JPH0693976B2 - Carbon dioxide separation membrane and carbon dioxide carrier - Google Patents
Carbon dioxide separation membrane and carbon dioxide carrierInfo
- Publication number
- JPH0693976B2 JPH0693976B2 JP4316104A JP31610492A JPH0693976B2 JP H0693976 B2 JPH0693976 B2 JP H0693976B2 JP 4316104 A JP4316104 A JP 4316104A JP 31610492 A JP31610492 A JP 31610492A JP H0693976 B2 JPH0693976 B2 JP H0693976B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- separation membrane
- carrier
- rhodium
- membrane
- 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.)
- Expired - Lifetime
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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膜及びそれに用
いる二酸化炭素キャリヤー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 membrane for separating and concentrating carbon dioxide in a mixed gas and a carbon dioxide carrier used for the membrane.
【０００２】[0002]
【従来の技術】金属錯体をキャリヤーとして用いた分離
膜としては、Ｊ．Ｍｅｍｂ．Ｓｃｉ，３１，３１（１９
８７）に示されているように、空気から酸素を分離する
酸素分離膜が知られている。この分離膜は、コバルト錯
体溶液を多孔質膜に含浸させて形成しもので、酸素の透
過速度Ｑｏ2＝２．１×１０-6ｃｍ3／ｃｍ2・ｓ・ｃｍ
Ｈｇ，分離係数α＝２６の特性が得られたと報告されて
いる。二酸化炭素の分離・濃縮に金属錯体をキャリヤー
とする分離膜を用いた例は見当らないが、類似の研究と
しては、Ｊ．Ｃｈｅｍ．Ｓｃｉ．Ｄａｌｔｏｎ，７０８
（１９７７）やＪ．Ａｍ．Ｃｈｅｍ．Ｓｃｉ，９８，１
６１５（１９７６）等に示されるように、遷移金属錯体
が二酸化炭素を吸着することが知られている。しかし、
二酸化炭素分離膜のキャリヤーとして用いるには、二酸
化炭素を可逆的に吸脱着する性能が必要で、これまでの
ところ二酸化炭素のキャリヤーとしてはたらく錯体は知
られていない。2. Description of the Related Art Separation membranes using a metal complex as a carrier are described in J. Memb. Sci, 31 , 31 (19
As shown in 87), an oxygen separation membrane that separates oxygen from air is known. This separation membrane is formed by impregnating a cobalt complex solution into a porous membrane, and has an oxygen permeation rate Qo 2 = 2.1 × 10 −6 cm 3 / cm 2 · s · cm.
It is reported that the characteristics of Hg and separation factor α = 26 were obtained. No example using a separation membrane using a metal complex as a carrier for carbon dioxide separation / concentration is found, but similar studies include J. Chem. Sci. Dalton, 708
(1977) and J. Am. Chem. Sci, 98 , 1
615 (1976), it is known that a transition metal complex adsorbs carbon dioxide. But,
To be used as a carrier for a carbon dioxide separation membrane, the ability to reversibly adsorb and desorb carbon dioxide is required, and so far no complex has been known to act as a carrier for carbon dioxide.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、二酸化炭素
透過特性にすぐれた二酸化炭素分離膜及びそれに用いる
二酸化炭素キャリヤー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 membrane having excellent carbon dioxide permeation characteristics and a carbon dioxide carrier used for the membrane.
【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、特定のロジウム錯
体をキャリヤーとして用いた液膜が二酸化炭素分離膜と
して作用することを見出し、本発明を完成するに至っ
た。即ち、本発明によれば、少なくともロジウムとジエ
ン化合物を含む有機金属錯体を溶媒に溶解した溶液と、
該溶液を保持するための支持体とからなることを特徴と
する二酸化炭素分離膜が提供される。また、本発明によ
れば、少なくともロジウムとジエン化合物を含む有機金
属錯体からなる二酸化炭素キャリヤーが提供される。Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a liquid membrane using a specific rhodium complex as a carrier acts as a carbon dioxide separation membrane. The present invention has been completed. That is, according to the present invention, a solution obtained by dissolving an organometallic complex containing at least rhodium and a diene compound in a solvent,
A carbon dioxide separation membrane is provided, which comprises a support for holding the solution. Further, according to the present invention, there is provided a carbon dioxide carrier comprising an organometallic complex containing at least rhodium and a diene compound.
