as that of B-type silica gel at a high relative pressure. It can be said that.
・前記窒素吸着能は、ＢＥＴ法を用いて算出した値である。
（３）請求項３の発明は、
全細孔面積に対し、細孔径が１．０〜１．５ｎｍである細孔の細孔面積の割合が２０〜５０（好ましくは２７〜４７）％であり、細孔径が１．５〜２ｎｍである細孔の細孔面積の割合が２０〜３５（好ましくは２６〜２９）％であり、細孔径が２〜４ｎｍである細孔の細孔面積の割合が２０〜４０（好ましくは２１〜３６）％であり、細孔径が４〜１０ｎｍである細孔の細孔面積の割合が３〜１５（好ましくは７〜１０）％であり、細孔径が１０ｎｍ以上である細孔の細孔面積の割合が０．５〜３（好ましくは０．６〜２）％であることを特徴とする請求項１又は２記載のシリカ吸着材を要旨とする。
The nitrogen adsorption capacity is a value calculated using the BET method.
(3) The invention of claim 3
The ratio of the pore area of the pore having a pore diameter of 1.0 to 1.5 nm to the total pore area is 20 to 50 (preferably 27 to 47)%, and the pore diameter is 1.5 to 2 nm. The ratio of the pore area of the pores is 20 to 35 (preferably 26 to 29)%, and the ratio of the pore area of the pores whose pore diameter is 2 to 4 nm is 20 to 40 (preferably 21 to 21). 36)%, the ratio of the pore area of the pores having a pore diameter of 4 to 10 nm is 3 to 15 (preferably 7 to 10)%, and the pore area of the pores having a pore diameter of 10 nm or more The silica adsorbent according to claim 1 or 2, characterized in that the ratio is 0.5 to 3 (preferably 0.6 to 2)%.
本発明のシリカ吸着材は、細孔径が広く分布しているので、吸着対象物質の相対圧が低いときから高いときまで吸着性能が高く、しかも吸着特性におけるヒステリシスが小さい。 Since the silica adsorbent of the present invention has a wide pore size distribution, the adsorption performance is high from the time when the relative pressure of the substance to be adsorbed is low to the time when it is high, and the hysteresis in the adsorption characteristics is small.
・前記細孔面積の割合は、図１に示すような窒素吸着等温線に基づき、ＤＨ法を用いて、図２に示すような細孔径分布を求め、その細孔径分布から算出した値である。
（４）請求項４の発明は、
請求項１〜３のいずれかに記載のシリカ吸着材の製造方法であって、
原料として，ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを用いることを特徴とするシリカ吸着材の製造方法を要旨とする。
The ratio of the pore area is a value calculated from the pore diameter distribution obtained from the pore diameter distribution as shown in FIG. 2 using the DH method based on the nitrogen adsorption isotherm as shown in FIG. .
(4) The invention of claim 4
A method for producing a silica adsorbent according to any one of claims 1 to 3,
The gist is a method for producing a silica adsorbent characterized by using sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less as a raw material.
本発明では、ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを用いることにより，様々な粒子径を持つシリカ粒子を得ることが出来、そのシリカ粒子を用いて、吸着対象物質の相対圧が低いときから高いときまで吸着性能が高く、しかも吸着特性におけるヒステリシスが小さいシリカ吸着材を製造することができる。 In the present invention, silica particles having various particle diameters can be obtained by using sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less. Can be used to manufacture a silica adsorbent having high adsorption performance and low hysteresis in adsorption characteristics from the time when the relative pressure of the substance to be adsorbed is low to when it is high.
・前記ケイ酸ソーダとしては、シリカ濃度が２５％以上のものが好適である。また、ケイ酸ソーダの粘度は８０°Ｃにおいて粘度５００ポイズ以上が好適である。
（５）請求項５の発明は、
前記ケイ酸ソーダを粉砕する工程と、
粉砕したケイ酸ソーダを酸処理及び／又は水洗する工程と、
乾燥させる工程と、を有することを特徴とする請求項４記載のシリカ吸着材の製造方法を要旨とする。
-The sodium silicate having a silica concentration of 25% or more is suitable. The viscosity of sodium silicate is preferably at least 500 poise at 80 ° C.
