JPS6090041A - Preparation of carbon monoxide absorbing and separating agent - Google Patents
Preparation of carbon monoxide absorbing and separating agentInfo
- Publication number
- JPS6090041A JPS6090041A JP58196123A JP19612383A JPS6090041A JP S6090041 A JPS6090041 A JP S6090041A JP 58196123 A JP58196123 A JP 58196123A JP 19612383 A JP19612383 A JP 19612383A JP S6090041 A JPS6090041 A JP S6090041A
- Authority
- JP
- Japan
- Prior art keywords
- carbon monoxide
- org
- halide
- absorbent
- aromatic rings
- 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.)
- Granted
Links
Abstract
Description
【発明の詳細な説明】
木発明は一酸化戻素（以下Ｃｏ Ｊ 吸収分除剤の製造
方法に関し、特にＧＯを選択的に吸収し、かつ水に対す
る劣化性が少ない固体状の上記分離剤の製造方法に関す
る。[Detailed Description of the Invention] The present invention relates to a method for producing a back oxide monoxide (hereinafter referred to as Co Regarding the manufacturing method.
従来、ガス分離用剤として式ＭＩ ＭＢ Ｘ ｎ・芳香
族（町：Ｃｕ等のＮ１−８族の金属、Ｍ、： ｈｌ！等
のｆｇ Ｍ −Ａ族の金属、Ｘ：ハロゲン、芳香族二０
６〜，２の単環式芳香族炭化水素又はハロゲン化芳香族
炭化水素〕の二金属塩錯体の芳香族炭化水素又はハロゲ
ン化芳香族炭化水素浴液からなる成体状の吸収剤（％開
昭５７−２１３２８号公報〕、０ｕＡｌ！Ｘ４（Ｘ ”
ハμグン原子ハ浦する二金属塩（特公昭４Ｂ−３５０４
１号）寺が提案されているが、これらはいずれもグロビ
レン等の不飽相戻化水素ガスを吸収分＃ｖＩするための
ものであシ、またガス吸収有効成分自体が不安定であっ
て、特に被処理カス中に水分が存在すると短期間に吸収
性能を方化してしまうという欠点があった。Conventionally, gas separation agents have been used with the formula MI MB 0
A solid absorbent (% Kaisho 57-21328], 0uAl!
Bimetallic salt containing atomic atoms (Special Publication Showa 4B-3504)
No. 1) Temple has been proposed, but these are all for absorbing unsaturated phase-reverted hydrogen gas such as globylene, and the effective gas absorption ingredient itself is unstable. In particular, if water is present in the waste to be treated, the absorption performance deteriorates in a short period of time.
Ｒ近になって、■ハロゲン化鋼（１）、ハロクン化アル
ミニウム（句、芳香族炭化水素よシなる液体吸収Ｍ（特
開昭５８−２４３２１号公＠〕、■ハロゲン化ｍ （Ｉ
Ｊ 、ハロゲン化アルミニウム（ＪＪｉ八ポリスチレン
頑ニジなる固体状の吸収剤（％開開５８−４９４５６号
公報）、■ハロゲン化銅（ＩＬハロゲン化アルミニウム
（ＩＪ１活性炭又はグラファイトよシなる固体状の吸収
剤（％開昭５８１２４５１６号公＠）’を用いて、製鉄
所、製油θｒ１石油化学工場等で副生するＣＯ含有混合
ガス中から、曾成化学のＡＮ原料として有用ン工Ｃｏ
を選択的に吸収分離丁句方款が提案された。When approaching R, ■halogenated steel (1), aluminum halide (phrase, liquid absorption M such as aromatic hydrocarbons (Japanese Patent Application Laid-open No. 58-24321), ■halogenated m (I
J, aluminum halide (JJi solid absorbent such as 8 polystyrene (% JP-A No. 58-49456), ■ copper halide (IL aluminum halide (IJ1 solid absorbent such as activated carbon or graphite) (%Kokai No. 58124516@)' was used to extract CO, which is useful as an AN raw material for Sosei Chemical, from the CO-containing mixed gas by-produced in steel plants, oil refineries, petrochemical plants, etc.
A method of selective absorption and separation was proposed.
しかし、上記■の成体状吸収Ａｌｌは、削述の不飽相炭
化水素吸収剤と同様、水分に対する劣化性が着るしく、
長期間安定してＧＯを吸収分離することはできない。上
−〇の固体吸収剤も耐水劣化性が低く、しかもハロゲン
化鋼ｔｌ）と八はグン化アルミニウム＋Ｉ［Ｕ’に担持
し得る賞が少ないという問題があシ、また上記■の活性
炭等で固体吸収剤としたものは、水に対１−る劣化性は
少ないものの、活性炭はＣＯに限らず、混合ガス中の他
の成分をも多蓋に鉄層してしまい、ＣＯの選択性に欠け
るという難点を有している。However, like the unsaturated phase hydrocarbon absorbent mentioned above, the adult absorbent alloy mentioned in (2) above seems to be prone to deterioration due to moisture.
