JP2879057B2 - Carbon dioxide separation enhanced transport membrane - Google Patents
Carbon dioxide separation enhanced transport membraneInfo
- Publication number
- JP2879057B2 JP2879057B2 JP7079758A JP7975895A JP2879057B2 JP 2879057 B2 JP2879057 B2 JP 2879057B2 JP 7079758 A JP7079758 A JP 7079758A JP 7975895 A JP7975895 A JP 7975895A JP 2879057 B2 JP2879057 B2 JP 2879057B2
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- JP
- Japan
- Prior art keywords
- carbon dioxide
- membrane
- carrier
- gas
- separation
- 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.)
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- Separation Using Semi-Permeable Membranes (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、混合ガス中の二酸化炭
素を分離、濃縮するための二酸化炭素分離促進輸送膜に
関するものである。特に、混合ガス中に二酸化炭素以外
の酸性ガスが不純物として含まれている場合でも、有効
に作用する二酸化炭素分離促進輸送膜に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a carbon dioxide separation and transport membrane for separating and concentrating carbon dioxide in a mixed gas. In particular, the present invention relates to a carbon dioxide separation-accelerated transport membrane that functions effectively even when a mixed gas contains an acidic gas other than carbon dioxide as an impurity.
【０００２】[0002]
【従来の技術】二酸化炭素に親和性を有する物質（二酸
化炭素キャリヤー）を含む分離膜としては、アルカリ金
属炭酸塩水溶液、アルカノールアミン等を用いた液膜が
知られている。これらの膜は、二酸化炭素の分離透過性
能にすぐれているものの、その特性は未だ十分なもので
はなく、特に、混合ガス中に不純物として二酸化炭素以
外の酸性ガスが含まれている場合、著しく性能が低下す
るという問題がある。近年、地球温暖化問題を反映し、
燃焼排ガスからの二酸化炭素の分離回収技術の分野に膜
分離技術を用いることが検討されているが、これら燃焼
排ガスの中にはイオウ酸化物、窒素酸化物等の二酸化炭
素以外の酸性ガスが不純物として含まれている場合が多
く、これらの不純物による膜性能低下に対する対策技術
の必要性が指摘されている（膜シンポジウム９４’予稿
集，Ｎｏ．６，６５（１９９４）、ＩＣＣＤＲ−２予稿
集，２４（１９９４）。2. Description of the Related Art As a separation membrane containing a substance having an affinity for carbon dioxide (carbon dioxide carrier), a liquid membrane using an aqueous solution of an alkali metal carbonate, an alkanolamine or the like is known. Although these membranes have excellent carbon dioxide separation and permeation performance, their characteristics are not yet sufficient, especially when mixed gas contains acidic gas other than carbon dioxide as impurities. Is reduced. In recent years, reflecting global warming issues,
The use of membrane separation technology in the field of technology for separating and recovering carbon dioxide from flue gas is being studied, but acid gases other than carbon dioxide, such as sulfur oxides and nitrogen oxides, are present in these flue gases. In many cases, it is pointed out that the necessity of a countermeasure technique for the film performance degradation due to these impurities is required (Membrane Symposium 94 'Proceedings, No. 6, 65 (1994), ICDR-2 Proceedings, 24 (1994).
【０００３】[0003]
【発明が解決しようとする課題】本発明は、二酸化炭素
以外の酸性ガスを不純物として含む混合ガスに対して
も、二酸化炭素透過特性にすぐれた二酸化炭素分離促進
輸送膜を提供することをその課題とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a carbon dioxide separation-enhanced transport membrane having excellent carbon dioxide permeation characteristics even for a mixed gas containing an acidic gas other than carbon dioxide as an impurity. And
【０００４】[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、可逆的に二酸化炭素
と反応し、その反応物から二酸化炭素を放出する物質と
二酸化炭素以外の酸性ガスと可逆的に反応し、その反応
物から当該酸性ガスを放出する物質を含む溶液を膜中に
保持させたことを特徴とする二酸化炭素分離促進輸送膜
が提供される。ここで、可逆的に二酸化炭素と反応し、
その反応物から二酸化炭素を放出する物質を二酸化炭素
キャリヤーと称する。また、二酸化炭素以外の酸性ガス
と可逆的に反応し、その反応物から当該酸性ガスを放出
する物質を酸性ガスキャリヤーと称する。Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, according to the present invention, it reacts reversibly with carbon dioxide, reacts reversibly with a substance releasing carbon dioxide from the reactant and an acid gas other than carbon dioxide, and releases the acid gas from the reactant A carbon dioxide separation-enhanced transport membrane, characterized in that a solution containing a substance to be retained is retained in the membrane. Here, it reacts reversibly with carbon dioxide,
The substance that releases carbon dioxide from the reactants is called a carbon dioxide carrier. A substance that reversibly reacts with an acid gas other than carbon dioxide and releases the acid gas from the reaction product is referred to as an acid gas carrier.
