JP4209485B2 - Fixed bed catalyst layer for catalytic reaction between solute in aqueous solution and poorly water-soluble gas, and reaction method using the same - Google Patents
Fixed bed catalyst layer for catalytic reaction between solute in aqueous solution and poorly water-soluble gas, and reaction method using the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は水溶液中溶質と難水溶性気体との接触反応用固定床触媒層及びそれを用いた反応方法に関するものである。この反応には、例えば、水素や酸素又は空気と、水溶液中の塩、硫化物又は有機物との反応が包含される。
【０００２】
【従来の技術】
難水溶性気体と水溶液中に含まれる溶質とを反応させるために、それらの反応成分を固定床触媒層中で接触させることは広く行われている。例えば、このような反応方法としては、酸素と水溶液中に含まれている硫化ナトリウム（Ｎａ2Ｓ）とを反応させてポリサルファイド（Ｎａ2Ｓｘ（ｘ＝２〜５））を生成させるために、活性炭からなる固定床触媒層に酸素（又は空気）と硫化ナトリウムを含む水溶液とを導入し、接触反応させる方法が知られている。
また、このような反応方法において、難水溶性気体分子の触媒表面への拡散を促進させて反応効率を向上させるために、フッ素系樹脂等の撥水性物質を触媒粒子表面に付着結合させることも知られている（特公昭５２−３８９８２号、特開昭５８−１７７１５１号、ＵＳＰ４０７３７４８号、ＵＳＰ４０２４２２９号等）。
しかしながら、このような従来の方法では、触媒粒子表面に対する撥水性物質の付着結合により、触媒の有効表面が減少するために、触媒を長時間にわたって高活性に保持することが困難であった。また、触媒粒子にフッ素系樹脂を付着結合させることは、触媒調製を煩雑にするとともに、使用済み触媒からのそのフッ素樹脂の分離回収を困難にした。従って、従来の触媒においては、触媒の活性劣化の問題や触媒コストが高くなるという問題を含む上、使用済み触媒の再生処理や廃棄処理が困難であるという使用済み触媒の処理上の問題を含むものであった。
【０００３】
【発明が解決しようとする課題】
本発明は、水溶液中での難水溶性気体の触媒表面への拡散性がよく、かつ長時間にわたって高い触媒活性を保持し、さらに、触媒コストの問題及び使用済み触媒の処理上の問題を有しない固定床触媒層及びそれを用いた反応方法を提供することをその課題とする。
【０００４】
【課題を解決するための手段】
本発明者らは、前記課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに至った。即ち、本発明によれば、水溶液中溶質と難水溶性気体との接触反応用固定床触媒層であって、該触媒層中の触媒が活性炭であると共に、触媒層中に水接触角６０度以上の樹脂からなる疎水性物質を前記触媒から独立した粒子又は成形物として０．５〜５０重量%含有させたことを特徴とする固定床触媒層が提供される。また、本発明によれば、水溶液中溶質と難水溶性気体とを固定床触媒層中で接触反応させる方法において、該触媒層として前記固定床触媒層を用い、気液並流下向流で反応させることを特徴とする水溶液中溶質と難水溶性気体との反応方法が提供される。
【０００５】
【発明の実施の形態】
本発明の固定床触媒層（以下、単に触媒層とも言う）において、その触媒としては、従来公知の粒子状又は短繊維状の活性炭触媒が好適に用いられる。このような活性炭触媒の寸法は、固定床触媒層の形成に適したものであればよく、粒子状触媒の場合、その平均粒径は０．２〜４mm、好ましくは０．５〜４mmである。