GO cannot be stably absorbed and separated for a long period of time. The solid absorbent shown above also has low resistance to water deterioration, and there is also the problem that there is little support for halogenated steel (tl) and aluminum gunkide + I[U', and activated carbon etc. mentioned above Although solid absorbents have less deterioration with respect to water, activated carbon does not only cover CO but also other components in the mixed gas, making it difficult to select CO. It has the disadvantage of being lacking.
本発明は、これらの欠点を排除し、ＣＯの高選択性吸収
分原性能７ｆｔ彌すると共に、水に対する劣化性が極め
て少ない自体状のＣＯ吸収分離剤を製造し得る方法を提
案するものである。The present invention eliminates these drawbacks and proposes a method for producing a CO absorption/separation agent in its own form that has a highly selective CO absorption capacity of 7 ft and has extremely low deterioration with water. .
すなわち本発明は、ハロゲン化鋼（ＩＪ、ハロゲン化ア
ルミニウム（匈および芳香環を２個以上有する有倹化合
物の有慎層線浴欣を、多孔性無機ば化物に十分接触させ
、次いで遊離有機溶媒を除去することを特徴とする一酸
化炭素吸収分離剤の製造方法に閃するものである。That is, the present invention involves bringing a halogenated steel (IJ), aluminum halide (aluminum halide), and a sintered layer bath coat of a halogenated compound having two or more aromatic rings into sufficient contact with a porous inorganic compound, and then adding a free organic solvent to the porous inorganic compound. The present invention is inspired by a method for producing a carbon monoxide absorbing and separating agent characterized by removing carbon monoxide.
本発明方法におけるハロゲン化銅（ＩＪのハロゲンとし
ては、塩素、臭素、ヨウ素、フッ素のいずれも有効であ
るが、コストや入手のし易さ等から通常は塩化第１蛸が
使用される。As the halogen of copper halide (IJ) in the method of the present invention, any of chlorine, bromine, iodine, and fluorine are effective, but chlorine is usually used because of its cost and availability.
ハロゲン化アルミニウム（ｌＩＪのノ・ロゲンとしても
、塩素、臭素、ヨウ素、フッ素のいずれも有効であるが
、通常は上記と同様の理由て塩化アルミニウムが使用さ
れる。なお、ハロゲン化アルミニウム（匈は一般に不純
物を含むので、昇華法等によって梢製して用いられるが
、前記した従来の俗液法のように重度に梢衾する必要は
ない。Although chlorine, bromine, iodine, and fluorine are all effective as the halogen for aluminum halide (lIJ), aluminum chloride is usually used for the same reason as above. Since it generally contains impurities, it is used after being prepared using a sublimation method or the like, but there is no need for heavy sublimation as in the above-mentioned conventional liquid method.
また、本発明方法における芳香環を２個以上有する有機
化合物としては、ジフェニルメタン等比較的低分子量の
ものから、分子麓数万の直鎖状ポリスチレン等芳香族性
ポリマー等が挙げられる。しかし、調製法の問題等から
有機浴剤に陥屏注の直鎖状ポリスチレン又はその誘導体
が好ましい。斯る直鎖状ポリスチレンの分子量としては
２００以上、好ましくは５００〜５ｏｏｏｏ、更に好ま
しくは８００〜１００００ものである。Further, examples of the organic compound having two or more aromatic rings in the method of the present invention include those having a relatively low molecular weight such as diphenylmethane, and aromatic polymers such as linear polystyrene having tens of thousands of molecular weights. However, due to problems with the preparation method, linear polystyrene or its derivatives, which are used in organic bath agents, are preferred. The molecular weight of such linear polystyrene is 200 or more, preferably 500 to 5000, and more preferably 800 to 10,000.
また、本発明方法で使用される有機溶媒に１解するもの
ならは、上記のポリスチレンの誘導体や変成体であって
もよい。Further, the above-mentioned polystyrene derivatives or modified products may be used as long as they are compatible with the organic solvent used in the method of the present invention.
更に、木兄りＪ方法における壱俵爵媒としては、ベンゼ
ン、トルエン、キシレン等の芳香族化合物、二硫化炭素
、ジクロルメタン等汎用のものが使用される。Furthermore, as the solvent in the Kinori J method, general-purpose solvents such as aromatic compounds such as benzene, toluene, and xylene, carbon disulfide, and dichloromethane are used.
ただし、上記ハロゲン化鋼（１）、ハロゲン化アルミニ
ウム（句および芳香環を２個以上有する有機化合物′ｆ
ｔ浴解１る能力がない溶媒、あるいはこれら化合物を分
解、還元、あるいは酸化する溶媒は好ましくない。例え
は、四塩化炭素やクロロホルムは上記芳香族化合物に比
し）・四ゲン化アルミニウムｔＮＪの俗解性が著しく低
く、本発明方法に使用することは不通である。また、一
般的に溶媒中に水が宮まれる４ｉ１会はハロゲン化アル
ミニウム（１０が部分的に分解され、固形分とハロゲン
酸を発生するので、使用静媒中への水分の混入は厳に避
けるべきである。However, the above-mentioned halogenated steel (1), aluminum halide (phrase and organic compound having two or more aromatic rings)
Solvents that are incapable of t-bath decomposition, or solvents that decompose, reduce, or oxidize these compounds are not preferred. For example, carbon tetrachloride and chloroform (compared to the above-mentioned aromatic compounds) and aluminum tetragenide (tNJ) are significantly less common and cannot be used in the method of the present invention. In addition, in the case of 4I1, where water is generally present in the solvent, aluminum halide (10) is partially decomposed and generates solid content and halogen acid. Should be avoided.