【０００５】本発明で用いる二酸化炭素キャリヤーとし
ては、従来公知の各種のものを用いることができる。こ
の場合の二酸化炭素キャリヤーは、二酸化炭素と親和性
を有する物質であり、塩基性を示す各種の無機及び有機
物質が用いられる。本発明で好ましく用いられる二酸化
炭素キャリヤーは、アルカリ金属炭酸塩及び／又はアル
カリ金属重炭酸塩、アルカリ金属炭酸塩及び／又はアル
カリ金属重炭酸塩とアルカリ金属イオンと錯体を形成す
る多座配位子との混合物、アルカノールアミン等を挙げ
ることができる。As the carbon dioxide carrier used in the present invention, various known carbon dioxide carriers can be used. The carbon dioxide carrier in this case is a substance having an affinity for carbon dioxide, and various inorganic and organic substances showing basicity are used. The carbon dioxide carrier preferably used in the present invention is an alkali metal carbonate and / or an alkali metal bicarbonate, a polydentate ligand which forms a complex with an alkali metal ion and an alkali metal bicarbonate. And alkanolamines.
【０００６】二酸化炭素キャリヤーとして用いられる前
記アルカリ金属炭酸塩としては、炭酸リチウム、炭酸ナ
トリウム、炭酸カリウム、炭酸ルビジウム、炭酸セシウ
ムを挙げることができる。アルカリ金属重炭酸塩として
は、炭酸水素リチウム、炭酸水素ナトリウム、炭酸水素
カリウム、炭酸水素ルビジウム、炭酸水素セシウムを挙
げることができる。Examples of the alkali metal carbonate used as a carbon dioxide carrier include lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, and cesium carbonate. Examples of the alkali metal bicarbonate include lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, rubidium hydrogen carbonate, and cesium hydrogen carbonate.
【０００７】アルカノールアミンとしては、モノエタノ
ールアミン、ジエタノールアミン、トリエタノールアミ
ン、モノプロパノールアミン、ジプロパノールアミン、
トリプロパノールアミン等各種のものを挙げることがで
きる。The alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine,
Various things such as tripropanolamine can be mentioned.
【０００８】二酸化炭素キャリヤーは、前記したものに
限られるものではなく、二酸化炭素と親和性を有するも
のであればよく、有機酸のアルカリ金属塩等各種のもの
を用いることができる。[0008] The carbon dioxide carrier is not limited to those described above, but may be any one having an affinity for carbon dioxide, and various types such as alkali metal salts of organic acids can be used.
【０００９】アルカリ金属イオンと錯体を形成する多座
配位子としては、従来公知のもの、例えば、１２−クラ
ウン−４、１５−クラウン−５、１８−クラウン−６、
ベンゾ−１２−クラウン−４、ベンゾ−１５−クラウン
−５、ベンゾ−１８−クラウン−６、ジベンゾ−１２−
クラウン−４、ジベンゾ−１５−クラウン−５、ジベン
ゾ−１８−クラウン−６、ジシクロヘキシル−１２−ク
ラウン−４、ジシクロヘキシル−１５−クラウン−５、
ジシクロヘキシル−１８−クラウン−６、ｎ−オクチル
−１２−クラウン−４、ｎ−オクチル−１５−クラウン
−５、ｎ−オクチル−１８−クラウン−６等の環状ポリ
エーテル；クリプタンド〔２．１〕、クリプタンド
〔２．２〕等の環状ポリエーテルアミン；クリプタンド
〔２．２．１〕、クリプタンド〔２．２．２〕等の双環
状ポリエーテルアミン、１，４，７，１０，１３，１６
−ヘキサアザシクロオクタデカン、８−アザアデニン等
の環状ポリアミン；ポリエチレングリコール、ポリエチ
レングリコールモノアルキルエーテル、ポリプロピレン
グリコール等の非環状ポリエーテル；エチレンジアミン
四酢酸、イミノ二酢酸、ニトリロ三酢酸、ヒドロキシエ
チルイミノ二酢酸、ｔｒａｎｓ−１，２−ジアミノシク
ロヘキサン−Ｎ，Ｎ，Ｎ′，Ｎ′−四酢酸、エチレンジ
エチルトリアミン−Ｎ，Ｎ，Ｎ′，Ｎ″，Ｎ″−五酢
酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒド
ロキシエチルグリシン等のポリアミノカルボン酸；エチ
レンジアミンテトラキス（メチレンホスホン酸）、ニト
リロトリス（メチレンホスホン酸）等のポリアミノリン
酸；クエン酸等のオキシカルボン酸；縮合リン酸；エチ
レンジアミン、ジエチレントリアミン、トリエチレンテ
トラミン等のポリアミン；アセチルアセトン、オキシン
の他、グリシン、ヘミン、クロロフィル、バリノマイシ
ン、ナイジェリシン等の天然物及びその誘導体を用いる
ことができる。As the polydentate ligand forming a complex with an alkali metal ion, conventionally known ones, for example, 12-crown-4, 15-crown-5, 18-crown-6,
Benzo-12-crown-4, benzo-15-crown-5, benzo-18-crown-6, dibenzo-12-
Crown-4, dibenzo-15-crown-5, dibenzo-18-crown-6, dicyclohexyl-12-crown-4, dicyclohexyl-15-crown-5,
Cyclic polyethers such as dicyclohexyl-18-crown-6, n-octyl-12-crown-4, n-octyl-15-crown-5, n-octyl-18-crown-6; cryptand [2.1], Cyclic polyetheramines such as cryptand [2.2]; bicyclic polyetheramines such as cryptand [2.2.1] and cryptand [2.2.2]; 1,4,7,10,13,16
-Cyclic polyamines such as hexaazacyclooctadecane and 8-azaadenine; non-cyclic polyethers such as polyethylene glycol, polyethylene glycol monoalkyl ether and polypropylene glycol; ethylenediaminetetraacetic acid, iminodiacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid, trans-1,2-diaminocyclohexane-N, N, N ', N'-tetraacetic acid, ethylenediethyltriamine-N, N, N', N ", N" -pentaacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethyl Polyaminocarboxylic acids such as glycine; polyaminophosphoric acids such as ethylenediaminetetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid); oxycarboxylic acids such as citric acid; condensed phosphoric acid; Rentoriamin, polyamines such as triethylenetetramine; acetylacetone, other oxine can be used glycine, hemin, chlorophyll, valinomycin, natural products and their derivatives such as nigericin.