【０００５】本発明の二酸化炭素分離膜（以下、単に分
離膜とも言う）は、少なくともロジウムとジエン化合物
を含む有機金属錯体（以下、単にロジウム錯体とも言
う）を二酸化炭素キャリヤーとして含むものである。本
発明で用いるロジウム錯体は、その錯体構造中にロジウ
ムとその配位子としてのジエン化合物を含むものであれ
ばよく、他の金属原子や配位子を含むものであってもよ
い。ジエン化合物としては、ロジウムに配位可能なもの
であればよく、特に、ビシクロアルカジエンの使用が好
ましい。また、ジエン化合物とともに用いることのでき
る他の有機配位子としては、ケト基を複数個有するポリ
ケトン化合物等が挙げられる。ロジウム錯体の具体例を
示すと、例えば、以下のものが例示される。The carbon dioxide separation membrane of the present invention (hereinafter, also simply referred to as a separation membrane) contains an organometallic complex containing at least rhodium and a diene compound (hereinafter also simply referred to as a rhodium complex) as a carbon dioxide carrier. The rhodium complex used in the present invention may be one containing rhodium and a diene compound as its ligand in its complex structure, and may also contain other metal atoms or ligands. Any diene compound may be used as long as it can coordinate with rhodium, and it is particularly preferable to use bicycloalkadiene. Other organic ligands that can be used together with the diene compound include polyketone compounds having a plurality of keto groups. The following are examples of specific examples of the rhodium complex.
【０００６】[0006]
【化１】 [Chemical 1]
【０００７】本発明の分離膜を製造するには、先ず、前
記ロジウム錯体を有機溶媒に溶解させて溶液を作る。有
機溶媒としては、ロジウム錯体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、窒素や、
硫黄、酸素等のヘテロ原子を含む極性有機溶媒、特に複
素環系有機溶媒が、そのロジウム錯体に対する溶解性の
点で好ましく使用される。このような極性有機溶媒とし
ては、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、ピロール、トリア
ゾール、ピリジン、ピラジン等の１個以上の窒素を含む
複素環化合物またはそれらの誘導体、ピロリジン、ピペ
リジン、ピペラジン等の１個以上の窒素を含む環状化合
物またはそれらの誘導体、エチレンジアミン、エタノー
ルアミン等のアミン系化合物、アニリンまたはその誘導
体、ジメチルホルムアミド、ジメチルアセトアミド等の
アミド化合物、ジメチルスルホキシド、チオフェン等の
イオウ含有環状化合物、フラン誘導体等の酸素含有環状
化合物等が挙げられる。また、本発明においては、分離
膜の安定性の点から、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℃以上の有機溶媒を使用するのがよい。有機溶媒中の
ロジウム錯体濃度はできるだけ高濃度であることが望ま
しいが、通常、０．１モル／ｌ以上、好ましくは０．２
モル／ｌ以上である。To manufacture the separation membrane of the present invention, first, the rhodium complex is dissolved in an organic solvent to form a solution. Any organic solvent can be used as long as it can dissolve the rhodium complex. In general, nitrogen,
A polar organic solvent containing a hetero atom such as sulfur or oxygen, particularly a heterocyclic organic solvent is preferably used in view of its solubility in the rhodium complex. Examples of such a polar organic solvent include imidazole compounds, imidazole compounds such as N-substituted imidazoles such as N-methylimidazole, N-propylimidazole, N-phenylimidazole, N-benzylimidazole, pyrrole and triazole. , Pyridine, pyrazine and other heterocyclic compounds containing one or more nitrogen or derivatives thereof, pyrrolidine, piperidine, piperazine and other cyclic compounds containing one or more nitrogen or derivatives thereof, amine compounds such as ethylenediamine and ethanolamine Examples thereof include compounds, aniline or a derivative thereof, amide compounds such as dimethylformamide and dimethylacetamide, sulfur-containing cyclic compounds such as dimethyl sulfoxide and thiophene, and oxygen-containing cyclic compounds such as furan derivatives. Further, in the present invention, from the viewpoint of the stability of the separation membrane, the organic solvent has a boiling point as high as possible, usually a boiling point of 100 ° C. or higher, preferably 15
It is preferable to use an organic solvent at 0 ° C or higher. The concentration of the rhodium complex in the organic solvent is desirably as high as possible, but is usually 0.1 mol / l or more, preferably 0.2 mol / l or more.
Mol / l or more.
【０００８】前記のようにして得られたロジウム錯体の
有機溶媒溶液は、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
ラス等が挙げられる。また、その形状は、膜状、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。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、２００μｍ以下、好ましく
は１００μｍ以下である。前記支持体にロジウム錯体溶
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のがよい。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
炭素を回収することができる。The organic solvent solution of the rhodium complex obtained as described above is impregnated and held on the support to form a separation membrane. As the support, 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 materials include various porous materials such as plastics, ceramics, metals, and glass. Further, the shape thereof can be various shapes such as a film shape, a hollow fiber shape, a cylindrical shape, a woven cloth shape, a non-woven cloth shape, and a paper shape. The thickness of the separation membrane is preferably as thin as possible, but is usually 200 μm or less, preferably 100 μm or less. The separation membrane formed by impregnating and holding the rhodium complex solution in the support has one side acting as a carbon dioxide adsorbing surface and the other side acting as a carbon dioxide releasing surface. When the support is a hollow fiber, it is preferable to use the outside of the hollow fiber as the carbon dioxide adsorbing surface and the inside of the hollow fiber as the carbon dioxide releasing surface. Such a separation membrane using hollow fibers as a support puts the hollow fibers in a mixed gas, permeates carbon dioxide from the outer surface of the hollow fibers into the hollow fibers, and collects concentrated carbon dioxide from the inside of the hollow fibers. can do.