また、本発明方法で得られる吸収分離剤は、後述するよ
うな錯塩と担体の無機酸化物とが一体化したものである
が、その錯塩のハロゲン化アルミニウム側が担体の無機
酸化物と、芳香環を２個以上有する有機化合物と、有機
溶媒との緬同作用によシ疎水性に保たれていると推定さ
れ、このような構成のものを均一に形成するにハ、ハ四
ゲン化Ｍ （１）、ハロゲン化アルミニウム（１１７，
芳香Ｒを２個以上有する有機化合物は勿論、後述する加
温操作等によってこれらから形成さ１＋シる化会物（錯
塩）を十分に浴解する龍力な有Ｊ〜る有機ｔ６媒を使用
することか好ましい。In addition, the absorption/separation agent obtained by the method of the present invention is a product in which a complex salt and an inorganic oxide as a carrier are integrated as described below, and the aluminum halide side of the complex salt is an inorganic oxide as a carrier and an aromatic ring. It is presumed that the hydrophobic property is maintained due to the synergistic interaction between an organic compound having two or more of M and an organic solvent. 1), aluminum halide (117,
In addition to organic compounds having two or more aromatic R atoms, an organic t6 medium with the ability to fully dissolve 1+ complexes (complex salts) formed from these by the heating operation described below is used. It is preferable to do so.
従って、本発明方法においては、ベンゼン、トルエン、
キシレン等の芳香族化合物が好ましい一１１磯俗媒とし
て挙げられる。Therefore, in the method of the present invention, benzene, toluene,
Aromatic compounds such as xylene are mentioned as preferred solvents.
本発明方法において、上記のハロゲン化銅（υとハロゲ
ン化アルミニウム（即は、有機層線に別々に、あるいは
共に１屏させ、かつ芳香１１’２詔以上イ〕１゛る有機
化合物′？：硝加、浴解させる。In the method of the present invention, the above-mentioned copper halide (υ) and aluminum halide (i.e., an organic compound '?' which is applied separately or together to an organic layer and has an aroma of 11'2 or more): Add nitrification and dissolve in bath.
これを多孔性態＋Ａ酸化物に十分接触させる。接触方法
は、含浸法、θ積法、噴霧法等が採用され、ｌよかでも
必要以上にイイ磯Ｙ６媒を使用せす、ズ（（磯故化物の
細孔容積にはは見合う■の蔭欣搬で十分な含浸法が一般
的である。This is brought into sufficient contact with the porous +A oxide. As for the contact method, impregnation method, θ volume method, spray method, etc. are adopted. The impregnation method is generally used, which is sufficient in a transparent manner.
ところで、木兄り」方法による吸収分離剤としての能力
は、銅が１価の状態で作用しているときに、著しいＣＯ
選択性、吸収性な示す。この鋼を１楢で保持する動きを
付つのがハロケン化アルミニウム（旬であり、特に以下
に述べる錯塩中に両者が等モルて例えばａｕＡ／Ｘ４（
Ｘ”ハロゲン、以下同じ）等として〕存在しているとき
に能力が最大となると考えられる。By the way, the ability of the Kienori method as an absorption/separation agent is that when copper is acting in a monovalent state, it can significantly reduce CO2.
Shows selectivity and absorption. The movement to hold this steel in one layer is aluminum halide (in particular, in the complex salt described below, equimolar amounts of both are present, such as auA/X4 (
It is thought that the ability is maximized when the halogen is present (as "X" halogen, the same hereinafter), etc.
そこで本発明方法においては、このような錯塩を形成す
るために、上述の有磯層線浴欣を多孔性無機酸化物に十
分接触させた後に、水分がない状態で、好ましくは小活
性ガス中で、４０〜６０Ｃ１４〜２時間の加温操作を行
う。この加温操作によシ、Ｏｕ （ＩＪ 、 Ａ／ （
同、有機層線に起因する有機化合物、Ｘからなる錯塩が
形成され、また該錯塩は上述したようにづ月俸の無機酸
化物とも、更には芳香Ｒを２個以上有する有機化合物と
も何らかの結合を形成するものと推定される。そして、
この加温操作によシ、遊離の有機面線も一部除去される
。Therefore, in the method of the present invention, in order to form such a complex salt, the above-mentioned aliso layer wire bath salt is brought into sufficient contact with the porous inorganic oxide, and then, in the absence of moisture, preferably in a small active gas. At 40-60C, a heating operation is performed for 14-2 hours. Through this heating operation, Ou (IJ, A/ (
Similarly, a complex salt consisting of the organic compound X caused by the organic layer line is formed, and as mentioned above, the complex salt has some kind of bond with the inorganic oxide of the sulfuric acid and also with the organic compound having two or more aromatic R. It is estimated that it will form. and,
This heating operation also partially removes free organic surface lines.