【０００６】
本発明において、触媒層中に含有される疎水性物質は、その水接触角が６０度以上、好ましくは７０度以上、より好ましくは８０度以上の樹脂であり、その水接触角の上限値は、通常、１２０度である。このような樹脂としては、ポリエチレン、ポリプロピレン、ポリスチレン、ポリ塩化ビニル、含フッ素樹脂等のビニル系樹脂の他、ポリアセタール、ポリエチレンテレフタレート、ポリカーボネート、ポリウレタン、ユレア樹脂、フェノール樹脂、ケイ素樹脂等が挙げられる。
【０００７】
本発明において、前記疎水性物質は、触媒層中に触媒から独立した粒子又は成形体として含有させる。粒子として含有させる場合、その粒子は破砕粒子や成形粒子であることができる。その平均粒径は０．２〜４ｍｍ、好ましくは０．５〜４ｍｍである。好ましい疎水性物質は、触媒粒子と見かけ比重が同程度のものである。
【０００８】
疎水性物質の成形体には、前記粒子以外の形状のもの、例えば、線状体、棒状体、筒状体、ネット状体、繊維、織布、編布等が包含される。これらの成形体において、線状体又は棒状体の場合、その直径は０．１〜４ｍｍ、好ましくは０．５〜２ｍｍで、その長さは１〜１０００ｍｍ、好ましくは５〜３００ｍｍである。筒状体の場合、その外径は０．５〜５．０ｍｍ、好ましくは１．０〜４．０ｍｍ、肉厚は０．０１〜２．０ｍｍ、好ましくは０．１〜１．０ｍｍであり、その長さは１〜１０００ｍｍ、好ましくは５〜３００ｍｍである。ネット状体の場合、そのネットを構成する繊維又は糸の太さは０．０１〜１．０μｍ、好ましくは０．１〜１．０μｍであり、網目の寸法は、４〜１００メッシュ、好ましくは１０〜５０メッシュである。繊維の場合、その太さは１００〜１０００デニール、好ましくは２００〜１０００デニールであり、その長さは１００〜５０００ｍｍ、好ましくは１０００〜５０００ｍｍである。
疎水性物質の触媒層中の含有量は、０．５重量％以上、好ましくは１０重量％以上である。その上限値は、通常、５０重量％以下、好ましくは３０重量％以下である。
【０００９】
本発明の触媒層は、難水溶性気体と水溶液中溶質との反応に適用される。
このような反応としては、従来公知の反応を示すことができ、例えば、水溶液中の硫化ナトリウムと酸素との反応（Ｎａ2Ｓ＋Ｏ2→Ｎａ2Ｓｘ、Ｎａ2Ｓ2Ｏ3）や、水溶液中に溶解している有機物と酸素又は水素との反応、水溶液中に溶解している硝酸塩と水素との反応等が挙げられる。
難水溶性気体は、反応条件における気体の水溶液に対する溶解度が０．１ｋｇｍｏｌ／ｍ3以下の気体であり、このような気体には、酸素、水素、空気、炭化水素等が包含される。
【００１０】
本発明の触媒層を用いて反応を行うには、触媒層中に水溶液を流通させるとともに、難水溶性気体を向流的又は並流的に流通させる。この場合、その反応温度及び圧力は、その水溶液が液状を示す温度及び圧力であり、好ましくは常圧で１００℃以下の温度である。
本発明の方法を好ましく実施するには、溶質を含む水溶液と難水溶性気体とを、触媒層中を気液並流下向流（トリクルフロー）として流通させる。この場合、その気体の線速は、空塔速度で５０ｍ／ｈｒ以上、好ましくは１００ｍ／ｈｒ以上に保持するのが好ましい。その上限値は、通常、１０００ｍ／ｈｒ程度である。
【００１１】
【発明の効果】
前記のようにして、本発明の触媒層中に水溶液と気体とを流通接触させることにより、水溶液中の反応性溶質と反応性気体とを効率よく反応させることができる。
触媒層中で原料水溶液と気体とを接触させると、気体の一部は水溶液中に溶解し、水溶液中に溶解した気体は触媒表面へ拡散するが、本発明の触媒層の場合、その気体の拡散効率はその疎水性物質の作用により高められ、反応効率は向上する。