【００１０】上記の内、塩を形成するものについては、
それを使用することができる（部分塩を含む）。又、多
座配位子を数種類混合して添加することも可能である。Of the above, those which form salts are:
It can be used (including partial salts). It is also possible to mix and add several kinds of polydentate ligands.
【００１１】本発明で用いる二酸化炭素以外の酸性ガス
キャリヤーとしては、従来公知の各種のものを用いるこ
とができる。二酸化炭素以外の酸性ガスとして、燃焼排
ガス中に不純物として含まれるイオウ酸化物を例に挙げ
ると、本発明で好ましく用いられるイオウ酸化物キャリ
ヤーとしては、亜硫酸リチウム、亜硫酸ナトリウム、亜
硫酸カリウム、亜硫酸ルビジウム、亜硫酸セシウム等の
アルカリ金属亜硫酸塩、亜硫酸水素リチウム、亜硫酸水
素ナトリウム、亜硫酸水素カリウム、亜硫酸水素ルビジ
ウム、亜硫酸水素セシウム等のアルカリ金属亜硫酸水素
塩、ジメチルスルホキシド、スルホラン、スルホレン等
のイオウ含有化合物、クエン酸ナトリウム等のアルカリ
金属のクエン酸塩、エチレンジアミン四酢酸鉄等の遷移
金属錯体等各種のものを挙げることができる。As the acidic gas carrier other than carbon dioxide used in the present invention, various known carriers can be used. As an acid gas other than carbon dioxide, for example, a sulfur oxide contained as an impurity in a combustion exhaust gas, as a sulfur oxide carrier preferably used in the present invention, lithium sulfite, sodium sulfite, potassium sulfite, rubidium sulfite, Alkali metal sulfites such as cesium sulfite, lithium hydrogen sulfite, sodium hydrogen sulfite, potassium hydrogen sulfite, rubidium hydrogen sulfite, alkali metal hydrogen sulfite such as cesium hydrogen sulfite, dimethyl sulfoxide, sulfolane, sulfur-containing compounds such as sulfolene, citric acid Examples thereof include citrates of alkali metals such as sodium, and transition metal complexes such as iron ethylenediaminetetraacetate.
【００１２】同様に二酸化炭素以外の酸性ガスとして窒
素酸化物を例にとると、本発明で好ましく用いられる窒
素酸化物キャリヤーとして、亜硝酸リチウム、亜硝酸ナ
トリウム、亜硝酸カリウム、亜硝酸ルビジウム、亜硝酸
セシウム等のアルカリ金属亜硝酸塩、エチレンジアミン
四酢酸鉄等の遷移金属錯体等を挙げることができる。Similarly, taking nitrogen oxide as an example of an acid gas other than carbon dioxide, lithium nitrite, sodium nitrite, potassium nitrite, rubidium nitrite, and nitrite are preferred as nitrogen oxide carriers preferably used in the present invention. Examples thereof include alkali metal nitrites such as cesium, and transition metal complexes such as iron ethylenediaminetetraacetate.
【００１３】二酸化炭素以外の酸性ガスキャリヤーは、
前記したものに限られるものではなく、二酸化炭素以外
の酸性ガスと親和性を有するものであればよく、また２
種以上のものを混合して用いてもよい。The acid gas carrier other than carbon dioxide is
It is not limited to those described above, but may be any as long as it has an affinity for an acidic gas other than carbon dioxide.
A mixture of more than one species may be used.