なお、上記の加Ｔｍ沫作は、有礪層線爵液を多孔性無機
酸化物に接触される前であってもよい。Note that the above-mentioned Tm addition may be performed before the layer-forming liquid is brought into contact with the porous inorganic oxide.
ハロゲン化銅（１）とハロゲン化アルミニウム（母の比
は、上述したようにモル比で１：１が好ましく、余剰の
ハロゲン化アルミニウム（旬が存在しないようにするこ
とが望ましい。As mentioned above, the molar ratio of copper halide (1) to aluminum halide (base) is preferably 1:1, and it is desirable that there is no excess aluminum halide.
有磯層線浴欣の一度は、ハロゲン化銅＋ＩＪ 、ハロゲ
ン化アルミニウム（坦および芳香環を２個以上有１−る
有機化合物が浴解し得る礫度であればよ（、特に芳香ｉ
Ｒを２個以上有する’４ｇ磯化合物が十分に均一に俗鳩
づ°ることが必要である。一般的には、ハロゲン化銅（
１）、ハロケン化アルミニウム（坦および芳香環を２個
以上有する有機化合物のトータルが無機酸化物に対して
５〜５゜ｗｔ％担持される俗液劇度および道であれはよ
い。When using the Ariiso layer bath, copper halide + IJ, aluminum halide (flat and an organic compound having two or more aromatic rings) can be dissolved in the bath (in particular, aromatic i
It is necessary that the '4g iso compound having two or more R's is distributed sufficiently uniformly. Generally, copper halide (
1) Aluminum halide (a total of 5 to 5% by weight of organic compounds having two or more flat and aromatic rings is supported on the inorganic oxide) is acceptable.
また、芳香環を２１１１！１１以上有する有機化合物は
、ハロゲン化５ｌｉｄ （１７ｓハロゲン化アルミニウ
ム（切に対し、爪血比で０．２〜５、特に０．４〜２の
郭囲が好ましい。Further, the organic compound having 2111!11 or more aromatic rings is preferably halogenated 5lid (17s aluminum halide) with a nail blood ratio of 0.2 to 5, particularly 0.4 to 2.
また、多孔性焦観ｔｙ、化物は、ハロゲン化銅（υ、ハ
ロゲン化アルミニウムｔｆｆｌＪおよび芳香Ｒ’ｒ２１
固以上有する有機化合物が十分に分散し得る龍カ′４ｒ
：持つものが反用される。ただし０ｕ（１）を還元、ば
化せず、しかもハロゲン化アルミニウム（功を分屏しな
いものである必要がある。In addition, porous photic ty, compound is copper halide (υ, aluminum halide tfflJ and aromatic R'r21
Ryuka'4r in which organic compounds having more than
: What you have is used against you. However, it must be a material that does not reduce or oxidize Ou(1), and must not be an aluminum halide.
斯る多孔性無機酸化物としては、遊離水な含まないもの
で、かつ十分な表面積を持つものが好ましい。表面積は
余り太き過ぎると、必要以上に銅ないしアルミニウムを
固定不活性化したり、細孔が小さくなり過ぎて錯塩の分
散性を低下させる。従って、１１０へ１２０ｏ℃、好ま
しくは４５０へ１１００’Ｃ，より好ましくは５００〜
９００℃で焼され、ＢＩＩＣＴ表面積で４０〜４００
ｍ２７Ｉ 、好ましくは５０〜５５０ｍ２／Ｉのものが
使用される。具体的には、アルミナ。Such a porous inorganic oxide is preferably one that does not contain free water and has a sufficient surface area. If the surface area is too large, copper or aluminum will be fixed and inactivated more than necessary, or the pores will become too small, reducing the dispersibility of the complex salt. Therefore, 110 to 120°C, preferably 450 to 1100°C, more preferably 500 to
Baked at 900℃, BIICT surface area is 40-400
m27I, preferably 50 to 550 m2/I, is used. Specifically, alumina.
シリカ、シリカアルミナ、チタニア、シリカマグネシア
、ジルコニア、アルミナマグネシア等が挙げられる。な
かでも優れた分散担持性を示すものは、アルミナ、シリ
カ、シリカアルミナである。これらのものは、特に、そ
の調節され得る細孔構造のため、芳香環を２個以上有す
る有機化合物を均一に分散固定化する。この能力に最も
優れるのはアルミナである。Examples include silica, silica alumina, titania, silica magnesia, zirconia, alumina magnesia, and the like. Among them, alumina, silica, and silica alumina exhibit excellent dispersion and support properties. In particular, because of their adjustable pore structure, they uniformly disperse and immobilize organic compounds having two or more aromatic rings. Alumina has the best ability to do this.
本発明方法においては前述の接触、加温操作の後、遊離
有機溶媒を減圧除去する。このとき前述と同様の加温（
すなわち、水分のない状態。In the method of the present invention, after the above-mentioned contacting and heating operations, the free organic solvent is removed under reduced pressure. At this time, heating (
In other words, without water.