また、本発明の触媒層の場合、その添加した疎水性物質が粒子又は成形物として存在し、触媒と一体に結合するものでないことから、触媒の有効表面積の減少がなく、長時間にわたって触媒活性を保持することができる。さらに、使用後における触媒処理が容易であるという利点も有する。即ち、触媒に添加した疎水性物質は、これを触媒から分離回収することが容易である。特に、疎水性物質の形状及び／又は寸法を触媒の形状や寸法と異ったものにすることにより、疎水性物質の触媒からの分離性を著しく向上させることができる。
【００１２】
【実施例】
次に本発明を実施例によりさらに詳細に説明する。
【００１３】
比較例１
内径４５．３ｍｍφ、長さ３，６５８ｍｍの反応器を有する固定床流通式反応装置を用いて硫化ソーダの空気による酸化反応試験を実施した。この場合硫化ソーダと空気は、これを固定条中を気液並流下向流（トリクルフロー）として流通させた。実験条件を以下に示す。この場合、固定床触媒としては、１．５ｍｍ径の活性炭触媒を用いた。実験条件
液組成
硫化ソーダ（Ｎａ2Ｏとして）：３３ｇ／ｌ
水酸化ナトリウム（Ｎａ2Ｏとして）：８０ｇ／ｌ
炭酸ソーダ（Ｎａ2Ｏとして）：２０ｇ／ｌ
温度 ：８０℃
圧力 ：〜３ｋｇ／ｃｍ2Ｇ
空気の空塔速度 ：１２２ｍ／ｈｒ〜３０９ｍ／ｈｒ
流空時速度 ：２／Ｈｒ
空気／液比 ：表中に記載
前記実験結果を表１に示す。
【００１４】
【表１】
実施例１
比較例１において、触媒として比較例１で示した活性炭と２ｍｍ径のポリプロピレン粒子を重量比で、それぞれ９０：１０、８０：２０及び７０：３０となるように混合したものを用いた以外は同様にして実験を行った。その結果を表２に示す。
【００１６】
【表２】
比較例２
比較例１において、触媒として０．８ｍｍ径の活性炭触媒を用いた以外は同様にして実験を行った。その結果を表３に示す。
【００１８】
【表３】
実施例２
比較例１において、触媒として比較例２で用いた活性炭にポリプロピレン粒子、塩化ビニル粒子、ポリアセタール粒子、テフロン粒子及びアンスラサイトをそれぞれ活性炭との重量比が８０：２０となるように混合したものを用いた以外は同様にして実験を行った。その結果を表４に示す。
【００２０】
【表４】
比較例３
比較例１において、４．０ｍｍ径の活性炭触媒を用いた以外は同様にして実験を行った。その結果を表５に示す。
【００２２】
【表５】
実施例３
比較例１において、触媒として比較例３で用いた活性炭触媒ととも繊維状ポリプロピレン、網状ポリプロピレン及びポリエチレンテレフタレート（ＰＥＴ）破砕片をそれぞれ混合したものを用いた以外は同様にして実験を行った。その結果を表６に示す。
【００２４】
【表６】
前記表６において、（ ）内に示したｗｔ％は触媒槽における各物質の割合を示す。
また、表６に示した各物質の寸法は以下の通りである。
（１）繊維状ポリプロピレン
直径 ：０．１μｍ
シート幅：４０ｍｍ
長さ ：３．５ｍ
（２）網状ポリプロピレン
形状 ：ネットリング
外径 ：２７．２ｍｍ
長さ ：３．５ｍ
（３）ＰＥＴ破砕片
縦 ：約１０ｍｍ
横 ：約５ｍｍ
厚さ ：約０．５ｍｍ[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fixed bed catalyst layer for contact reaction between a solute in an aqueous solution and a hardly water-soluble gas, and a reaction method using the same. This reaction includes, for example, a reaction of hydrogen, oxygen, or air with a salt, sulfide, or organic substance in an aqueous solution.