【００１４】本発明の分離膜を製造するには、先ず、前
記二酸化炭素キャリヤーと二酸化炭素以外の酸性ガスキ
ャリヤーを溶媒に溶解させて溶液を作る。溶媒として
は、二酸化炭素キャリヤーと二酸化炭素以外の酸性ガス
キャリヤーを溶解し得るものであれば任意のものが使用
可能である。一般的には、水や極性有機溶媒あるいは水
と極性有機溶媒との混合液が用いられる。極性有機溶媒
としては、窒素や、硫黄、酸素等のヘテロ原子を含むも
の、例えば、イミダゾールや、Ｎ−メチルイミダゾー
ル、Ｎ−プロピルイミダゾール、Ｎ−フェニルイミダゾ
ール、Ｎ−ベンジルイミダゾール等のＮ−置換イミダゾ
ール等のイミダゾール系化合物の他、ジメチルスルホキ
シド、ジオクチルスルホキシド等のジアルキルスルホキ
シド、Ｎ，Ｎ−ジアルキルホルムアミド、Ｎ，Ｎ−ジオ
クチルホルムアミド等のＮ，Ｎ−ジアルキルホルムアミ
ド等が挙げられる。また、本発明においては、分離膜の
安定性の点から、極性有機溶媒としては、できるだけ高
沸点のもの、通常、沸点１００℃以上、好ましくは１５
０℃以上のものを使用するのがよい。In order to produce the separation membrane of the present invention, first, a solution is prepared by dissolving the carbon dioxide carrier and an acidic gas carrier other than carbon dioxide in a solvent. Any solvent can be used as long as it can dissolve a carbon dioxide carrier and an acidic gas carrier other than carbon dioxide. Generally, water, a polar organic solvent, or a mixture of water and a polar organic solvent is used. Examples of the polar organic solvent include those containing hetero atoms such as nitrogen, sulfur, and oxygen, for example, imidazole, N-methylimidazole, N-propylimidazole, N-phenylimidazole, N-substituted imidazoles such as N-benzylimidazole, and the like. And dialkylsulfoxides such as dimethylsulfoxide and dioctylsulfoxide; N, N-dialkylformamides such as N, N-dialkylformamide and N, N-dioctylformamide. Further, in the present invention, from the viewpoint of the stability of the separation membrane, the polar organic solvent having a boiling point as high as possible, usually having a boiling point of 100 ° C. or higher, preferably 15 ° C. or higher.
It is preferable to use one at 0 ° C. or higher.
【００１５】二酸化炭素キャリヤーの例であるアルカリ
金属炭酸塩及び／又はアルカリ金属重炭酸塩の濃度は、
０．１〜５．０ｍｏｌ／ｌ好ましくは１．０〜４．０ｍ
ｏｌ／ｌである。アルカリ金属イオンと錯体を形成する
多座配位子の溶液中濃度は、０．００１〜１．０ｍｏｌ
／ｌ、好ましくは０．０１〜０．１ｍｏｌ／ｌである。
また、二酸化炭素と親和性を有する物質の他の例である
アルカノールアミンの溶液中濃度は１０重量％以上にす
ることが好ましい。The concentration of alkali metal carbonate and / or alkali metal bicarbonate, which is an example of a carbon dioxide carrier, is:
0.1-5.0 mol / l, preferably 1.0-4.0 m
ol / l. The concentration of the polydentate ligand forming a complex with the alkali metal ion in the solution is 0.001 to 1.0 mol.
/ L, preferably 0.01 to 0.1 mol / l.
The concentration of an alkanolamine, which is another example of a substance having an affinity for carbon dioxide, in a solution is preferably 10% by weight or more.
【００１６】二酸化炭素以外の酸性ガスキャリヤーの濃
度は、０．０１〜５．０ｍｏｌ／ｌ、好ましくは０．０
５〜１．０ｍｏｌ／ｌである。二酸化炭素キャリヤー及
び二酸化炭素以外の酸性ガスキャリヤーの濃度が低すぎ
ると、キャリヤー効果が低くなりすぎて好ましくなく、
一方濃度が高すぎると二酸化炭素の移動速度が遅くなり
すぎて好ましくない。The concentration of the acidic gas carrier other than carbon dioxide is 0.01 to 5.0 mol / l, preferably 0.0 to 5.0 mol / l.
5 to 1.0 mol / l. If the concentration of the carbon dioxide carrier and the acid gas carrier other than carbon dioxide is too low, the carrier effect becomes too low, which is not preferable.
On the other hand, if the concentration is too high, the moving speed of carbon dioxide becomes too slow, which is not preferable.
【００１７】前記のようにして得られた二酸化炭素キャ
リヤーと二酸化炭素以外の酸性ガスキャリヤーを含む溶
液は、分離膜とするために、支持体に含浸保持される。
支持体としては、溶液を液膜として保持し得るものであ
ればどのようなものでも使用可能であり、特に制約され
ない。このようなものとしては、各種の多孔質材料、例
えば、プラスチック、セラミックス、金属、ガラス等の
多孔質体や、ゲル材料、例えば、架橋構造を有するポリ
アクリル酸等が挙げられる。また、その形状は、平膜
状、スパイラル状、中空糸状、筒体状、織布状、不織布
状、紙状等の各種の形状であることができる。また、キ
ャリアーは、溶液を含浸保持する方法の他に、膜中にイ
オン結合又は共有結合等で結合することもできる。分離
膜の厚さは、できるだけ薄厚であるのが望ましいが、通
常、５００μｍ以下、好ましくは２００μｍ以下であ
る。前記支持体に二酸化炭素キャリヤーと二酸化炭素以
外の酸性ガスキャリヤーを含む溶液を含浸保持させて形
成した分離膜は、その一方の側が二酸化炭素吸着面とし
て作用し、その反対の側が二酸化炭素放出面として作用
する。支持体が中空糸の場合には、中空糸の外側を二酸
化炭素吸着面として用い、中空糸の内側を二酸化炭素放
出面として用いるか、又はその逆に用いる。このような
中空糸を支持体とした分離膜は、その中空糸を混合ガス
中に置き、その中空糸外面から二酸化炭素を中空糸内部
に透過させ、中空糸内部から濃縮された二酸化炭素を回
収するか、又はその逆に、中空糸内面から二酸化炭素を
中空糸外面に透過させ、中空糸外部に濃縮された二酸化
炭素を回収することができる。The solution containing the carbon dioxide carrier and the acidic gas carrier other than carbon dioxide obtained as described above is impregnated and held on a support to form a separation membrane.
