JPH09227572A - Gas-storing organometallic complex, its production, gas-storing apparatus and automobile furnished with gas-storing apparatus - Google Patents
Gas-storing organometallic complex, its production, gas-storing apparatus and automobile furnished with gas-storing apparatusInfo
- Publication number
- JPH09227572A JPH09227572A JP4081896A JP4081896A JPH09227572A JP H09227572 A JPH09227572 A JP H09227572A JP 4081896 A JP4081896 A JP 4081896A JP 4081896 A JP4081896 A JP 4081896A JP H09227572 A JPH09227572 A JP H09227572A
- Authority
- JP
- Japan
- Prior art keywords
- gas
- organic ligand
- complex
- metal ion
- storing
- 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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Links
Landscapes
- Filling Or Discharging Of Gas Storage Vessels (AREA)
- Engine Equipment That Uses Special Cycles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、新規な金属錯体に
関し、その結晶構造中に分子を収納しうる空隙を有し、
ガスを貯蔵する能力を有する金属錯体に関する。本発明
の目的は、金属錯体として新規な構造を持ち、新しい用
途として用いられ得る、あるいは、より高い機能を実現
可能な金属錯体を提供することにある。また本発明は、
前記金属錯体を使用したガス貯蔵装置、及び前記ガス貯
蔵装置を装備した交通輸送手段、特に自動車にも関す
る。さらに、本発明にかかる金属錯体は、反応触媒やそ
の担体、ガス組成物中の特定の成分を吸着除去して精製
する処理剤や、処理装置にも使用可能である。TECHNICAL FIELD The present invention relates to a novel metal complex, which has voids capable of accommodating molecules in its crystal structure,
It relates to metal complexes having the ability to store gas. An object of the present invention is to provide a metal complex which has a novel structure as a metal complex and can be used for a new application or can realize a higher function. The present invention also provides
The present invention also relates to a gas storage device using the metal complex, and a transportation means, particularly an automobile, equipped with the gas storage device. Further, the metal complex according to the present invention can be used for a reaction catalyst, a carrier thereof, a treating agent for adsorbing and removing a specific component in a gas composition, and a treating apparatus.
【0002】[0002]
【従来の技術】可燃性のガスを貯蔵する技術としては、
単に加圧し、体積を圧縮して高圧でボンベに充填する方
法、冷却して液化し、断熱された容器に充填する方法、
アセチレンのように、比較的低い圧力にしか圧縮できな
いガスをアセトン等の溶剤に溶解してボンベに充填する
方法等が知られている。ガスをエネルギー源として使用
する交通輸送手段としては、ボンベに充填したLPガス
を燃料とした乗用車が知られている。2. Description of the Related Art As a technique for storing flammable gas,
Simply pressurize, compress the volume and fill the cylinder at high pressure, cool to liquefy and fill the insulated container,
There is known a method in which a gas, such as acetylene, which can be compressed only at a relatively low pressure is dissolved in a solvent such as acetone and then filled in a cylinder. As a transportation means that uses gas as an energy source, a passenger car using LP gas filled in a cylinder as a fuel is known.
【0003】[0003]
【発明が解決しようとする課題】ガスを貯蔵する方法に
おいて、単に加圧するだけの方法では、高圧にするため
の特殊な加圧装置が必要である上に、水素ガス、メタン
ガス等に使用される20MPa(200kgf/c
m2 )にも及ぶ高圧に耐える性能を確保するためボンベ
の重量が極めて重くなり、取り扱い、搬送が困難であ
る。また、液化する方法も特殊な圧縮装置と冷却装置を
必要とし、容器も保温性能を確保するために特殊な構造
のものを必要とする。さらに、溶剤を使用するものは、
ガス中に溶剤の蒸気が混入する上に、溶剤分だけ搬送重
量が余分にかかり、無駄であると共に、特殊なガスにし
か使用できない。近年、水素を貯蔵する多孔質の合金が
開発されたが、高価であり、ガス成分の種類が限定的で
ある。In the method of storing gas, in the method of simply pressurizing, a special pressurizing device for increasing the pressure is required, and it is used for hydrogen gas, methane gas and the like. 20 MPa (200 kgf / c
In order to secure the ability to withstand a high pressure of up to m 2 ), the weight of the cylinder becomes extremely heavy and it is difficult to handle and convey. Further, the liquefying method also requires a special compression device and cooling device, and the container also needs a special structure in order to ensure heat retention performance. Furthermore, those that use solvents
In addition to the solvent vapor being mixed in the gas, the transport weight is added by the amount of the solvent, which is wasteful and can be used only for a special gas. In recent years, porous alloys for storing hydrogen have been developed, but they are expensive and the kinds of gas components are limited.