[0002]
[Prior art]
In order to react a poorly water-soluble gas and a solute contained in an aqueous solution, it is widely performed to contact these reaction components in a fixed bed catalyst layer. For example, as such a reaction method, in order to generate polysulfide (Na 2 Sx (x = 2 to 5)) by reacting oxygen and sodium sulfide (Na 2 S) contained in an aqueous solution, A method is known in which oxygen (or air) and an aqueous solution containing sodium sulfide are introduced into a fixed bed catalyst layer made of activated carbon to cause a catalytic reaction.
In such a reaction method, a water-repellent substance such as a fluororesin may be attached and bonded to the surface of the catalyst particles in order to promote diffusion of poorly water-soluble gas molecules to the catalyst surface and improve reaction efficiency. It is known (Japanese Patent Publication No. 52-38982, Japanese Patent Laid-Open No. 58-177151, US Pat. No. 4,073,748, US Pat. No. 4,024,229, etc.).
However, in such a conventional method, since the effective surface of the catalyst is reduced due to the adhesive bonding of the water-repellent substance to the surface of the catalyst particles, it is difficult to keep the catalyst highly active for a long time. Moreover, attaching and bonding the fluorine resin to the catalyst particles complicates catalyst preparation and makes it difficult to separate and recover the fluorine resin from the used catalyst. Therefore, the conventional catalyst includes the problem of catalyst activation deterioration and the problem that the catalyst cost is high, and also includes the problem of used catalyst processing such that it is difficult to regenerate and discard the used catalyst. It was a thing.
[0003]
[Problems to be solved by the invention]
The present invention has good diffusibility of a hardly water-soluble gas to the catalyst surface in an aqueous solution and maintains a high catalytic activity for a long time, and further has a problem of catalyst cost and a problem of treatment of used catalyst. It is an object of the present invention to provide a fixed bed catalyst layer that is not used and a reaction method using the same.
[0004]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, according to the present invention, a fixed bed catalyst layer for contact reaction between a solute in an aqueous solution and a hardly water-soluble gas, the catalyst in the catalyst layer is activated carbon, and a water contact angle of 60 degrees in the catalyst layer. fixed bed catalyst layer is provided, it characterized that it contained 0.5 to 50% by weight of a hydrophobic substance having the above resin as discrete particles or moldings from the catalyst. Further, according to the present invention, in the method of contacting and reacting a solute in an aqueous solution and a hardly water-soluble gas in a fixed bed catalyst layer, the fixed bed catalyst layer is used as the catalyst layer, and the reaction is performed in gas-liquid cocurrent downflow. There is provided a method for reacting a solute in an aqueous solution with a hardly water-soluble gas, characterized in that
[0005]
DETAILED DESCRIPTION OF THE INVENTION
In the fixed bed catalyst layer of the present invention (hereinafter also simply referred to as the catalyst layer), a conventionally known particulate or short fiber activated carbon catalyst is preferably used as the catalyst. The size of such an activated carbon catalyst is not particularly limited as long as it is suitable for forming a fixed bed catalyst layer. In the case of a particulate catalyst, the average particle size is 0.2 to 4 mm, preferably 0.5 to 4 mm. .
[0006]
In the present invention, the hydrophobic substance contained in the catalyst layer is a resin having a water contact angle of 60 degrees or more, preferably 70 degrees or more, more preferably 80 degrees or more , and the upper limit value of the water contact angle is Usually, it is 120 degrees. Examples of such a resin include polyacetal, polyethylene terephthalate, polycarbonate, polyurethane, urea resin, phenol resin, silicon resin and the like, in addition to vinyl resins such as polyethylene, polypropylene, polystyrene, polyvinyl chloride, and fluorine-containing resins .