(5) The invention of claim 5
Crushing the sodium silicate,
Acid-treating and / or washing with water the pulverized sodium silicate,
The method for producing a silica adsorbent according to claim 4, comprising a drying step.
本発明では、ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを、例えば３ｍｍ以下に粉砕する。尚、上記のケイ酸ソーダは，常温では過冷却ガラスの様をなし，極僅かな流動性はあるものの粉砕機等により微粉化することが可能である。 In the present invention, sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less is pulverized to, for example, 3 mm or less. In addition, the above-mentioned sodium silicate is like a supercooled glass at room temperature and can be pulverized by a pulverizer or the like although it has a very slight fluidity.
次に、粉砕したケイ酸ソーダを酸により中和するか、水洗する。このとき、ゾル状態を経ない、若しくはゾル状態を限りなく短くすることができ、その結果として、ケイ酸ソーダのシリカ骨格に近い粒子がそのまま現れ、シリカの１次粒子がランダムとなり、様々な細孔径を持つシリカ粒子を得ることが出来る。 Next, the ground sodium silicate is neutralized with an acid or washed with water. At this time, the sol state does not pass or the sol state can be shortened as much as possible. As a result, particles close to the silica skeleton of sodium silicate appear as they are, and the silica primary particles become random, and various fine particles are obtained. Silica particles having a pore size can be obtained.
また、粉砕したケイ酸ソーダを酸処理及び／又は水洗する工程において、中和されたアルカリが抜け出ることによりマイクロ孔が多く発生するので、表面積も大きくなる。そのため、本発明で製造されるシリカ吸着材は、細孔径が様々なサイズとなり、しかも表面積が大きいので、吸着対象物質の相対圧が低いときから高いときまで吸着性能が高く、しかも吸着特性におけるヒステリシスが小さい。
（６）請求項６の発明は、
請求項１〜３のいずれかに記載のシリカ吸着材の製造方法であって、
ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを，酸により脱アルカリする工程を有することを特徴とするシリカ吸着材の製造方法を要旨とする。
Further, in the step of acid treatment and / or washing with water for the pulverized sodium silicate, many micropores are generated by the neutralized alkali coming out, and the surface area is also increased. Therefore, the silica adsorbent produced in the present invention has various pore sizes and a large surface area, so that the adsorption performance is high from the time when the relative pressure of the substance to be adsorbed is low to high, and the hysteresis in the adsorption characteristics. Is small.
(6) The invention of claim 6
A method for producing a silica adsorbent according to any one of claims 1 to 3,
The gist of the present invention is a method for producing a silica adsorbent characterized by having a step of dealkalizing sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less with an acid.
本発明では、例えば、微粉化されたケイ酸ソーダを５０％以上の硫酸によって脱アルカリを行うので，ゾル状態を経ないか、若しくはゾル状態が限りなく短くなり、１次粒子径がランダムなシリカ粒子が得られる。また，中和されたアルカリが抜け出ることによりマイクロ孔が多く発生するので，シリカ粒子の表面積も大きくなる。 In the present invention, for example, finely divided sodium silicate is dealkalized with 50% or more sulfuric acid, so that it does not go through the sol state or the sol state becomes extremely short, and the primary particle size is random. Particles are obtained. Moreover, since many micropores are generated when the neutralized alkali escapes, the surface area of the silica particles also increases.
そのため、上記のようにして得られるシリカ粒子から成るシリカ吸着材は、吸着対象物質の相対圧が低いときから高いときまで吸着性能が高く、しかも吸着特性におけるヒステリシスが小さい。 Therefore, the silica adsorbent composed of the silica particles obtained as described above has high adsorption performance from the time when the relative pressure of the substance to be adsorbed is low to high, and has a small hysteresis in the adsorption characteristics.
・前記ケイ酸ソーダとしては、８０°Ｃにおける粘度が５００ポイズ以上のものが好ましい。 -As said sodium silicate, the thing in which the viscosity in 80 degreeC is 500 poise or more is preferable.