【0004】これに対し、ジカルボン酸銅錯体として、
層状構造を有する錯体が見いだされ、その構造を利用し
た用途として、ガスの吸着・吸蔵による貯蔵、触媒、分
子ふるい等の機能が期待されている。これらの錯体は、
その結晶構造中に空間を有し、その空間の大きさと構成
成分の特性に応じ種々のガス成分を吸着・貯蔵しうるも
のであることが解明されつつあり、さらに各種の金属錯
体の開発が期待される。また、本発明においては、LP
ガス以外のガス燃料をもエネルギー源とすることがで
き、かつ軽量な貯蔵装置を装備する交通輸送手段も提供
する。On the other hand, as a dicarboxylic acid copper complex,
A complex having a layered structure has been found, and the applications utilizing the structure are expected to have functions such as storage by gas adsorption / occlusion, a catalyst, and a molecular sieve. These complexes are
It has been elucidated that it has a space in its crystal structure and can adsorb and store various gas components depending on the size of the space and the characteristics of the constituents, and further development of various metal complexes is expected. To be done. Further, in the present invention, LP
A gas transportation other than gas can also be used as an energy source, and a transportation means equipped with a lightweight storage device is also provided.
【0005】[0005]
【課題を解決するための手段】本発明は、2価の金属イ
オン、剛直な骨格の両末端に前記金属イオンに配位可能
な原子を有する2座配位可能な有機配位子、及び2,3
−ピラジンジカルボン酸より構成され、層状構造を有
し、ガス貯蔵可能な有機金属錯体に関する。前記金属錯
体を構成する及び剛直な骨格の両末端に前記金属イオン
に配位可能な原子を有する2座配位可能な有機配位子
は、ピラジン、4,4’−ビピリジル、トランス−1,
2−ビス(4−ピリジル)エチレン、1,4−ジシアノ
ベンゼン、4,4’−ジシアノビフェニル、1,2−ジ
シアノエチレン、1,4−ビス(4−ピリジル)ベンゼ
ンより選択される有機配位子である。The present invention relates to a divalent metal ion, a bidentate coordinating organic ligand having an atom capable of coordinating with the metal ion at both ends of a rigid skeleton, and 2 , 3
-It relates to an organometallic complex composed of pyrazine dicarboxylic acid, having a layered structure and capable of storing gas. The bidentate-coordinating organic ligand which comprises the metal complex and has atoms capable of coordinating with the metal ion at both ends of the rigid skeleton is pyrazine, 4,4′-bipyridyl, trans-1,
Organic coordination selected from 2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2-dicyanoethylene, 1,4-bis (4-pyridyl) benzene Is a child.
【0006】このような錯体としては、特に2価の金属
イオンとして銅イオン(Cu2+)を使用した、As such a complex, copper ion (Cu 2+ ) is used as a divalent metal ion.
【化3】Cu2(bpy)(byzdc)2 (bpyは4,4’−ビピリジル、byzdcは2,3
−ピラジンジカルボン酸を表す。)にて表される金属錯
体が好ましい。Embedded image Cu 2 (bpy) (byzdc) 2 (bpy is 4,4′-bipyridyl, byzdc is 2,3
-Represents pyrazine dicarboxylic acid. ) A metal complex represented by
【0007】本発明に使用される有機配位子は、剛直な
分子構造を有し、その作用によりガスを吸着・貯蔵しう
る結晶格子中の空間が形成される。「剛直な分子構造」
とは、C−C結合等のように回転可能な結合を含まず、
従って、金属に配位可能な原子間の距離が変動しない分
子構造であることを意味する。このような分子の両末端
に、金属イオンに配位可能な、窒素等の原子を有してい
る配位子が好適である。配位可能な原子は、有機配位子
の分子の両末端に、分子内で点対称に存在していること
が特に好ましい。The organic ligand used in the present invention has a rigid molecular structure, and its action forms a space in the crystal lattice capable of adsorbing and storing gas. "Rigid molecular structure"
And does not include a rotatable bond such as C-C bond,
Therefore, it means a molecular structure in which the distance between the atoms capable of coordinating to the metal does not change. A ligand having an atom such as nitrogen capable of coordinating with a metal ion at both ends of such a molecule is preferable. It is particularly preferable that the coordinable atoms are present in the molecule of the organic ligand at both ends thereof in point symmetry within the molecule.