好ましくは不活性ガス中で４０〜６０℃の加温）を加え
ることもできる。この除去操作は液相状態の有機溶媒が
な（なるまで行うことが重要である。何故なら１本発明
方法による固体状吸収分離剤が十分な耐水性を発揮する
のはＯｕ （ＩｌとＡＩ！（１１１１が完全に多孔性無
機酸化物担体に固定化し、かつ芳香環を２個以上有する
有機化合物が分散固定化している場合であり、遊離有機
溶媒が液相状態で細孔内に保持されたままであると、前
述の従来の液体状吸収剤にみられるように水によって容
易にＣＯの選択吸収性能を劣化し℃しまうからである。It is also possible to add heating (preferably at 40 to 60° C. in an inert gas). It is important to carry out this removal operation until the organic solvent is in a liquid phase.This is because the solid absorbing and separating agent according to the method of the present invention exhibits sufficient water resistance. (This is a case where 1111 is completely immobilized on a porous inorganic oxide support, and an organic compound having two or more aromatic rings is dispersed and immobilized, and the free organic solvent is retained in the pores in a liquid phase.) This is because, if it is present, the selective absorption performance of CO is easily deteriorated by water, as seen in the conventional liquid absorbent described above, and the CO absorption performance is easily reduced to ℃.
火工、実ＪｉＭ例をあげて本発明方法を更に具体的に説
明する。The method of the present invention will be explained in more detail using pyrotechnic and actual JiM examples.
〔実施例１〕
塩化アルミニウム（至）は、市販の特級試薬（ここでは
キシダ化学工業μ株］製のもの）を昇華法により精製し
木純物を取り除いて用い、トルエンは市販の特級試薬（
ここでは和光純薬工朶（（株］＃のもの）を金属ナトリ
ウムで脱水後。[Example 1] Aluminum chloride (solium) was used by purifying a commercially available special grade reagent (in this case, manufactured by Kishida Kagaku Kogyo μ Co., Ltd.) by sublimation method to remove wood pure substances, and toluene was used by using a commercially available special grade reagent (here, manufactured by Kishida Kagaku Kogyo μ Co., Ltd.).
Here, Wako Pure Chemical Industries (#) was dehydrated with metallic sodium.
蒸留して使用した。塩化＠（■）は市販の特級試薬（こ
こでは小島化学薬品ｃ株３製のもの）をそのまま使用し
た。It was distilled and used. For chloride (■), a commercially available special grade reagent (in this case, manufactured by Kojima Chemicals C Stock 3) was used as is.
乾燥蟹素下で、２００ｍのロータリーエバポレーター中
に上記の塩化アルミニウム（ｎｇ ｏ、ａ ｙ（４ａ
ｍｏｌ ）、上記の塩化銅（１） ０，６１１ Ｃ６ｗ
ｏｏｌ）および分子、１ｄ２２００のポリスチレン１．
９Ｙ入れ、トルエン２０ｄを加えて溶屏し、ロータリー
エバポレーターを回転し、かきまぜつつ、６０Ｃで２時
間加熱保温した。なお、上記の窒素は市販の窒素（ここ
では帝国酸素ｃ株］製の純ｉ ９９．９９９％のもの）
を使用直前に市販のモレキュラーシープ５Ａ（ここでは
日化梢工（株Ｊ製のもの）ａ’充填した塔に通過させて
精製したものを使用した。The above aluminum chloride (ng o, a y (4a
mol ), above copper chloride (1) 0,611 C6w
ool) and molecules, 1d2200 polystyrene 1.
9 Y was added, 20 d of toluene was added and melted, and heated and kept at 60 C for 2 hours while stirring by rotating a rotary evaporator. The above nitrogen is commercially available nitrogen (here, pure i 99.999% manufactured by Teikoku Sanso C strain).
Immediately before use, the product was purified by passing it through a column filled with commercially available Molecular Sheep 5A (in this case, manufactured by Nikka Kozuko Co., Ltd. J) a'.
一方、別の２０ ｏｍｌロータリーエバポレーターに、
５５０Ｃにて３時間焼成されて市販されているアルミナ
Ａ担体（触媒化成製の平均細孔直径１０８！、ＢＥＴ
ｉ面積２５０ ！１１２／ Ｉ ） ’ｔ’１０．９入
れ、真空ポンプを用いてナスフラスコ内部を十分に脱気
した後、この中に滴下ロートを用いて、先に脚壁した塩
化アルミニウム（蛎、塩化鋼（υおよびポリスチレンの
トルエン静液を加えた。１０分間か（はんヲ続けたのち
、ロータリーエバボレータル内を減圧Ｃ６Ｃ６ｍ５Ｈに
して一昼夜放直し、トルエンを十分に除去して吸収剤を
ｒＪ＠製した。Meanwhile, in another 20 oml rotary evaporator,
Commercially available alumina A carrier calcined at 550C for 3 hours (average pore diameter 108! manufactured by Catalyst Kasei Co., Ltd., BET)
i area 250! 112/I) 't' 10.9, and after sufficiently deaerating the inside of the eggplant flask using a vacuum pump, using a dropping funnel, add aluminum chloride (chub, chloride steel) into the flask using a dropping funnel. υ and a toluene static solution of polystyrene were added. After continuing for 10 minutes, the inside of the rotary evaporator was reduced to C6C6m5H and left overnight to sufficiently remove toluene and prepare an absorbent.