本発明のシリカ吸着材は、低相対圧においては、Ａ型シリカゲルと同様に吸着能が高く、また、高相対圧においてはＢ型シリカゲルと同様に吸着能が高い。従って、本発明のシリカ吸着材は、低相対圧から高相対圧まで、高い吸着能を発揮することができる。 The silica adsorbent of the present invention has a high adsorbing ability at a low relative pressure as in the case of A-type silica gel, and a high adsorbing ability at a high relative pressure as in the case of B-type silica gel. Therefore, the silica adsorbent of the present invention can exhibit a high adsorbing ability from a low relative pressure to a high relative pressure.
また、本発明のシリカ吸着材は、吸着特性におけるヒステリシスが小さい。そのため、高相対圧にて多量の物質を吸着した後、その物質の相対圧が低下した場合は、直ちに吸着していた物質を放出することができる。つまり、本発明のシリカ吸着材は、相対圧の変化に応じて、物質の吸着、放出を行うことができるので、例えば、調湿剤として優れている。 Further, the silica adsorbent of the present invention has a small hysteresis in the adsorption characteristics. Therefore, after adsorbing a large amount of substance at a high relative pressure, if the relative pressure of the substance decreases, the adsorbed substance can be released immediately. That is, the silica adsorbent of the present invention is excellent as a humidity control agent, for example, because it can adsorb and release substances according to changes in relative pressure.
発明を実施するための最良の形態を実施例を用いて説明する。 The best mode for carrying out the invention will be described with reference to examples.
ａ）まず、本実施例１のシリカ吸着材の原料となるケイ酸ソーダの製造方法を説明する。蓋付ステンレスビーカーにホワイトカーボン１００ｇ，４８％ＮａＯＨ５０．８ｇと水１７１．４ｇを加えて、８０℃の蒸気中で２時間加熱し、その後、室温まで冷却した。すると、透明な水ガラス状の組成物が得られた。 a) First, the manufacturing method of the sodium silicate used as the raw material of the silica adsorbent of the present Example 1 is demonstrated. White carbon 100 g, 48% NaOH 50.8 g and water 171.4 g were added to a stainless beaker with a lid, heated in steam at 80 ° C. for 2 hours, and then cooled to room temperature. Then, a transparent water glass-like composition was obtained.
得られた組成物を、次の方法で分析した。つまり、Ｎａ２Ｏについては、原子吸光法によりその組成比を求めた。その測定方法は、ＪＩＳ ｋ１４０８（ケイ酸ソーダ）に基づく方法である。ＳｉＯ２については、組成物を１０００°Ｃで強熱して残った固形物の重量から、上記の方法で算出したＮａ２Ｏの量を差し引くことで、その組成比を求めた。この分析の結果、組成物全体に対するＳｉＯ２の重量比は２９．６％であり、ＳｉＯ２／Ｎａ２Ｏ（モル比）は５．２であった。 The obtained composition was analyzed by the following method. That is, the composition ratio of Na 2 O was determined by atomic absorption method. The measurement method is based on JIS k1408 (sodium silicate). The SiO 2, from the weight of the remaining solid was ignited the composition in 1000 ° C, by subtracting the amount of Na 2 O calculated by the above method, was determined its composition ratio. As a result of this analysis, the weight ratio of SiO 2 to the entire composition was 29.6%, and the SiO 2 / Na 2 O (molar ratio) was 5.2.
ｂ）次に、ケイ酸ソーダを用いてシリカ吸着材を製造する方法を説明する。
まず、前記ａ）で得られたケイ酸ソーダを粉砕機を用いて２ｍｍ以下に粉砕した。そして、粉砕したケイ酸ソーダを９８％硫酸により、室温（例えば２０°Ｃ）の条件で３分間酸処理を行い、シリカ吸着材とした。
b) Next, a method for producing a silica adsorbent using sodium silicate will be described.