【0008】本発明の金属錯体は、2価の金属イオンの
溶液、剛直な骨格の両末端に前記金属イオンに配位可能
な原子を有する2座配位可能な有機配位子、及び2,3
−ピラジンジカルボン酸の溶液を所定比率で混合し、反
応させて得られるものであり、結晶の成長に適した条件
を選択して合成される。The metal complex of the present invention comprises a solution of a divalent metal ion, a bidentate coordinating organic ligand having atoms capable of coordinating with the metal ion at both ends of a rigid skeleton, and 2, Three
It is obtained by mixing and reacting a solution of pyrazinedicarboxylic acid at a predetermined ratio, and is synthesized by selecting conditions suitable for crystal growth.
【0009】本発明はガス貯蔵装置にも関する。例とし
ては図3に示され、この図に基づいて説明すると、ガス
貯蔵装置1は、ガスの出入り口4a、4bを備えた耐圧
容器2の内部に形成された空間5に、2価の金属イオ
ン、剛直な骨格の両末端に前記金属イオンに配位可能な
原子を有する2座配位可能な有機配位子、及び2,3−
ピラジンジカルボン酸より構成され、層状構造を有し、
ガス貯蔵可能な3次元有機金属錯体3を収納して構成さ
れる。かかる貯蔵装置は、簡易な充填装置を使用してガ
スを充填することができると共に、ガス吸着能を有する
金属錯体を収納しているため内圧の低い状態で多くのガ
スを貯蔵することができ、貯蔵装置自体の構造も簡易で
かつ軽量に設計することが可能であり、内燃機関、燃料
電池等の燃料となるメタン、天然ガス等を容易に搬送す
ることが可能となる。したがって、かかる貯蔵装置は、
自動車、船舶等の交通輸送手段、およびこれらに使用さ
れる発電機、冷凍機等の付属設備のエネルギー供給源と
して使用が可能である。The invention also relates to a gas storage device. An example is shown in FIG. 3, and will be described based on this figure. In the gas storage device 1, a divalent metal ion is placed in a space 5 formed inside a pressure resistant container 2 provided with gas inlets and outlets 4a and 4b. A bidentate-coordinating organic ligand having atoms capable of coordinating with the metal ion at both ends of a rigid skeleton, and 2,3-
It is composed of pyrazine dicarboxylic acid and has a layered structure,
It is configured by housing a three-dimensional organometallic complex 3 capable of storing gas. Such a storage device can be filled with a gas by using a simple filling device, and can store a large amount of gas in a state of low internal pressure because it contains a metal complex having a gas adsorbing ability, The structure of the storage device itself can be designed to be simple and lightweight, and it becomes possible to easily transport methane, natural gas, etc., which are fuels for the internal combustion engine, the fuel cell and the like. Therefore, such a storage device is
It can be used as an energy supply source for transportation means such as automobiles and ships, and auxiliary equipment such as generators and refrigerators used therefor.
【0010】前記ガス貯蔵装置に収納して使用するガス
貯蔵可能な金属錯体は、2座配位可能な有機配位子とし
て、ピラジン、4,4’−ビピリジル、トランス−1,
2−ビス(4−ピリジル)エチレン、1,4−ジシアノ
ベンゼン、4,4’−ジシアノビフェニル、1,2−ジ
シアノエチレン、1,4−ビス(4−ピリジル)ベンゼ
ンより選択される有機配位子を使用したものであること
が好ましい。かかる配位子を使用した金属錯体が、ガス
を吸着しうる結晶格子空間を形成しうるからである。こ
れらの金属錯体のうち、特に、その化学構造が前記〔化
3〕にて表されるものであることが好ましい。その理由
は、4,4’−ビピリジルが、その化学構造上メタンの
吸着貯蔵に適した結晶格子空間を形成するからである。
また、1,4−ビス(4−ピリジル)ベンゼンも、同様
の理由により、好ましい錯体を形成する。The gas-storable metal complex used in the gas storage device is pyrazine, 4,4'-bipyridyl, trans-1, as a bidentate coordinating organic ligand.
