JPH0693977B2 - Carbon dioxide separation membrane and carbon dioxide carrier - Google Patents
Carbon dioxide separation membrane and carbon dioxide carrierInfo
- Publication number
- JPH0693977B2 JPH0693977B2 JP4316105A JP31610592A JPH0693977B2 JP H0693977 B2 JPH0693977 B2 JP H0693977B2 JP 4316105 A JP4316105 A JP 4316105A JP 31610592 A JP31610592 A JP 31610592A JP H0693977 B2 JPH0693977 B2 JP H0693977B2
- Authority
- JP
- Japan
- Prior art keywords
- carbon dioxide
- separation membrane
- carrier
- membrane
- molybdenum
- 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、特定のモリブデン
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、モリブデンのカルボニル錯
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、モリブデンのカルボ
ニル錯体からなる二酸化炭素キャリヤーが提供される。As a result of intensive studies to solve the above problems, the present inventors have found that a liquid membrane using a specific molybdenum complex as a carrier acts as a carbon dioxide separation membrane. The present invention has been completed. That is, according to the present invention, there is provided a carbon dioxide separation membrane comprising a solution in which a carbonyl complex of molybdenum is dissolved in a solvent and a support for holding the solution. The present invention also provides a carbon dioxide carrier comprising a molybdenum carbonyl complex.
【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、モリブデンのカルボニル錯体（以
下、単にモリブデン錯体とも言う）を二酸化炭素キャリ
ヤーとして含むものである。本発明で用いるモリブデン
のカルボニル錯体は、配位子としてカルボニルを含有す
るものであればよいが、さらに、有機配位子を含有する
ことができる。この場合の有機配位子は、モリブデン原
子に配位し得るものであればよく、含窒素複素環化合物
や、環状ポリエン化合物が好ましく使用される。モリブ
テン錯体の具体例を示すと、例えば、シス−テトラカル
ボニル−ビス（ピペリジン）モリブデニウム、ビシクロ
〔２，２，１〕ヘプタ−２，５−ジエンモリブデニウム
テトラカルボニル、トロピリウムモリブデニウムトリカ
ルボニル、シクロヘプタトリエンモリブデニウムトリカ
ルボニル、シクロヘプタジエニルモリブデニウムトリカ
ルボニルダイマー等が挙げられる。The carbon dioxide separation membrane (hereinafter, also simply referred to as a separation membrane) of the present invention contains a carbonyl complex of molybdenum (hereinafter also simply referred to as a molybdenum complex) as a carbon dioxide carrier. The carbonyl complex of molybdenum used in the present invention may be one containing carbonyl as a ligand, and may further contain an organic ligand. In this case, the organic ligand may be one capable of coordinating with a molybdenum atom, and a nitrogen-containing heterocyclic compound or a cyclic polyene compound is preferably used. Specific examples of the molybdenum complex include, for example, cis-tetracarbonyl-bis (piperidine) molybdenium, bicyclo [2,2,1] hepta-2,5-diene molybdenium tetracarbonyl, tropylium molybdenium tricarbonyl, Examples thereof include cycloheptatriene molybdenium tricarbonyl and cycloheptadienyl molybdenium tricarbonyl dimer.
【０００６】本発明の分離膜を製造するには、先ず、前
記モリブデン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、モリブデン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、そのモリブデン錯体に対する溶
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や、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、ジメチルスルホキジド、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１５０℃以上の有機溶媒を使用するのがよい。有機
溶媒中のモリブデン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 molybdenum complex is dissolved in an organic solvent to form a solution.
Any organic solvent can be used as long as it can dissolve the molybdenum complex. Generally, a polar organic solvent containing a hetero atom such as nitrogen or sulfur or oxygen, particularly a heterocyclic organic solvent is preferably used in terms of its solubility in the molybdenum complex. Examples of such polar organic solvent include imidazole, N-methylimidazole, N-propylimidazole, N-phenylimidazole, N-substituted imidazole and other imidazole-based compounds such as pyrrole, and pyrrole,
Heterocyclic compounds containing one or more nitrogens such as triazole, pyridine, pyrazine or their derivatives, and cyclic compounds containing one or more nitrogens such as pyrrolidine, piperidine, piperazine or their derivatives, ethylenediamine,
Examples thereof include amine compounds such as ethanolamine, aniline or a derivative thereof, amide compounds such as dimethylformamide and dimethylacetamide, sulfur-containing cyclic compounds such as dimethylsulfoxide and thiophene, and oxygen-containing cyclic compounds such as furan derivatives. Further, in the present invention, from the viewpoint of stability of the separation membrane, it is preferable to use an organic solvent having a boiling point as high as possible, usually an organic solvent having a boiling point of 100 ° C. or higher, preferably 150 ° C. or higher. The concentration of the molybdenum complex in the organic solvent is preferably as high as possible, but is usually 0.1 mol / l or more, preferably 0.2 mol / l or more.