[0007]
In the present invention, the hydrophobic substance is contained in the catalyst layer as particles or molded bodies independent of the catalyst. When contained as particles, the particles can be crushed particles or shaped particles. The average particle diameter is 0.2 to 4 mm, preferably 0.5 to 4 mm. A preferred hydrophobic substance is one having an apparent specific gravity similar to that of the catalyst particles.
[0008]
The molded body of the hydrophobic substance includes a shape other than the particles, for example, a linear body, a rod-shaped body, a cylindrical body, a net-shaped body, a fiber, a woven fabric, a knitted fabric and the like. In these molded bodies, in the case of a linear body or a rod-shaped body, the diameter is 0.1 to 4 mm, preferably 0.5 to 2 mm, and the length is 1 to 1000 mm, preferably 5 to 300 mm. In the case of a cylindrical body, the outer diameter is 0.5 to 5.0 mm, preferably 1.0 to 4.0 mm, and the wall thickness is 0.01 to 2.0 mm, preferably 0.1 to 1.0 mm. The length is 1-1000 mm, preferably 5-300 mm. In the case of a net-like body, the thickness of the fiber or thread constituting the net is 0.01 to 1.0 μm, preferably 0.1 to 1.0 μm, and the mesh size is 4 to 100 mesh, preferably 10-50 mesh. In the case of fibers, the thickness is 100 to 1000 denier, preferably 200 to 1000 denier, and the length is 100 to 5000 mm, preferably 1000 to 5000 mm.
The content of the hydrophobic substance in the catalyst layer is 0.5% by weight or more, preferably 10% by weight or more. The upper limit is usually 50% by weight or less, preferably 30% by weight or less.
[0009]
The catalyst layer of the present invention is applied to the reaction between a hardly water-soluble gas and a solute in an aqueous solution.
As such a reaction, a conventionally known reaction can be shown. For example, a reaction between sodium sulfide and oxygen in an aqueous solution (Na 2 S + O 2 → Na 2 Sx, Na 2 S 2 O 3 ), or in an aqueous solution Reaction of an organic substance dissolved in oxygen with oxygen or hydrogen, reaction of nitrate dissolved in an aqueous solution with hydrogen, and the like.
The hardly water-soluble gas is a gas having a solubility in a gas aqueous solution of 0.1 kgmol / m 3 or less under the reaction conditions, and such gas includes oxygen, hydrogen, air, hydrocarbons, and the like.
[0010]
In order to carry out the reaction using the catalyst layer of the present invention, an aqueous solution is circulated in the catalyst layer, and a hardly water-soluble gas is circulated countercurrently or cocurrently. In this case, the reaction temperature and pressure are the temperature and pressure at which the aqueous solution is in a liquid state, and preferably 100 ° C. or less at normal pressure.
In order to preferably carry out the method of the present invention, an aqueous solution containing a solute and a hardly water-soluble gas are circulated in the catalyst layer as a gas-liquid co-current downflow (tricle flow). In this case, the linear velocity of the gas is preferably maintained at a superficial velocity of 50 m / hr or more, preferably 100 m / hr or more. The upper limit is usually about 1000 m / hr.
[0011]
【The invention's effect】
As described above, the reactive solute and the reactive gas in the aqueous solution can be efficiently reacted by bringing the aqueous solution and the gas into flow contact with each other in the catalyst layer of the present invention.
When the raw material aqueous solution is brought into contact with the gas in the catalyst layer, a part of the gas is dissolved in the aqueous solution, and the gas dissolved in the aqueous solution diffuses to the catalyst surface. In the case of the catalyst layer of the present invention, the gas The diffusion efficiency is enhanced by the action of the hydrophobic substance, and the reaction efficiency is improved.
In addition, in the case of the catalyst layer of the present invention, the added hydrophobic substance exists as particles or a molded product and is not bonded integrally with the catalyst, so there is no reduction in the effective surface area of the catalyst, and the catalytic activity over a long period of time. Can be held. Furthermore, there is an advantage that the catalyst treatment after use is easy. That is, the hydrophobic substance added to the catalyst can be easily separated and recovered from the catalyst. In particular, by making the shape and / or size of the hydrophobic substance different from the shape and size of the catalyst, the separability of the hydrophobic substance from the catalyst can be remarkably improved.