Organic coordination selected from 2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2-dicyanoethylene, 1,4-bis (4-pyridyl) benzene It is preferable to use a child. This is because the metal complex using such a ligand can form a crystal lattice space capable of adsorbing gas. Of these metal complexes, those having a chemical structure represented by the above [Chemical Formula 3] are particularly preferable. The reason is that 4,4'-bipyridyl forms a crystal lattice space suitable for adsorptive storage of methane due to its chemical structure.
In addition, 1,4-bis (4-pyridyl) benzene also forms a preferable complex for the same reason.
【0011】[0011]
【発明の実施の形態】本発明は、2価の金属イオン、剛
直な骨格の両末端に前記金属イオンに配位可能な原子を
有する2座配位可能な有機配位子、及び2,3−ピラジ
ンジカルボン酸より構成され、層状構造を有し、ガス貯
蔵可能な3次元有機金属錯体に関する。このような金属
錯体は、その層状構造に基づく層間に比較的大きな空間
を形成し、その空間はガス分子を収納しうる大きさであ
るため、ガスを吸着、貯蔵する性能が得られるものと推
定される。BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a divalent metal ion, a bidentate-coordinating organic ligand having atoms capable of coordinating to the metal ion at both ends of a rigid skeleton, and 2,3 -A three-dimensional organometallic complex composed of pyrazine dicarboxylic acid, having a layered structure and capable of storing gas. Such a metal complex forms a relatively large space between layers based on its layered structure, and since the space has a size capable of accommodating gas molecules, it is presumed that gas adsorption and storage performance can be obtained. To be done.
【0012】本発明の金属錯体を構成する2座配位可能
な有機配位子は、ピラジン、4,4’−ビピリジル、ト
ランス−1,2−ビス(4−ピリジル)エチレン、1,
4−ジシアノベンゼン、4,4’−ジシアノビフェニ
ル、1,2−ジシアノエチレン、1,4−ビス(4−ピ
リジル)ベンゼンより選択される有機配位子であること
が好ましい。かかる配位子は、分子の両末端に金属イオ
ンに配位可能な原子、好ましくは窒素原子を有し、かつ
分子に剛直性があるため、その両末端、好ましくは分子
内の点対称の位置に存在する窒素原子が、それぞれ別の
金属イオンに配位し、その(金属イオン−配位子)の繰
り返し構造が錯体の結晶格子中で形成され、このような
格子が場合によっては積層された構造を形成することに
より、ガス貯蔵可能な層状構造が形成されるものと考え
られる。配位子中の、金属に配位した原子、ここでは窒
素原子間の距離はこの配位子により決定されるため、当
該配位子の選択により、吸着される分子の大きさが変更
でき、従って、貯蔵しうるガス成分の選択も可能とな
る。また、原料化合物である金属塩の陰イオンによって
も変動しうる。Bidentate-coordinating organic ligands constituting the metal complex of the present invention include pyrazine, 4,4'-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 1, and 1.
An organic ligand selected from 4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2-dicyanoethylene, and 1,4-bis (4-pyridyl) benzene is preferable. Such a ligand has an atom capable of coordinating with a metal ion, preferably a nitrogen atom, at both ends of the molecule, and since the molecule has rigidity, both ends thereof, preferably the position of point symmetry in the molecule. The nitrogen atoms present in each coordinate to different metal ions, the (metal ion-ligand) repeating structure is formed in the crystal lattice of the complex, and such lattices are optionally stacked. It is believed that the formation of the structure forms a gas-storable layered structure. Since the distance between the atoms coordinated to the metal, here the nitrogen atom, in the ligand is determined by this ligand, the size of the adsorbed molecule can be changed by selecting the ligand, Therefore, it becomes possible to select a gas component that can be stored. It may also change depending on the anion of the metal salt that is the raw material compound.