First, the sodium silicate obtained in a) was pulverized to 2 mm or less using a pulverizer. Then, the pulverized sodium silicate was acid-treated with 98% sulfuric acid at room temperature (for example, 20 ° C.) for 3 minutes to obtain a silica adsorbent.
ｃ）次に、シリカ吸着材の特性を測定した。具体的には、図１に示すように、ＢＥＴ法による窒素吸着法によりシリカ吸着材１ｇあたりに吸着する窒素量を測定したところ、相対圧０．２において２０７ｍＬ／ｇ，相対圧０．５において２８０ｍＬ／ｇ，相対圧０．９において５０８ｍＬ／ｇであった。また、図１の窒素吸着等温曲線に基づき、ＢＥＴプロット法により、比表面積を測定したところ、７２９ｍ２／ｇであり、全細孔容積は０．８７ｃｍ３／ｇであった。これらの結果を下記表１に示す。 c) Next, the characteristics of the silica adsorbent were measured. Specifically, as shown in FIG. 1, when the amount of nitrogen adsorbed per 1 g of silica adsorbent was measured by a nitrogen adsorption method by the BET method, it was 207 mL / g at a relative pressure of 0.2 and 0.5 at a relative pressure of 0.5. It was 508 mL / g at a relative pressure of 0.9 at 280 mL / g. Moreover, when the specific surface area was measured by the BET plot method based on the nitrogen adsorption isothermal curve of FIG. 1, it was 729 m < 2 > / g and the total pore volume was 0.87 cm < 3 > / g. These results are shown in Table 1 below.
更に、図１の窒素吸着等温曲線に基づき、ＤＨ（Ｄｏｌｌｉｍｏｒｅ−Ｈｅｌ）法を用いて、図２に示すように、細孔径ごとの頻度を算出した。尚、図２にて横軸は細孔径であり、縦軸は頻度である。細孔径の区分ごとに、その区分に属する細孔の細孔面積の、全細孔表面積に対する割合を表１に示す。 Further, based on the nitrogen adsorption isotherm of FIG. 1, the frequency for each pore diameter was calculated using the DH (Dollimore-Hel) method as shown in FIG. In FIG. 2, the horizontal axis represents the pore diameter, and the vertical axis represents the frequency. Table 1 shows the ratio of the pore area of the pores belonging to each category to the total pore surface area for each category of pore diameter.
また、本実施例１のシリカ吸着材は、図１に示すように、吸着特性におけるヒステリシスが小さい。そのため、高相対圧にて物質（例えば水）を吸着した後、その物質の相対圧が低下した場合は、直ちに吸着していた物質を放出することができる。つまり、本実施例１のシリカ吸着材は、相対圧の変化に応じて、物質の吸着、放出を行うことができるので、例えば、調湿剤として優れている。 Further, as shown in FIG. 1, the silica adsorbent of Example 1 has a small hysteresis in the adsorption characteristics. Therefore, after adsorbing a substance (for example, water) at a high relative pressure, the adsorbed substance can be immediately released when the relative pressure of the substance decreases. That is, the silica adsorbent of Example 1 is excellent as a humidity control agent, for example, because it can adsorb and release substances according to changes in relative pressure.
ａ）まず、本実施例２のシリカ吸着材の原料となるケイ酸ソーダの製造方法を説明する。蓋付ステンレスビーカーにホワイトカーボン１００ｇ，４８％ＮａＯＨ３７．５ｇと水７７．７ｇを加えて、８０℃の蒸気中で２時間加熱し、その後、室温まで冷却した。すると、透明な水ガラス状の組成物が得られた。 a) First, the manufacturing method of the sodium silicate used as the raw material of the silica adsorbent of the present Example 2 is demonstrated. White carbon 100g, 48% NaOH 37.5g and water 77.7g were added to a stainless beaker with a lid, heated in steam at 80 ° C for 2 hours, and then cooled to room temperature. Then, a transparent water glass-like composition was obtained.
得られた組成物を、前記実施例１と同様の方法で分析した。この分析の結果、組成物全体に対するＳｉＯ２の重量比は４４．１％であり、ＳｉＯ２／Ｎａ２Ｏ（モル比）は７．０であった。 The obtained composition was analyzed in the same manner as in Example 1. As a result of this analysis, the weight ratio of SiO 2 to the entire composition was 44.1%, and the SiO 2 / Na 2 O (molar ratio) was 7.0.