Any support can be used as long as it can hold the solution as a liquid film, and is not particularly limited. Examples of such a material include various porous materials, for example, porous materials such as plastic, ceramics, metal, and glass, and gel materials, for example, polyacrylic acid having a crosslinked structure. The shape can be various shapes such as a flat membrane shape, a spiral shape, a hollow fiber shape, a tubular shape, a woven fabric shape, a nonwoven fabric shape, and a paper shape. The carrier may be bonded to the membrane by ionic bonding or covalent bonding in addition to the method of impregnating and holding the solution. The thickness of the separation membrane is desirably as thin as possible, but is usually 500 μm or less, preferably 200 μm or less. A separation membrane formed by impregnating and holding a solution containing a carbon dioxide carrier and an acid gas carrier other than carbon dioxide on the support, one side of which acts as a carbon dioxide adsorption surface, and the other side serves as a carbon dioxide emission surface. Works. When the support is a hollow fiber, the outside of the hollow fiber is used as a carbon dioxide adsorption surface, and the inside of the hollow fiber is used as a carbon dioxide emission surface, or vice versa. A separation membrane using such a hollow fiber as a support, the hollow fiber is placed in a mixed gas, carbon dioxide permeates from the outer surface of the hollow fiber into the hollow fiber, and the concentrated carbon dioxide is recovered from the hollow fiber inside. Alternatively, conversely, carbon dioxide can be transmitted from the inner surface of the hollow fiber to the outer surface of the hollow fiber, and the carbon dioxide concentrated outside the hollow fiber can be recovered.
【００１８】本発明の分離膜を用いて二酸化炭素をそれ
を含む混合ガスから分離回収あるいは分離濃縮するに
は、分離膜を透過セルに装着し、その膜の片側に二酸化
炭素を含む混合ガスを接触させ、その混合ガス側の圧力
を、それとは反対側の圧力よりも高く保持する。通常、
混合ガス側と反対側は、減圧又は真空に保持する。In order to separate and recover or separate and concentrate carbon dioxide from a mixed gas containing the same using the separation membrane of the present invention, the separation membrane is mounted on a permeation cell, and the mixed gas containing carbon dioxide is placed on one side of the membrane. Contact and maintain the pressure on the mixed gas side higher than the pressure on the opposite side. Normal,
The side opposite to the mixed gas side is kept under reduced pressure or vacuum.
【００１９】このようにして混合ガスを分離膜の片側に
接触させると、混合ガス中の各成分は、いずれも、膜の
両側の分圧差により、分離膜中を拡散透過するが、二酸
化炭素以外の成分はキャリヤー作用を受けないのに対
し、二酸化炭素はキャリヤー作用を受ける。従って、二
酸化炭素の膜透過量は、膜の両側の分圧差による透過量
に、そのキャリヤー輸送による透過量が加わったものと
なる。即ち、分離膜中のキャリヤーが二酸化炭素を選択
的に吸着し、膜中を拡散して、混合ガスが接触する側と
は反対側（透過側）で二酸化炭素を放出するというサイ
クルをくり返し、その結果、二酸化炭素の透過量のみを
増大させることができる。このキャリヤー作用による二
酸化炭素透過量は、キャリヤー作用によらず分圧差のみ
によるガス成分の透過量に比べると、著しく大きい。従
って、二酸化炭素キャリヤーを含む分離膜の透過速度と
分離係数は、二酸化炭素キャリヤーを含まない分離膜に
比べ飛躍的に増大する。一方、分離対象である混合ガス
中に二酸化炭素以外の酸性ガス、例えば、イオウ酸化物
のＳＯ2が不純物として含まれている場合、アルカリ金
属炭酸塩及び／又はアルカリ金属重炭酸塩をキャリヤー
とした分離膜では、ＳＯ2が分離膜中へ溶解し亜硫酸
（Ｈ2ＳＯ3）又は一部酸化されて硫酸（Ｈ2ＳＯ4）とな
って蓄積し、分離膜（液膜）のｐＨを下げるものと推定
される。その結果、二酸化炭素の分離膜中への溶解反応 ＣＯ2＋Ｈ2Ｏ → Ｈ+＋ＨＣＯ3 - の進行が阻害され、二酸化炭素の分離膜中への溶解度が
低下するため、分離膜の透過性能はキャリヤー作用を有
しない膜性能レベルに低下する。またアルカノールアミ
ンをキャリヤーとした分離膜では、分離膜中へ溶解した
ＳＯ2とアルカノールアミンが再生不能な化合物を形成
するため、アルカノールアミンのＣＯ2吸着・輸送機能
を阻害し、その結果、分離膜の透過性能はキャリヤー作
用を有しない膜性能レベルに低下する。When the mixed gas is brought into contact with one side of the separation membrane in this way, all of the components in the mixed gas diffuse and permeate through the separation membrane due to the partial pressure difference on both sides of the membrane. Does not have a carrier effect, whereas carbon dioxide does. Accordingly, the amount of carbon dioxide permeated through the membrane is the sum of the permeated amount due to the partial pressure difference on both sides of the membrane and the permeated amount due to carrier transport. That is, the carrier in the separation membrane selectively adsorbs carbon dioxide, diffuses in the membrane, and releases the carbon dioxide on the side opposite to the side where the mixed gas comes into contact (permeation side). As a result, only the amount of permeated carbon dioxide can be increased. The amount of carbon dioxide permeated by the carrier effect is significantly larger than the amount of gas component permeated only by the partial pressure difference without being affected by the carrier effect. Therefore, the permeation rate and the separation coefficient of the separation membrane containing the carbon dioxide carrier are dramatically increased as compared with the separation membrane not containing the carbon dioxide carrier. On the other hand, when the mixed gas to be separated contains an acidic gas other than carbon dioxide, for example, SO 2 of sulfur oxide as an impurity, alkali metal carbonate and / or alkali metal bicarbonate was used as the carrier. In a separation membrane, SO 2 dissolves in the separation membrane and is sulfuric acid (H 2 SO 3 ) or partially oxidized and accumulated as sulfuric acid (H 2 SO 4 ) to lower the pH of the separation membrane (liquid membrane). It is estimated to be. As a result, the progress of the dissolution reaction of carbon dioxide in the separation membrane CO 2 + H 2 O → H + + HCO 3 − is inhibited, and the solubility of carbon dioxide in the separation membrane is reduced. Degrades to membrane performance level without carrier action. In a separation membrane using alkanolamine as a carrier, SO 2 dissolved in the separation membrane and the alkanolamine form a non-renewable compound, thereby inhibiting the alkanolamine's CO 2 adsorption / transport function. As a result, the separation membrane Is reduced to a membrane performance level without carrier action.