【0013】前記錯体に適する金属イオンとしては、ベ
リリウム、マグネシウム、カルシウム、ストロンチウ
ム、バリウム等のアルカリ土類金属イオン、鉄、コバル
ト、ニッケル、パラジウム等のVIII族の金属イオ
ン、銅、亜鉛、カドミウム、水銀、鉛、マンガン等の金
属イオンが使用でき、これらの金属イオンの硫酸塩、硝
酸塩、過塩素酸塩、テトラフルオロほう酸塩、ヘキサフ
ルオロりん酸塩、ハロゲン塩、炭酸塩、蟻酸塩、酢酸塩
等を前記金属イオンの原料として使用することができ
る。特に、金属イオンとして銅イオンを使用したものが
好ましく、この場合、使用する原料としては、硫酸銅、
硝酸銅、炭酸銅等の無機塩、蟻酸銅、酢酸銅等の有機塩
を使用することができる。Suitable metal ions for the complex include alkaline earth metal ions such as beryllium, magnesium, calcium, strontium and barium, Group VIII metal ions such as iron, cobalt, nickel and palladium, copper, zinc and cadmium. Metal ions such as mercury, lead and manganese can be used. Sulfates, nitrates, perchlorates, tetrafluoroborates, hexafluorophosphates, halogens, carbonates, formates and acetates of these metal ions can be used. Etc. can be used as a raw material of the metal ion. In particular, those using copper ions as metal ions are preferable, and in this case, the raw material used is copper sulfate,
Inorganic salts such as copper nitrate and copper carbonate, and organic salts such as copper formate and copper acetate can be used.
【0014】金属錯体は、金属イオン塩の溶液、有機配
位子の溶液、及び2,3−ピラジンジカルボン酸の溶液
を混合し、反応させ、錯体化することにより得られるも
のであり、各原料の比率が所定の比となるように混合
し、均一に攪拌したのち、所定の条件で反応させ、錯体
の結晶を生成させる。反応条件は、金属イオンと配位子
の組み合わせによって異なるが、外見上は粉体であって
も、結晶がある程度の大きさに成長しないと結晶中の空
間が十分に得られない。好ましくは、室温に近い条件で
長時間反応させる。必要に応じ、加熱による反応の促
進、溶剤の蒸発等を行ってもよい。反応温度は−10℃
〜100℃、好ましくは10℃〜60℃である。The metal complex is obtained by mixing a solution of a metal ion salt, a solution of an organic ligand, and a solution of 2,3-pyrazinedicarboxylic acid, reacting them, and complexing them. Are mixed so that the ratio becomes a predetermined ratio, and the mixture is stirred uniformly and then reacted under predetermined conditions to form a crystal of a complex. The reaction conditions differ depending on the combination of the metal ion and the ligand, but even if the powder is apparent, a sufficient space in the crystal cannot be obtained unless the crystal grows to a certain size. Preferably, the reaction is carried out for a long time under conditions close to room temperature. If necessary, the reaction may be promoted by heating and the solvent may be evaporated. Reaction temperature is -10 ℃
-100 ° C, preferably 10 ° C-60 ° C.
【0015】本発明において、金属塩を溶解させる溶剤
としては、水、アセトン、の他メタノール、エタノール
等のアルコール類、その他金属に強く配位しないで金属
塩を溶解するものが好ましく、単独で又は混合して使用
する。また、有機配位子を溶解させる溶剤としても強く
金属に配位しないものが使用可能であり、水の他、アセ
トン、MEK、MIBK等のケトン類、酢酸エチル、酢
酸ブチル等のエステル類、メタノールやエタノール等の
アルコール類、アセトニトリル、テトラヒドロフラン、
ジオキサン、ジメチルホルムアミド、ジメチルアセトア
ミド、トルエン、ヘキサン等の有機溶剤を単独で又は混
合して使用する。In the present invention, the solvent for dissolving the metal salt is preferably water, acetone, alcohols such as methanol and ethanol, and other solvents capable of dissolving the metal salt without being strongly coordinated with the metal, either alone or Use by mixing. Further, as a solvent for dissolving the organic ligand, a solvent that does not strongly coordinate to a metal can be used. In addition to water, ketones such as acetone, MEK and MIBK, esters such as ethyl acetate and butyl acetate, and methanol. And alcohols such as ethanol, acetonitrile, tetrahydrofuran,
Organic solvents such as dioxane, dimethylformamide, dimethylacetamide, toluene and hexane are used alone or in combination.
【0016】本発明の金属錯体を製造するのに使用する
前記溶剤は、相互に均一に混和するもの、相互に混和せ
ず相分離するもの、いずれの組み合わせも使用できる。
「混和」する場合とは、例えば、水とアセトン、水とエ
タノール等のように、いかなる比率でも均一に相溶する
組み合わせの他、ある一定の組成範囲のみで均一に相溶
する水とメチルエチルケトン(MEK)等の組み合わせ
でもかまわない。溶剤は、原料化合物の溶解性、溶剤自
体の相溶性、生成する錯体の溶解度、反応への影響等を
考慮して選択される。水とヘキサンのように、完全に相
分離する溶剤の組み合わせによると、分離した界面に結
晶が生成する。The above-mentioned solvents used for producing the metal complex of the present invention may be those which are uniformly miscible with each other or those which are phase-separated without being miscible with each other.