この吸収剤の性能な確認するため、２００ｍＪの四−タ
リーエバボレーター内に該吸収剤を人ｔＬ１ａｔｍの一
酸化炭素と堕累の混合ガス（−酸化炭素分圧０．７９
ａｔｒｎ 、 ｇ素分圧０．２１ ａｔｍ ）１２乞入
れた容器と結合し、ロータリーエバポレーターを回転し
かきまぜつつ、２６Ｃで一酸化炭素の吸収操作を行った
。この吸収操作は一酸化炭素と窒素の混合ガスをエアー
ポンプを用いて、１．４詔／ｍｉｎで循環して吸収剤の
上を通過させることによシイテつだ。なお、該−酸化炭
素と窒素の混合ガスは市販品（ここでは５Ｊ！鉄化学工
菓（株３製の純反ＣＯ： ７８．８２％Ｎ２：２１．１
８％のものノン使用Ｉ＆前に市販の脱酸素塔（日化稍工
し株）装のもの〕を通過させて精製したものを使用した
。In order to confirm the performance of this absorbent, the absorbent was placed in a 200 mJ four-tally evaporator with a mixed gas of carbon monoxide and decomposition (-carbon oxide partial pressure 0.79).
Atrn, g partial pressure 0.21 atm) 12 It was connected to a container filled with water, and carbon monoxide was absorbed at 26C while a rotary evaporator was being rotated and agitated. This absorption operation is carried out by circulating a mixed gas of carbon monoxide and nitrogen at a rate of 1.4 g/min using an air pump and passing it over the absorbent. The mixed gas of carbon oxide and nitrogen is a commercially available product (5J! Pure anti-CO manufactured by Tetsu Kagaku Koka Co., Ltd. 3: 78.82% N2: 21.1).
An 8% product was purified by passing it through a commercially available deoxygenation tower (Nikkasho Kogyo Co., Ltd.) before use).
一酸化炭素吸収量は、ガスビューレット法ニよシ２６Ｃ
で６＋１ｊ定した。−酸化炭素の吸収は迅速で、１０分
後の一酸化炭素吸収蓋は１ 、 Ｏｍ ｍｏｌであった
。The amount of carbon monoxide absorbed is 26C using the gas buret method.
6+1j was determined. - The absorption of carbon oxide was rapid, and the carbon monoxide absorption cap after 10 minutes was 1.0 mmol.
次に、吸収剤）ｉｌａｔｍで９００に加熱し、吸収した
一酸化炭素な放出させた。Next, it was heated to 900°C with an absorbent (Ilatm) to release the absorbed carbon monoxide.
一方、窒素ガス（上述の市販品をＮ製したもの）１ノを
入れた容器と、蒸留水を入れた洗気びんを結合し、エア
ーポンプにて輩木ガスを洗気びんに通すことにょ＃）２
６Ｃの飽和水蒸気正分の水（２００００ｐｐｍ ）を窒
素ガス中に混入し、該ガスを上記の一酸化炭素放出後の
吸収剤の上に０．８４７ ｍｉｎで１０分間循環させた
（以下、この操作を水処理とい５）。On the other hand, combine a container containing nitrogen gas (N made from the commercially available product mentioned above) and an air washing bottle containing distilled water, and use an air pump to pass Nagi gas through the air washing bottle. #)2
Water (20,000 ppm) equal to 6C saturated steam was mixed into nitrogen gas, and the gas was circulated for 10 minutes at 0.847 min over the above absorbent after releasing carbon monoxide (hereinafter, this procedure This is called water treatment5).
その後、仁の吸収剤を２６０で、エバポレーターを回転
させなから１ ａｔｍの一酸化炭素と窒素の混合ガス（
−酸化炭素分圧Ｌ７９ ａｔｍ 、窒素分子ｆ： ０．
２１ ａｔｍ ） （上述の市販品を精製したもの〕１
！を入れた容器と結合し、エアーポンプを用いて吸収剤
の上を循環させて得度−ば化炭素の吸収操作を行った。After that, add a mixture of carbon monoxide and nitrogen gas (1 atm) while rotating the evaporator.
- Carbon oxide partial pressure L79 atm, nitrogen molecule f: 0.
21 atm) (purified from the above commercial product) 1
! The absorbent was connected to a container containing carbon, and an air pump was used to circulate the absorbent over the absorbent to absorb the carbon.
この場会の一酸化炭素の吸収も迅速であり、１０分浚に
は、ｊ、６ ｍ ｍａｔの−ば化炭素を吸収した。The absorption of carbon monoxide at this point was also rapid, and in 10 minutes of dredging, J, 6 m mat of carbon monoxide was absorbed.
次に吸収剤を、１ ａｔｍで９０Ｃに加熱し、吸収した
一酸化炭素を放出させた。The absorbent was then heated to 90C at 1 atm to release the absorbed carbon monoxide.
その仮、上述の水処理、吸収、放出を繰返し、−酸化炭
素の吸収量を６（す足した。この結果を後述の表−２に
示す。The above-mentioned water treatment, absorption, and release were repeated, and the absorbed amount of -carbon oxide was increased by 6. The results are shown in Table 2 below.