【００２０】本発明の二酸化炭素分離促進輸送膜を、二
酸化炭素以外の酸性ガス、たとえばイオウ酸化物のＳＯ
2を不純物として含む混合ガスからの二酸化炭素の分
離、濃縮に用いた場合、二酸化炭素は上記のキャリヤー
作用によって高い透過性能を示すとともに、二酸化炭素
以外の酸性ガスキャリヤーがＳＯ2に対して二酸化炭素
キャリヤーと類似の作用を及ぼし、ＳＯ2の分離膜中へ
の蓄積を防ぐため、膜性能の低下を抑えることができ
る。すなわち、ＳＯ2は分離膜の原料ガス側で次式に従
い膜中へ溶解する。The membrane for promoting and transporting carbon dioxide of the present invention is treated with an acidic gas other than carbon dioxide, for example, SO 2 of sulfur oxide.
When carbon dioxide is used to separate and concentrate carbon dioxide from a mixed gas containing 2 as an impurity, carbon dioxide exhibits high permeation performance due to the above-described carrier action, and the acid gas carrier other than carbon dioxide emits carbon dioxide with respect to SO 2 . It acts similarly to the carrier and prevents the accumulation of SO 2 in the separation membrane, so that a decrease in membrane performance can be suppressed. That is, SO 2 is dissolved in the separation gas on the source gas side of the separation membrane according to the following equation.
【化１】 ＨＳＯ3~は膜中の濃度こう配に従って拡散し、分離膜の
反対側（透過側）で上式の逆反応によりＳＯ2を放出す
るというサイクルをくり返すため、分離膜中のＨ2ＳＯ3
又はＨ2ＳＯ4は、ある一定濃度以上には濃縮（蓄積）さ
れず、その結果、二酸化炭素キャリヤー作用への阻害効
果を抑制することができる。Embedded image HSO 3 ~ diffuses according to the concentration gradient in the membrane, and repeats the cycle of releasing SO 2 by the reverse reaction of the above formula on the opposite side (permeation side) of the separation membrane, so that H 2 SO 3 in the separation membrane is repeated.
Alternatively, H 2 SO 4 is not concentrated (accumulated) at a certain concentration or more, and as a result, the inhibitory effect on the carbon dioxide carrier action can be suppressed.
【００２１】また、本発明の二酸化炭素キャリヤーと二
酸化炭素以外の酸性ガスキャリヤーからなる二酸化炭素
分離促進輸送膜は、上記の様な分離膜以外にも、分離膜
法と吸収法の中間的なガス分離法である流動液膜法によ
る二酸化炭素の分離にも有効である。Further, the carbon dioxide separation promoting and transporting membrane comprising the carbon dioxide carrier and the acidic gas carrier other than carbon dioxide according to the present invention is not limited to the above-mentioned separation membrane, but is an intermediate gas between the separation membrane method and the absorption method. It is also effective for separation of carbon dioxide by a fluidized liquid membrane method which is a separation method.
【００２２】[0022]
【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。Next, the present invention will be described in more detail with reference to examples.