ｂ）次に、ケイ酸ソーダを用いてシリカ吸着材を製造する方法を説明する。
まず、前記ａ）で得られたケイ酸ソーダを粉砕機を用いて２ｍｍ以下に粉砕した。そして、粉砕したケイ酸ソーダを５０％硫酸により、室温（例えば２０°Ｃ）の条件で３分間酸処理を行い、シリカ吸着材とした。
b) Next, a method for producing a silica adsorbent using sodium silicate will be described.
First, the sodium silicate obtained in a) was pulverized to 2 mm or less using a pulverizer. Then, the pulverized sodium silicate was acid-treated with 50% sulfuric acid at room temperature (for example, 20 ° C.) for 3 minutes to obtain a silica adsorbent.
ｃ）次に、シリカ吸着材の特性を前記実施例１と同様に測定した。その結果を図１、図２、及び上記表１に示す。
本実施例２のシリカ吸着材は、前記実施例１と同様に、低相対圧から高相対圧に至るまで高い吸着能を発揮することができる。
c) Next, the characteristics of the silica adsorbent were measured in the same manner as in Example 1. The results are shown in FIGS. 1 and 2 and Table 1 above.
The silica adsorbent of Example 2 can exhibit high adsorbing ability from low relative pressure to high relative pressure, as in Example 1.
また、本実施例２のシリカ吸着材は、吸着特性におけるヒステリシスが小さいので、相対圧の変化に応じて、物質の吸着、放出を行うことができ、例えば、調湿剤として優れている。 Moreover, since the silica adsorbent of Example 2 has small hysteresis in the adsorption characteristics, it can adsorb and release substances according to changes in relative pressure, and is excellent as a humidity control agent, for example.
ａ）まず、本実施例３のシリカ吸着材の原料となるケイ酸ソーダの製造方法を説明する。蓋付ステンレスビーカーにホワイトカーボン１００ｇ，４８％ＮａＯＨ５０．７ｇと水１６８ｇを加えて、８０℃の蒸気中で２時間加熱し、その後、室温まで冷却した。すると、透明な水ガラス状の組成物が得られた。 a) First, the manufacturing method of the sodium silicate used as the raw material of the silica adsorbent of the present Example 3 is demonstrated. White carbon 100 g, 48% NaOH 50.7 g and water 168 g were added to a stainless beaker with a lid, heated in steam at 80 ° C. for 2 hours, and then cooled to room temperature. Then, a transparent water glass-like composition was obtained.
得られた組成物を、前記実施例１と同様の方法で分析した。この分析の結果、組成物全体に対するＳｉＯ２の重量比は２９．８％であり、ＳｉＯ２／Ｎａ２Ｏ（モル比）は５．２であった。 The obtained composition was analyzed in the same manner as in Example 1. As a result of this analysis, the weight ratio of SiO 2 to the entire composition was 29.8%, and the SiO 2 / Na 2 O (molar ratio) was 5.2.
ｂ）次に、ケイ酸ソーダを用いてシリカ吸着材を製造する方法を説明する。
まず、前記ａ）で得られたケイ酸ソーダを粉砕機を用いて２ｍｍ以下に粉砕した。そして、粉砕したケイ酸ソーダを２５％硫酸により、室温（例えば２０°Ｃ）の条件で３分間酸処理を行い、シリカ吸着材とした。
b) Next, a method for producing a silica adsorbent using sodium silicate will be described.
First, the sodium silicate obtained in a) was pulverized to 2 mm or less using a pulverizer. The pulverized sodium silicate was acid-treated with 25% sulfuric acid at room temperature (for example, 20 ° C.) for 3 minutes to obtain a silica adsorbent.