〔夷ＪＩ！！汐ｕ ２〜７ 〕
実施例１の有情層線、ポリスチレン、無機酸化物の代わ
シに表−１に示すものを使用した以外は笑り例１と同僚
の操作を行った。−ば化炭素の吸収量を表−２に合わせ
て示す。[Yi JI! ! U 2-7 ] The operations of Example 1 and those of colleagues were carried out, except that the materials shown in Table 1 were used in place of the sentient layer wire, polystyrene, and inorganic oxide of Example 1. -The absorption amount of carbon dioxide is also shown in Table-2.
戎−１
※シリカニＭ士ダヴィソン社製商品名ｒＤ ＧｆｉＬ（
５５０Ｇ焼成品、ａｇ’ｒ表面積６００ｍ２／ １１
）
※※アルミナＢ担体：アルミナＡＪＩＩ体（実施例１で
使用したもの）を更に８００
Ｃで焼成したもの（ＢＩＣＴ表面
積１５０ ｍ２／ Ｅｌ ）
〔比較例１〕
乾燥窒素下で、２００ｍＡ’の二ロナスフラスコ中に０
．８１ （６ｍｒｎｏｌ）の塩化アルミニウム（■）。Ebisu-1 *Sirikani Mshi Davison product name rD GfiL (
550G fired product, ag'r surface area 600m2/11
) ※※Alumina B carrier: Alumina AJII body (used in Example 1) further calcined at 800 C (BICT surface area 150 m2/El) [Comparative Example 1] 200 mA' Nironas under dry nitrogen 0 in flask
．． 81 (6 mrnol) of aluminum chloride (■).
０．６７７ （６ｍｍｏ／）の塩化銅Ｃ１）および１ｇ
のポリスチレン（分子量２２００ ）を入れ、トルエン
２０ＴＬｌを加えて溶解し、磁気か（はん機を用いてか
きまぜつつ、６０℃で２時間加熱保温して液体状吸収剤
を調製した。0.677 (6 mmo/) of copper chloride C1) and 1 g
Polystyrene (molecular weight: 2200) was added thereto, and 20 TL of toluene was added to dissolve it. The mixture was heated and kept at 60° C. for 2 hours while stirring using a magnetic toner to prepare a liquid absorbent.
２００ゴの二ロナスフラスコ内に上記の液体状吸収剤を
入れ、１ ａｔｍ 、の−酸化炭素と窒素の混合ガス（
−酸化炭素分圧０，７９ ａｔｍ 、窒素分圧０．２１
ａｔｍ ） （実施例１と同じ市販品を精製したもの
を使用、以下同じ〕１１３を入れた容器と結合し磁気か
（はん機を用いてかきまぜつつ２６℃で一酸化炭素を吸
収させた。該−酸化炭素と窒素の混合ガスはエアーポン
プを用いて。The above liquid absorbent was placed in a 200g Nironas flask, and 1 atm of a mixed gas of carbon oxide and nitrogen (
- Carbon oxide partial pressure 0.79 atm, nitrogen partial pressure 0.21
atm) (A purified commercially available product as in Example 1 was used, the same applies hereinafter).The mixture was combined with a container containing 113, and carbon monoxide was absorbed at 26° C. while stirring using a magnetic hammer. The mixed gas of carbon oxide and nitrogen is produced using an air pump.
Ｌ４ 、ｅ ／ ｍｉｎで循環して吸収剤の上を通過さ
せた。It was passed over the absorbent with circulation at L4, e/min.
一酸化炭素吸収量はガスビューレット法により２６℃で
測定した。−酸化炭素の吸収は迅速で、１０分後の一酸
化炭素吸収量は１．６ ｍｍｏ／であった。The amount of carbon monoxide absorbed was measured at 26°C by the gas buret method. - The absorption of carbon oxide was rapid, and the amount of carbon monoxide absorbed after 10 minutes was 1.6 mmo/.
次に吸収剤を１ ａｔｍ 、で９０℃に加熱し、吸収し
た一酸化炭素を放出させた。The absorbent was then heated to 90° C. at 1 atm to release the absorbed carbon monoxide.
一方、望素ガス（純度９９，９９９％）（実施例１と同
じ市販品を精製したものを使用）１４人れた容器と、蒸
留水を入れた洗気びんを結合し、エアポンプにて窒素ガ
スを洗気びんに通すことにより２６℃の飽和水蒸気圧の
水（２００００ｐｐｒｎ ）を窒素ガス中に混入し、該
ガスを上記−酸化炭素放出の吸収剤の上に０．８ Ｅ
／ ｍｉｎで１０分間循環さヒた。On the other hand, a container containing 14 people of desired oxygen gas (purity 99,999%) (used the same purified commercial product as in Example 1) was combined with an air washing bottle containing distilled water, and an air pump was used to remove nitrogen gas. Water (20,000 pprn) at saturated vapor pressure at 26°C is mixed into the nitrogen gas by passing the gas through a scrubbing bottle, and the gas is poured onto the carbon oxide release absorbent at 0.8 E.