[0012]
【Example】
Next, the present invention will be described in more detail with reference to examples.
[0013]
Comparative Example 1
An oxidation reaction test of sodium sulfide with air was performed using a fixed bed flow type reactor having an inner diameter of 45.3 mmφ and a length of 3,658 mm. In this case, sodium sulfide and air were circulated in the fixed strip as a gas-liquid co-current downflow (tricle flow). Experimental conditions are shown below. In this case, an activated carbon catalyst having a diameter of 1.5 mm was used as the fixed bed catalyst. Experimental conditions Liquid composition Sodium sulfide (as Na 2 O): 33 g / l
Sodium hydroxide (as Na 2 O): 80 g / l
Sodium carbonate (as Na 2 O): 20 g / l
Temperature: 80 ° C
Pressure: ~3kg / cm 2 G
Air superficial velocity: 122m / hr-309m / hr
Airtime speed: 2 / Hr
Air / liquid ratio: described in the table. The experimental results are shown in Table 1.
[0014]
[Table 1]
Example 1
The same as in Comparative Example 1, except that the catalyst used in Comparative Example 1 and 2 mm-diameter polypropylene particles were mixed in a weight ratio of 90:10, 80:20, and 70:30, respectively. The experiment was conducted. The results are shown in Table 2.
[0016]
[Table 2]
Comparative Example 2
In Comparative Example 1, an experiment was performed in the same manner except that a 0.8 mm diameter activated carbon catalyst was used as the catalyst. The results are shown in Table 3.
[0018]
[Table 3]
Example 2
In Comparative Example 1, the catalyst used was a mixture of the activated carbon used in Comparative Example 2 as a catalyst with polypropylene particles, vinyl chloride particles, polyacetal particles, Teflon particles, and anthracite so that the weight ratio to the activated carbon was 80:20. The experiment was conducted in the same manner except that. The results are shown in Table 4.
[0020]
[Table 4]
Comparative Example 3
An experiment was conducted in the same manner as in Comparative Example 1 except that a 4.0 mm diameter activated carbon catalyst was used. The results are shown in Table 5.
[0022]
[Table 5]
Example 3
In Comparative Example 1, the experiment was conducted in the same manner except that the activated carbon catalyst used in Comparative Example 3 was mixed with fibrous polypropylene, reticulated polypropylene, and polyethylene terephthalate (PET) fragments. The results are shown in Table 6.
[0024]
[Table 6]
In Table 6, wt% shown in parentheses indicates the ratio of each substance in the catalyst tank.
Moreover, the dimension of each substance shown in Table 6 is as follows.
(1) Fibrous polypropylene diameter: 0.1 μm
Sheet width: 40mm
Length: 3.5m
(2) Reticulated polypropylene shape: Net ring outer diameter: 27.2 mm
Length: 3.5m
(3) PET fragment length: about 10mm
Next: about 5mm
Thickness: about 0.5mm
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Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01209198A JP4209485B2 (en) | 1997-10-21 | 1998-01-06 | Fixed bed catalyst layer for catalytic reaction between solute in aqueous solution and poorly water-soluble gas, and reaction method using the same |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30656697 | 1997-10-21 | ||
| JP9-306566 | 1997-10-21 | ||
| JP01209198A JP4209485B2 (en) | 1997-10-21 | 1998-01-06 | Fixed bed catalyst layer for catalytic reaction between solute in aqueous solution and poorly water-soluble gas, and reaction method using the same |
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| Publication Number | Publication Date |
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| JPH11188254A JPH11188254A (en) | 1999-07-13 |
| JP4209485B2 true JP4209485B2 (en) | 2009-01-14 |
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