ｃ）次に、シリカ吸着材の特性を前記実施例１と同様に測定した。その結果を図１、図２、及び上記表１に示す。
本実施例３のシリカ吸着材は、前記実施例１と同様に、低相対圧から高相対圧に至るまで高い吸着能を発揮することができる。
c) Next, the characteristics of the silica adsorbent were measured in the same manner as in Example 1. The results are shown in FIGS. 1 and 2 and Table 1 above.
The silica adsorbent of Example 3 can exhibit high adsorbing ability from low relative pressure to high relative pressure, as in Example 1.
また、本実施例３のシリカ吸着材は、吸着特性におけるヒステリシスが小さいので、相対圧の変化に応じて、物質の吸着、放出を行うことができ、例えば、調湿剤として優れている。
（比較例１）
市販されているＡ形シリカゲル（富士シリシア化学（株）製）を比較例１のシリカ吸着材とし、前記実施例１のｃ）と同様に特性を測定した。その結果を図１、図２、及び上記表１に示す。
Further, since the silica adsorbent of Example 3 has a small hysteresis in the adsorption characteristics, it can adsorb and release substances according to changes in relative pressure, and is excellent as a humidity control agent, for example.
(Comparative Example 1)
A commercially available A-type silica gel (manufactured by Fuji Silysia Chemical Co., Ltd.) was used as the silica adsorbent of Comparative Example 1, and the characteristics were measured in the same manner as in Example 1 c). The results are shown in FIGS. 1 and 2 and Table 1 above.
比較例１のシリカ吸着材は、図２に示すように、実施例１〜３のシリカ吸着材と比べて、細孔径の分布が小さい方に偏っている。そのため、図１及び表１に示すように、相対圧が高いときには、吸着量が低くなっている。 As shown in FIG. 2, the silica adsorbent of Comparative Example 1 is biased toward a smaller pore diameter distribution as compared with the silica adsorbents of Examples 1 to 3. Therefore, as shown in FIG. 1 and Table 1, when the relative pressure is high, the adsorption amount is low.
（比較例２）
市販されているＢ形シリカゲル（富士シリシア化学（株）製）を比較例２のシリカ吸着材とし，前記実施例１のｃ）と同様に特性を測定した。その結果を図１、図２、及び上記表１に示す。
(Comparative Example 2)
A commercially available B-type silica gel (manufactured by Fuji Silysia Chemical Co., Ltd.) was used as the silica adsorbent of Comparative Example 2, and the characteristics were measured in the same manner as in Example 1 c). The results are shown in FIGS. 1 and 2 and Table 1 above.
比較例２のシリカ吸着材は、図２に示すように、細孔径の分布が、実施例１〜３に比べて、大きい方に偏っている。そのため、図１及び表１に示すように、相対圧が低いときには、吸着量が低くなっている。 As shown in FIG. 2, the silica adsorbent of Comparative Example 2 has a pore size distribution that is biased toward the larger side as compared with Examples 1-3. Therefore, as shown in FIG. 1 and Table 1, the amount of adsorption is low when the relative pressure is low.
また、図１に示すように、相対圧が０．５以上の範囲では吸着特性にヒステリシスが現れており、調湿材として使用しにくい。
（比較例３）
市販されているＩＤ型シリカゲル（富士シリシア化学（株）製）を比較例３のシリカ吸着材とし，前記実施例１のｃ）と同様に特性を測定した。その結果を図１、図２、及び上記表１に示す。
Moreover, as shown in FIG. 1, when the relative pressure is in the range of 0.5 or more, hysteresis appears in the adsorption characteristics and is difficult to use as a humidity control material.
(Comparative Example 3)
A commercially available ID type silica gel (manufactured by Fuji Silysia Chemical Ltd.) was used as the silica adsorbent of Comparative Example 3, and the characteristics were measured in the same manner as in Example 1 c). The results are shown in FIGS. 1 and 2 and Table 1 above.
比較例３のシリカ吸着材は、図２に示すように、細孔径の分布が、実施例１〜３に比べて、大きい方に偏っている。そのため、図１及び表１に示すように、相対圧が低いときには、吸着量が低くなっている。 As shown in FIG. 2, the silica adsorbent of Comparative Example 3 has a pore size distribution that is biased toward the larger side as compared with Examples 1-3. Therefore, as shown in FIG. 1 and Table 1, the amount of adsorption is low when the relative pressure is low.