【０００７】前記のようにして得られたモリブデン錯体
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。前記支持体にモリブデン錯
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 molybdenum complex obtained as described above is impregnated and held by the support to form a separation membrane. As the support, any material can be used as long as it can hold the solution as a liquid film,
There is no particular restriction. Examples of such materials include various porous materials such as plastics, ceramics, metals,
Examples thereof include 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 molybdenum complex solution on 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.
【０００８】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.
【０００９】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モリブデン錯体のキャリヤー作用を
受けないのに対し、二酸化炭素はモリブデン錯体のキャ
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、そのモリブデン
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モリブデン錯
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。このモ
リブデン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 molybdenum complex, while carbon dioxide is subject to the carrier action of the molybdenum complex. Therefore, the amount of carbon dioxide permeated through the membrane is the amount of permeation due to the partial pressure difference on both sides of the membrane plus the amount of permeation due to carrier transport of the molybdenum complex. That is, a cycle in which a molybdenum 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 molybdenum 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.
【００１０】[0010]
【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.
【００１１】実施例１ 下記構造式（Ｉ）で示されるシス−テトラカルボニル−
ビス（ピペリジン）モリブデニウムを０．４ｍｏｌ／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５００
ｍｌ／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。その結果を表１及
び図１に示す。また、表１に比較例１及び比較例の膜に
ついての測定経過をあわせて示す。本分離膜の特性は、
図１に示すように、測定開始後徐々に向上し、約５時間
経過後に安定した。この時の特性は、表１に示すよう
に、Ｑｃｏ2＝４．２×１０-5ｃｍ3／ｃｍ2・ｓ・ｃｍ
Ｈｇ，α＝３７であった。なお、Ｑｃｏ2は二酸化炭素
透過速度（ｃｍ3／ｃｍ2・ｓ・ｃｍＨｇ）を、αは分離
係数（Ｐｃｏ2／ＰＮ2＝Ｑｃｏ2／ＱＮ2）を示す。Example 1 Cis-tetracarbonyl-indicated by the following structural formula (I)
0.4 mol / l of bis (piperidine) molybdenium
Was dissolved in N-methylimidazole at a concentration of to obtain a uniform solution. Then, a hydrophilic polyvinylidene fluoride (PVdF) porous membrane (manufactured by Millipore, pore size 0.22 μm, film thickness 110 μm, porosity 75%) was immersed in this solution and then taken out, and the PVdF porous membrane was supported. An impregnated liquid film was prepared. 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. CO 2 / as test gas
A mixed gas of N 2 = 10/90 was used, and the flow rate was 500
It was supplied to the membrane at a total pressure of 1 atm at a flow rate of ml / min, and the permeation 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 and FIG. Further, Table 1 also shows the measurement progress of the films of Comparative Example 1 and Comparative Example. The characteristics of this separation membrane are
As shown in FIG. 1, it gradually improved after the start of measurement and became stable after about 5 hours. The characteristics at this time are, as shown in Table 1, Qco 2 = 4.2 × 10 −5 cm 3 / cm 2 · s · cm
Hg, α = 37. Note that Qco 2 represents the carbon dioxide permeation rate (cm 3 / cm 2 · s · cmHg), and α represents the separation coefficient (Pco 2 / PN 2 = Qco 2 / QN 2 ).
【化１】 [Chemical 1]
【００１２】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 characteristic of the polydimethylsiloxane film used as the base film was measured under the same conditions as in Example 1, and the result was Qco 2
= 1.0 × 10 −4 cm 3 / cm 2 · s · cm Hgα = 10
showed that.
【００１３】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.
【００１４】[0014]
【表１】 [Table 1]
【００１５】[0015]
【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.
【図１】本発明分離膜の二酸化炭素に関する透過特性を
示すグラフである。FIG. 1 is a graph showing carbon dioxide permeation characteristics of a separation membrane of the present invention.
───────────────────────────────────────────────────── 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)
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 of a carbonyl complex of molybdenum 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.
酸化炭素キャリヤー。4. A carbon dioxide carrier comprising a carbonyl complex of molybdenum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4316105A JPH0693977B2 (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 |
|---|---|---|---|
| JP4316105A JPH0693977B2 (en) | 1992-10-31 | 1992-10-31 | Carbon dioxide separation membrane and carbon dioxide carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06142467A JPH06142467A (en) | 1994-05-24 |
| JPH0693977B2 true JPH0693977B2 (en) | 1994-11-24 |
Family
ID=18073304
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4316105A Expired - Lifetime JPH0693977B2 (en) | 1992-10-31 | 1992-10-31 | Carbon dioxide separation membrane and carbon dioxide carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0693977B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7012288B2 (en) * | 2018-08-28 | 2022-01-28 | Ｊｆｅエンジニアリング株式会社 | A selective composite gas permeable membrane having a metal-organic framework layer and a method for producing the same. |
-
1992
- 1992-10-31 JP JP4316105A patent/JPH0693977B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06142467A (en) | 1994-05-24 |
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