【００２３】実施例１ 住友化学工業（株）製のスミカゲルＬ−５Ｈ（ナトリウ
ム塩）（水溶液状）を、親水化処理を施したポリフッ化
ビニリデン多孔膜（ミリポア社製ＧＶＷＰ、孔径０．２
２μｍ、膜厚１１０μｍ）上にスピンコート法（１５０
０ｒｐｍ、１２ｓｅｃ）又はディッピング法により塗布
した後、１２０℃で１時間熱処理して架橋した（架橋
膜）。この膜を２ｍｏｌ／ｌ濃度の炭酸カリウム（Ｋ2
ＣＯ3）と０．５ｍｏｌ／ｌ濃度の亜硫酸カリウム（Ｋ2
ＳＯ3）の水溶液中に３０分間浸漬し、二酸化炭素分離
促進輸送膜を作成した。テストガスとして、ＣＯ2１０
％のＣＯ2／Ｎ2混合ガス（ＳＯ2非含有ガス）を飽和水
蒸気圧下で流量２０ｍｌ／分、全圧１ａｔｍで前記で得
た膜（有効面積９．６２ｃｍ2）に供給し、透過側を減
圧とした。透過してきたガスをガスクロマトグラフで分
析し、ＣＯ2透過速度と分離係数を算出した。また、同
じ二酸化炭素促進輸送膜に、テストガスとしてＣＯ2１
０％、ＳＯ2１００ｐｐｍのＣＯ2／ＳＯ2／Ｎ2混合ガス
（ＳＯ2含有ガス）を上記ＳＯ2非含有ガスと同じ条件で
供給し、同様にＣＯ2透過速度と分離係数を算出した。
テストガスを供給し始めて、数日間連続的に運転し、膜
性能が安定したところでデータをとった。その結果を表
１に示す。Example 1 A polyvinylidene fluoride porous membrane (GVWP, Millipore, pore size 0.2) obtained by subjecting Sumika Gel L-5H (sodium salt) (aqueous solution) manufactured by Sumitomo Chemical Co., Ltd. to a hydrophilic treatment was used.
Spin coating (150 μm, 2 μm, film thickness: 110 μm).
(0 rpm, 12 sec) or by dipping, and then heat-treated at 120 ° C. for 1 hour to crosslink (crosslinked film). This film was treated with 2 mol / l potassium carbonate (K 2
CO 3 ) and 0.5 mol / l potassium sulfite (K 2
It was immersed in an aqueous solution of SO 3 ) for 30 minutes to form a carbon dioxide separation-accelerated transport membrane. As a test gas, CO 2 10
% CO 2 / N 2 mixed gas (SO 2 -free gas) is supplied to the membrane (effective area 9.62 cm 2 ) obtained above under a saturated steam pressure at a flow rate of 20 ml / min and a total pressure of 1 atm. The pressure was reduced. The permeated gas was analyzed by gas chromatography, and the CO 2 permeation rate and the separation coefficient were calculated. In addition, CO 2 1 was used as a test gas on the same
0%, SO 2 100 ppm of CO 2 / SO 2 / N 2 mixed gas (SO 2 containing gas) was supplied under the same conditions as in SO 2 free gas was calculated CO 2 permeation rate and the separation factor as well.
After supplying the test gas, it was operated continuously for several days, and data was taken when the membrane performance was stabilized. Table 1 shows the results.
【００２４】実施例２ 実施例１に示したのと同様の架橋膜を、２ｍｏｌ／ｌ濃
度の炭酸カリウムと０．１ｍｏｌ／ｌ濃度の亜硫酸カリ
ウムの水溶液中に３０分間浸漬し、二酸化炭素分離促進
輸送膜を作製した。この膜に実施例１と同様のＳＯ2非
含有ガス及びＳＯ2含有ガスを供給し、ＣＯ2透過速度と
分離係数を求めた。実施例１と同様一定時間経過後、膜
性能が安定したところでデータをとった。その結果を表
１に示す。Example 2 A crosslinked membrane similar to that shown in Example 1 was immersed in an aqueous solution of 2 mol / l potassium carbonate and 0.1 mol / l potassium sulfite for 30 minutes to promote carbon dioxide separation. A transport membrane was prepared. The same SO 2 -free gas and SO 2 -containing gas as in Example 1 were supplied to this membrane, and the CO 2 permeation rate and the separation coefficient were determined. Data was taken when the film performance became stable after a certain period of time, as in Example 1. Table 1 shows the results.
【００２５】比較例１ 実施例１に示したのと同様の架橋膜を２ｍｏｌ／ｌ濃度
の炭酸カリウム水溶液に３０分間浸漬し、二酸化炭素分
離促進輸送膜を作製した。この膜に実施例１と同様のＳ
Ｏ2非含有ガス及びＳＯ2含有ガスを供給し、ＣＯ2透過
速度と分離係数を求めた。実施例１と同様一定時間経過
後の安定した膜性能を表１に示す。 比較例２ 実施例１に示したのと同様の架橋膜を純水に３０分間浸
せきし、二酸化炭素分離促進輸送膜を作製した。この膜
に実施例１で用いたＳＯ2非含有ガスを供給し、ＣＯ2透
過速度と分離係数を求めた。実施例１と同様一定時間経
過後の安定した膜性能を表１に示す。Comparative Example 1 A crosslinked membrane similar to that shown in Example 1 was immersed in a 2 mol / l aqueous solution of potassium carbonate for 30 minutes to prepare a carbon dioxide separation promoting transport membrane. The same S as in Example 1 was applied to this film.
The O 2 -free gas and the SO 2 -containing gas were supplied, and the CO 2 permeation rate and the separation coefficient were determined. Table 1 shows the stable film performance after a lapse of a predetermined time as in Example 1. Comparative Example 2 A crosslinked membrane similar to that shown in Example 1 was immersed in pure water for 30 minutes to produce a carbon dioxide separation promoting transport membrane. The SO 2 -free gas used in Example 1 was supplied to this membrane, and the CO 2 permeation rate and the separation coefficient were determined. Table 1 shows the stable film performance after a lapse of a predetermined time as in Example 1.