また、図１に示すように、相対圧が０．７以上の範囲では吸着特性にヒステリシスが現れており、調湿材として使用しにくい。
尚、本発明は前記実施例になんら限定されるものではなく、本発明を逸脱しない範囲において種々の態様で実施しうることはいうまでもない。
Moreover, as shown in FIG. 1, when the relative pressure is in the range of 0.7 or more, hysteresis appears in the adsorption characteristics and is difficult to use as a humidity control material.
Needless to say, the present invention is not limited to the above-described embodiments, and can be implemented in various modes without departing from the scope of the present invention.
Claims (6)
細孔径が４〜１０ｎｍである細孔の細孔面積の割合が３〜１５％であり、細孔径が１０ｎｍ以上である細孔の細孔面積の割合が０．５〜３％であることを特徴とする請求項１又は２記載のシリカ吸着材。 The ratio of the pore area having a pore diameter of 1.0 to 1.5 nm to the total pore area is 20 to 50%, and the pore having a pore diameter of 1.5 to 2 nm The ratio of the area is 20 to 35%, the ratio of the pore area of the pores having a pore diameter of 2 to 4 nm is 20 to 40%,
The ratio of the pore area of the pore having a pore diameter of 4 to 10 nm is 3 to 15%, and the ratio of the pore area of the pore having a pore diameter of 10 nm or more is 0.5 to 3%. The silica adsorbent according to claim 1 or 2, characterized in that:
原料として，ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを用いることを特徴とするシリカ吸着材の製造方法。 A method for producing a silica adsorbent according to any one of claims 1 to 3,
A method for producing a silica adsorbent, characterized by using sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less as a raw material.
粉砕したケイ酸ソーダを酸処理及び／又は水洗する工程と、
乾燥させる工程と、を有することを特徴とする請求項４記載のシリカ吸着材の製造方法。 Crushing the sodium silicate,
Acid-treating and / or washing with water the pulverized sodium silicate,
The method for producing a silica adsorbent according to claim 4, further comprising a step of drying.
ＳｉＯ２／Ｎａ２Ｏ（モル比）が５．０以上８．０以下であるケイ酸ソーダを，酸により脱アルカリする工程を有することを特徴とするシリカ吸着材の製造方法。 A method for producing a silica adsorbent according to any one of claims 1 to 3,
A method for producing a silica adsorbent comprising a step of dealkalizing sodium silicate having a SiO 2 / Na 2 O (molar ratio) of 5.0 or more and 8.0 or less with an acid.
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| CN102980843A (en) * | 2012-12-24 | 2013-03-20 | 北京科技大学 | Method for detecting coke air hole characteristics |
| CN103769039A (en) * | 2014-01-27 | 2014-05-07 | 蹇守民 | Preparation method for adsorbent |
| US10941897B2 (en) | 2015-02-13 | 2021-03-09 | Lg Chem, Ltd. | Preparation method of silica aerogel-containing blanket and silica aerogel-containing blanket prepared by using the same |
| CN105060311A (en) * | 2015-08-25 | 2015-11-18 | 安徽良臣硅源材料有限公司 | Preparation method for waterproof silica gel bonded by hydrophilic groups |
| US10919772B2 (en) | 2015-11-03 | 2021-02-16 | Lg Chem, Ltd. | Method for preparing hydrophobic metal oxide-silica composite aerogel, and hydrophobic metal oxide-silica composite aerogel prepared thereby |
| EP3326970A4 (en) * | 2016-03-24 | 2018-08-22 | LG Chem, Ltd. | Silica aerogel production system |
| US11505657B2 (en) | 2016-03-24 | 2022-11-22 | Lg Chem, Ltd. | System and rotating blade unit for preparing silica aerogel |
| US11279622B2 (en) | 2016-09-12 | 2022-03-22 | Lg Chem, Ltd. | Method for producing silica aerogel and silica aerogel produced thereby |
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