In the case of “mixing”, for example, water and acetone, water and ethanol, and other combinations that are uniformly compatible at any ratio, as well as water and methyl ethyl ketone (which are compatible only within a certain composition range). A combination such as MEK) may be used. The solvent is selected in consideration of the solubility of the raw material compound, the compatibility of the solvent itself, the solubility of the complex formed, the influence on the reaction and the like. When a combination of solvents such as water and hexane that completely phase separates, crystals are formed at the separated interfaces.
【0017】得られた錯体は、常法により濾過し、乾燥
する。乾燥は、好ましくは、減圧下に、加熱して行う。
乾燥が不十分な場合は、結晶格子空間に溶剤分子が残
り、ガス吸着性能が十分に発揮されず、吸着後脱着され
たガスの溶剤含有率が高くなる。水等の低揮発性の溶剤
を使用した場合は、その水等と相溶する高揮発性の有機
溶剤にて洗浄し、さらに、これら水等の低揮発性の溶剤
と共沸する有機溶剤、例えば水に対してはエタノール、
アセトン等の親水性溶剤で洗浄したのち乾燥することも
好ましい態様である。The obtained complex is filtered by a conventional method and dried. Drying is preferably carried out by heating under reduced pressure.
If the drying is insufficient, solvent molecules remain in the crystal lattice space, the gas adsorption performance is not sufficiently exhibited, and the solvent content of the gas desorbed after adsorption increases. When using a low-volatile solvent such as water, wash with a highly volatile organic solvent compatible with the water, further, an organic solvent azeotropic with a low-volatile solvent such as water, For example, ethanol for water,
It is also a preferred embodiment to wash with a hydrophilic solvent such as acetone and then dry.
【0018】次に、本発明の錯体を使用したガス貯蔵装
置について図3に基づき説明する。ガス貯蔵装置2は、
ガス出入口を備えた、密閉容器であり、耐圧容器である
ことが好ましい。ガス出入口4a、4bは、容器本体に
別々に取り付けられていても良く、一つを兼用または2
重管構造としてもよい。圧力指示装置の取付は自由であ
る。容器本体内部の空間に、金属イオン、2座配位可能
な有機配位子、及び2,3−ピラジンジカルボン酸より
構成され、層状構造を有し、ガス貯蔵可能な3次元有機
金属錯体3を収納して構成される。容器本体内部は、収
納した錯体とガスの接触、ガスの流通を良くするために
区画5、棚6等を設け、また、錯体が粉体である場合に
はメッシュ状の材料にて前記区画5、棚6等を製作する
ことが好ましく、適当なバインダーを使用して顆粒状、
又はペレット状に成形することも好ましい態様である。
容器本体外周部、又は必要に応じて内部には、貯蔵する
ガス成分の、錯体への吸着、脱着を促進するための加熱
・冷却を行う装置を設けることも好ましい。なお、図3
の例では、ガスの流通を良くするために、空間7を設け
てある。Next, a gas storage device using the complex of the present invention will be described with reference to FIG. The gas storage device 2 is
It is a closed container provided with a gas inlet / outlet, and preferably a pressure resistant container. The gas inlets / outlets 4a and 4b may be separately attached to the container body, and may also serve as one or two.
A heavy pipe structure may be used. The pressure indicator can be attached freely. In the space inside the container body, a three-dimensional organometallic complex 3 composed of metal ions, an organic ligand capable of bidentate coordination, and 2,3-pyrazinedicarboxylic acid, having a layered structure and capable of storing gas is provided. It is configured to be stored. Inside the container body, a compartment 5, a shelf 6, etc. are provided in order to improve the contact between the stored complex and the gas and the flow of the gas. When the complex is a powder, the compartment 5 is made of a mesh material. , It is preferable to manufacture the shelves 6 and the like.
Alternatively, molding into pellets is also a preferred embodiment.
It is also preferable to provide a device for heating / cooling for promoting the adsorption and desorption of the gas component to be stored in the complex, on the outer peripheral portion of the container body or, if necessary, inside thereof. Note that FIG.
In the above example, the space 7 is provided in order to improve the flow of gas.