【００２６】[0026]
【表１】 ＊１：単位〔cm3(STP)/cm2・sec・cmHg〕 ＊２：α＝ＱCO2／ＱN2(CO2とN2の膜透過量比)[Table 1] * 1: Unit [cm 3 (STP) / cm 2 · sec · cmHg] * 2: α = QCO 2 / QN 2 (CO 2 and N 2 membrane permeation ratio)
【００２７】[0027]
【発明の効果】以上説明したように、本発明の二酸化炭
素分離促進輸送膜を用いることにより、二酸化炭素以外
の酸性ガスを不純物として含む混合ガスから選択的に二
酸化炭素を分離・濃縮することができる。特に本発明の
二酸化炭素分離促進輸送膜は、地球温暖化問題の対策技
術等の分野において、燃焼排ガスのようなイオウ酸化
物、窒素酸化物等の不純物を含んでいるガス中の二酸化
炭素を分離回収、再利用するための有効手段となり得る
ものである。As described above, by using the carbon dioxide separation promoting and transporting membrane of the present invention, carbon dioxide can be selectively separated and concentrated from a mixed gas containing an acidic gas other than carbon dioxide as an impurity. it can. In particular, the carbon dioxide separation and transport membrane of the present invention separates carbon dioxide in a gas containing impurities such as sulfur oxides and nitrogen oxides such as combustion exhaust gas in the field of countermeasures against global warming. It can be an effective means for collection and reuse.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 岡部 和弘 東京都港区西新橋２−８−11 第７東洋 海事ビル８階 財団法人地球環境産業技 術研究機構 ＣＯ２固定化等プロジェク ト室内 (72)発明者 中林 誠 東京都港区西新橋２−８−11 第７東洋 海事ビル８階 財団法人地球環境産業技 術研究機構 ＣＯ２固定化等プロジェク ト室内 (72)発明者 松宮 紀文 東京都港区西新橋２−８−11 第７東洋 海事ビル８階 財団法人地球環境産業技 術研究機構 ＣＯ２固定化等プロジェク ト室内 (72)発明者 真野 弘 東京都港区西新橋２−８−11 第７東洋 海事ビル８階 財団法人地球環境産業技 術研究機構 ＣＯ２固定化等プロジェク ト室内 (72)発明者 原谷 賢治 茨城県つくば市東１−１ 工業技術院物 質工学工業技術研究所内 審査官 吉水 純子 (56)参考文献 特開 平２−9425（ＪＰ，Ａ) 特開 昭64−70125（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) B01D 69/00 500 C01B 31/20 ──────────────────────────────────────────────────続 き Continuing from the front page (72) Inventor Kazuhiro Okabe 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8th Floor Project Room for CO2 Fixation, etc. (72) ) Inventor Makoto Nakabayashi 8th Floor, 7th Oriental Maritime Building, 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo Office for Global Environmental Innovation, Japan (72) Inventor: Kibumi Matsumiya Port of Tokyo Metropolitan Government 2-8-11 Nishi-Shimbashi-ku, Tokyo The 7th Oriental Maritime Building 8th Floor CO2 fixation project room (72) Inventor Hiroshi Mano 2-8-11 Nishi-Shimbashi, Minato-ku, Tokyo 7th Oriental Maritime Building 8th Floor CO2 Fixation Project Room, etc. (72) Inventor Kenji Haraya Ibara 1-1, Higashi 1-1, Tsukuba, Castle, Japan Examiner, Junko Yoshimizu, National Institute of Materials Science, National Institute of Advanced Industrial Science and Technology (56) References JP-A-2-9425 (JP, A) JP-A-64-70125 (JP, A) (58) ) Field surveyed (Int. Cl. 6 , DB name) B01D 69/00 500 C01B 31/20
Claims (1)
物から二酸化炭素を放出する物質と二酸化炭素以外の酸
性ガスと可逆的に反応し、その反応物から当該酸性ガス
を放出する物質を含む溶液を膜中に保持させたことを特
徴とする二酸化炭素分離促進輸送膜。1. A substance which reacts reversibly with carbon dioxide and releases carbon dioxide from the reactant and a substance which reacts reversibly with an acid gas other than carbon dioxide and releases the acid gas from the reactant. A carbon dioxide separation promoting transport membrane characterized in that a solution containing the same is held in the membrane.
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|---|---|---|---|
| JP7079758A JP2879057B2 (en) | 1995-03-10 | 1995-03-10 | Carbon dioxide separation enhanced transport membrane |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7079758A JP2879057B2 (en) | 1995-03-10 | 1995-03-10 | Carbon dioxide separation enhanced transport membrane |
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| Publication Number | Publication Date |
|---|---|
| JPH08243364A JPH08243364A (en) | 1996-09-24 |
| JP2879057B2 true JP2879057B2 (en) | 1999-04-05 |
Family
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4824443A (en) * | 1986-12-30 | 1989-04-25 | Bend Research, Inc. | Gas separation by composite solvent-swollen membranes |
| JPS6470125A (en) * | 1987-09-10 | 1989-03-15 | Asahi Glass Co Ltd | Separation of gas |
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1995
- 1995-03-10 JP JP7079758A patent/JP2879057B2/en not_active Expired - Lifetime
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