【０００９】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。混合ガ
ス側とは反対側は減圧、好ましくは真空に保持する。In order to separate and collect carbon dioxide from a mixed gas containing it using the separation membrane of the present invention, the separation membrane is attached to a permeation cell, and the mixed gas containing carbon dioxide is attached to one side of the membrane. Contact is made and the pressure on the mixed gas side is kept higher than the pressure on the opposite side. The side opposite to the mixed gas side is kept under reduced pressure, preferably vacuum.
【００１０】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ロジウム錯体のキャリヤー作用を受
けないのに対し、二酸化炭素はロジウム錯体のキャリヤ
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、そのロジウム錯体のキ
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としてのロジウム錯体が二酸
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。このロジウム錯
体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、本発明の分離膜に
おいては、二酸化炭素に関する透過特性、即ち、二酸化
炭素の透過速度と分離係数が飛躍的に増加したものであ
る。When the mixed gas is brought into contact with one side of the separation membrane in this way, each component in the mixed gas diffuses and permeates through the separation membrane due to the partial pressure difference between the both sides of the membrane, but other than carbon dioxide. The component is not subject to the carrier action of the rhodium complex, whereas carbon dioxide is subject to the carrier action of the rhodium complex. Therefore, the membrane permeation amount of carbon dioxide is the permeation amount due to the partial pressure difference between both sides of the membrane plus the permeation amount due to carrier transport of the rhodium complex. That is, a cycle in which a rhodium complex as a carrier in a separation membrane selectively adsorbs carbon dioxide, diffuses in the membrane, and releases carbon dioxide on the side (permeation side) opposite to the side in contact with the mixed gas. As a result, only the amount of permeation of carbon dioxide can be increased. The carbon dioxide permeation amount of the rhodium complex due to the carrier action is significantly larger than the gas component permeation amount due to only the partial pressure difference without depending on the carrier action. Therefore, in the separation membrane of the present invention, the permeation characteristics regarding carbon dioxide, that is, the permeation rate of carbon dioxide and the separation coefficient are dramatically increased.
【００１１】[0011]
【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。EXAMPLES Next, the present invention will be described in more detail by way of examples.
【００１２】実施例１ （ビシクロ〔２，２，１〕ヘプタ−２，５−ジエン）
（２，４−ペンタンジオナート）ロジウムを０．４ｍｏ
ｌ／ｌの濃度でＮ−メチルイミダゾールに溶解させて均
一な溶液を得た。次いで、この溶液中に親水化処理した
ポリフッ化ビニリデン（ＰＶｄＦ）多孔膜（ミリポア社
製、孔径０．２２μｍ、膜厚１１０μｍ、気孔率７５
％）を浸漬させたのち取出し、ＰＶｄＦ多孔膜を支持体
とした含浸型液膜を作製した。含浸溶液の流出を防ぐた
めに、含浸型液膜をポリジメチルシロキサン膜に重ね合
わせた積層膜として特性を評価した。テストガスとして
ＣＯ2／Ｎ2＝１０／９０の混合ガスを用い、これを流量
５００ｍｌ／分、全圧１ａｔｍで膜に供給し、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、透過速度と分離係数を算出した。結果を表１に
示す。表１に示すように、本分離膜の特性は、Ｑｃｏ2
＝１．５×１０-5ｃｍ3／ｃｍ2・ｓ・ｃｍＨｇ，α＝１
３であった。なお、Ｑｃｏ2は二酸化炭素透過速度（ｃ
ｍ3／ｃｍ2・ｓ・ｃｍＨｇ）を、αは分離係数（Ｐｃｏ
2／ＰＮ2＝Ｑｃｏ2／ＱＮ2）を示す。Example 1 (bicyclo [2,2,1] hepta-2,5-diene)
(2,4-Pentanedionate) rhodium 0.4mo
A uniform solution was obtained by dissolving in N-methylimidazole at a concentration of 1 / l. Then, a polyvinylidene fluoride (PVdF) porous membrane hydrophilized in this solution (manufactured by Millipore, pore diameter 0.22 μm, film thickness 110 μm, porosity 75)
%) Was taken out and then taken out to prepare an impregnated liquid film using the PVdF porous film as a support. In order to prevent the impregnation solution from flowing out, the characteristics were evaluated as a laminated film in which an impregnation type liquid film was laminated on a polydimethylsiloxane film. A mixed gas of CO 2 / N 2 = 10/90 was used as a test gas, which was supplied to the membrane at a flow rate of 500 ml / min and a total pressure of 1 atm, and the permeate side was depressurized. The permeated gas was analyzed by a gas chromatograph, and the permeation rate and the separation coefficient were calculated. The results are shown in Table 1. As shown in Table 1, the characteristics of this separation membrane are Qco 2
= 1.5 × 10 −5 cm 3 / cm 2 · s · cmHg, α = 1
It was 3. Qco 2 is the carbon dioxide permeation rate (c
m 3 / cm 2 · s · cmHg), α is the separation factor (Pco
2 / PN 2 = Qco 2 / QN 2 ) is shown.