/min for 10 minutes.
その後、この吸収剤を２６℃でエバボレークーを回転さ
せなから１ ａｔｍの一酸化炭素と窒素の混合ガス（−
酸化炭素分圧Ｑ、７９ ａｔｍ 画素分圧０．２１ ａ
ｔｍ ） １４３を入れた容器と結合し、エアーポンプ
を用いて吸収剤の上を循環させて再度−酸化炭素を吸収
させた。このときの−酸化炭素の吸収量はＯｍｍｏｅで
あった。Thereafter, this absorbent was heated to 26°C by rotating an evaporator and was heated to 1 atm of a mixed gas of carbon monoxide and nitrogen (-
Carbon oxide partial pressure Q, 79 atm Pixel partial pressure 0.21 a
tm) 143 and circulated over the absorbent using an air pump to absorb carbon oxide again. The amount of -carbon oxide absorbed at this time was Ommoe.
以上の実施列、比較例から明らかなように。As is clear from the above implementation series and comparative examples.
本発明方法で製造される一酸化炭素吸収分離剤は、水に
対する劣化性が極めて少な（、長期間安定して一酸化炭
素の吸収分離に供することができるものである。The carbon monoxide absorption and separation agent produced by the method of the present invention has extremely low deterioration with water (and can be stably used for absorption and separation of carbon monoxide for a long period of time).
代理人 内 １） 明 代理人 萩 原 亮 −Among agents: 1) Akira Agent Ryo Hagi Hara -
Claims (1)
によび芳香環を２個以上■する合壁化合物の＋ｉ磯′ｍ
媒浴欣ン、多孔性無磯戚化物に十分接〕執させ、仄いて
遊離有機層線を除去することを特徴とする一酸化炭素吸
収分離剤製造方法。 （２Ｊ 芳香環な２個以上有する有１表化合物として、
何機溶媒に靜）弾性の直鎖状ポリスチレン、その訪導体
又はその裳成体を使用することを特徴とする特許結水の
乾ｄ（υ記載の方法・（３） 多孔Ｇ ＭＥ、 ４０
Ｍ化物としてアルミナ、シリカ又はシリカアルミナを使
用することを特徴とする特ｆｆ請氷の範囲（１７又は（
２島己載の方法。(1) Halo saponified steel (υ, aluminum halide (according to the phrase +iiso'm of joint wall compounds with two or more aromatic rings)
1. A method for producing a carbon monoxide absorbing and separating agent, which comprises thoroughly contacting a porous solid material with a medium bath and removing free organic layers. (2J As a Table 1 compound having two or more aromatic rings,
A patented water drying method characterized by using elastic linear polystyrene, a conductor thereof, or a composite thereof (3) Porous G ME, 40
The range of features (17 or (
The method of posting 2 islands.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58196123A JPS6090041A (en) | 1983-10-21 | 1983-10-21 | Preparation of carbon monoxide absorbing and separating agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58196123A JPS6090041A (en) | 1983-10-21 | 1983-10-21 | Preparation of carbon monoxide absorbing and separating agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6090041A true JPS6090041A (en) | 1985-05-21 |
| JPS6211897B2 JPS6211897B2 (en) | 1987-03-16 |
Family
ID=16352621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58196123A Granted JPS6090041A (en) | 1983-10-21 | 1983-10-21 | Preparation of carbon monoxide absorbing and separating agent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6090041A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62108724A (en) * | 1985-11-08 | 1987-05-20 | Chiyoda Chem Eng & Constr Co Ltd | Method for adsorbing carbon monoxide |
| EP0472180A2 (en) * | 1990-08-23 | 1992-02-26 | Air Products And Chemicals, Inc. | Highly dispersed cuprous compositions |
| US20100204043A1 (en) * | 2007-06-04 | 2010-08-12 | Korea Institute Of Energy Research | Adsorbent for selective adsorption of carbon monoxide and process for preparation thereof |
| CN110314653A (en) * | 2019-07-16 | 2019-10-11 | 南京工业大学 | A kind of preparation and application of high stability monovalence copper modified metal organic framework material |
-
1983
- 1983-10-21 JP JP58196123A patent/JPS6090041A/en active Granted
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62108724A (en) * | 1985-11-08 | 1987-05-20 | Chiyoda Chem Eng & Constr Co Ltd | Method for adsorbing carbon monoxide |
| EP0472180A2 (en) * | 1990-08-23 | 1992-02-26 | Air Products And Chemicals, Inc. | Highly dispersed cuprous compositions |
| US20100204043A1 (en) * | 2007-06-04 | 2010-08-12 | Korea Institute Of Energy Research | Adsorbent for selective adsorption of carbon monoxide and process for preparation thereof |
| US8377842B2 (en) * | 2007-06-04 | 2013-02-19 | Korea Institute Of Energy Research | Adsorbent for selective adsorption of carbon monoxide and process for preparation thereof |
| CN110314653A (en) * | 2019-07-16 | 2019-10-11 | 南京工业大学 | A kind of preparation and application of high stability monovalence copper modified metal organic framework material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6211897B2 (en) | 1987-03-16 |
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