【００１３】比較例１ 基膜に用いたポリジメチルシロキサン膜のＣＯ2／Ｎ2透
過特性を実施例１と同じ条件で測定した結果、Ｑｃｏ2
＝１．０×１０-4ｃｍ3／ｃｍ2・ｓ・ｃｍＨｇα＝１０
を示した。Comparative Example 1 The CO 2 / N 2 permeation characteristics of the polydimethylsiloxane film used as the base film were measured under the same conditions as in Example 1, and as a result, Qco 2
= 1.0 × 10 −4 cm 3 / cm 2 · s · cm Hgα = 10
showed that.
【００１４】比較例２ 実施例１と同様な方法でキャリヤーを含まないＮ−メチ
ルイミダゾール溶媒のみの含浸型液膜を作製し、実施例
１と同じ条件でＣＯ2／Ｎ2透過特性を測定した結果、Ｑ
ｃｏ2＝５．６×１０-6ｃｍ3/ｃｍ2・Ｓ・ｃｍＨｇの結
果が得られた。Comparative Example 2 An impregnated liquid membrane containing only a N-methylimidazole solvent containing no carrier was prepared in the same manner as in Example 1, and the CO 2 / N 2 permeation characteristics were measured under the same conditions as in Example 1. As a result, Q
The result of co 2 = 5.6 × 10 −6 cm 3 / cm 2 · S · cmHg was obtained.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【発明の効果】以上説明したように、本発明の分離膜を
用いることにより、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。従って、本発明の分離膜
は、地球温暖化問題の対策技術としての二酸化炭素固定
化技術等の分野において、燃焼排ガスのような大量かつ
連続的に排出されるガス中の二酸化炭素を固定化、再利
用するためにの有効な手段となり得るものである。As described above, by using the separation membrane of the present invention, carbon dioxide can be selectively separated and concentrated from the mixed gas. Therefore, the separation membrane of the present invention, in the field of carbon dioxide fixation technology and the like as a countermeasure technology against the problem of global warming, immobilized carbon dioxide in a large amount and continuously discharged gas such as combustion exhaust gas, It can be an effective means for reuse.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 原谷 賢治 茨城県つくば市東１丁目１番地 工業技術 院化学技術研究所内 審査官 石橋 和美 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kenji Haratani 1-1, Higashi, Tsukuba, Ibaraki Prefecture Kazumi Ishibashi Examiner, Institute for Chemical Research, Institute of Industrial Technology
Claims (4)
む有機金属錯体を溶媒に溶解した溶液と、該溶液を保持
するための支持体とからなることを特徴とする二酸化炭
素分離膜。1. A carbon dioxide separation membrane comprising a solution in which an organometallic complex containing at least rhodium and a diene compound is dissolved in a solvent, and a support for holding the solution.
あることを特徴とする請求項１の二酸化炭素分離膜。2. The carbon dioxide separation membrane according to claim 1, wherein the solvent is a polar organic solvent containing a hetero atom.
体であることを特徴とする請求項１又は２の二酸化炭素
分離膜。3. The carbon dioxide separation membrane according to claim 1, wherein the support is a flat membrane-shaped or hollow fiber-shaped porous body.
む有機金属錯体からなる二酸化炭素キャリヤー。4. A carbon dioxide carrier comprising an organometallic complex containing at least rhodium and a diene compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4316104A JPH0693976B2 (en) | 1992-10-31 | 1992-10-31 | Carbon dioxide separation membrane and carbon dioxide carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4316104A JPH0693976B2 (en) | 1992-10-31 | 1992-10-31 | Carbon dioxide separation membrane and carbon dioxide carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06142466A JPH06142466A (en) | 1994-05-24 |
| JPH0693976B2 true JPH0693976B2 (en) | 1994-11-24 |
Family
ID=18073293
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4316104A Expired - Lifetime JPH0693976B2 (en) | 1992-10-31 | 1992-10-31 | Carbon dioxide separation membrane and carbon dioxide carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693976B2 (en) |
-
1992
- 1992-10-31 JP JP4316104A patent/JPH0693976B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06142466A (en) | 1994-05-24 |
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