【0019】ガス貯蔵容器に収納する金属錯体は、請求
項1または2に記載した錯体であり、かかる錯体の使用
により、比較的低い圧力にてガスが貯蔵可能となり、容
器にガスを充填するために特殊な加圧装置、冷却装置を
必要とせず、また特殊な断熱容器も必要とせずガスを貯
蔵・搬送することができる。本発明にかかるガス貯蔵容
器への、ガスの充填は、適当なガス加圧装置を介して貯
蔵容器にガスを送り込むことにより行う。この際、ガス
の金属錯体への吸着は通常発熱反応であるため、容器を
同時に冷却することが好ましい。本発明のガス貯蔵容器
から、貯蔵したガスを取り出すときは、取り出し側の圧
力を貯蔵装置に対し、相対的に低圧にし、同時に貯蔵装
置を加熱することにより促進する。The metal complex housed in the gas storage container is the complex described in claim 1 or 2, and by using such a complex, the gas can be stored at a relatively low pressure, and the container is filled with the gas. It does not require a special pressurizing device or cooling device, nor does it need a special heat insulating container to store and transport gas. The filling of the gas storage container according to the present invention with gas is performed by feeding the gas into the storage container via a suitable gas pressurizing device. At this time, since the adsorption of the gas to the metal complex is usually an exothermic reaction, it is preferable to cool the container at the same time. When the stored gas is taken out from the gas storage container of the present invention, the pressure on the take-out side is set to a relatively low pressure with respect to the storage device, and at the same time, the storage device is heated to promote it.
【0020】図4には、ガス貯蔵装置1を備えたガス自
動車9の概略構成を例示した。この例においては、ガス
自動車9は燃料供給源として、本発明のガス貯蔵性金属
錯体が収納されたガス貯蔵装置1を備えるとともにこの
ガス貯蔵装置1に貯蔵された天然ガス等の可燃性ガスを
燃料とする内燃機関としてのエンジン10を備えてい
る。この例の他、ガス燃料を利用した燃料電池をエネル
ギー源とし、モーターを駆動源とした自動車も可能であ
る。なお、図4に示す自動車に使用したガス貯蔵装置
は、図3のものとは別の実施例である。FIG. 4 exemplifies a schematic configuration of a gas vehicle 9 equipped with the gas storage device 1. In this example, the gas vehicle 9 includes, as a fuel supply source, a gas storage device 1 in which the gas-storing metal complex of the present invention is stored, and a flammable gas such as natural gas stored in the gas storage device 1 is used. The engine 10 is provided as an internal combustion engine that uses fuel. In addition to this example, an automobile using a fuel cell using gas fuel as an energy source and a motor as a drive source is also possible. The gas storage device used in the automobile shown in FIG. 4 is an embodiment different from that shown in FIG.
【0021】[0021]
【実施例】以下、本発明の実施例を説明する。 (錯体合成例1)硫酸銅0.02M水溶液50mlに、
ビピリジルの0.01M、2,3−ピラジンジカルボン
酸0.02Mのエタノール/水=1/1の混合溶媒溶液
50mlを加えて混合し、室温にて1日放置し、生じた
青色の沈殿物を吸引濾過した後、室温にて真空乾燥した
ところ、目的物である錯体が0.35g得られた。この
錯体を元素分析することにより、組成式が、 〔Cu2(bpy)(pyzdc)2〕n で表されるものであることが判明した。Embodiments of the present invention will be described below. (Complex Synthesis Example 1) In a 50 ml aqueous solution of 0.02 M copper sulfate,
50 ml of a mixed solvent solution of 0.01 M of bipyridyl and 0.02 M of 2,3-pyrazinedicarboxylic acid in ethanol / water = 1/1 was added and mixed, and the mixture was left at room temperature for 1 day to form a blue precipitate. After suction filtration, vacuum drying at room temperature gave 0.35 g of the target complex. Elemental analysis of this complex has revealed that the composition formula is represented by [Cu 2 (bpy) (pyzdc) 2 ] n .
【0022】この結晶についてX線回折を行い、構造を
解析した結果、Cuとpyzdcが形成する層構造がb
pyによって連結されて多層構造となって結晶を構成し
ており、この層間にガスを貯蔵しうる空間が形成されて
いるものと推定される。この層構造を模式的に示したの
が図1である。The crystal was analyzed by X-ray diffraction and the structure was analyzed. As a result, the layer structure formed by Cu and pyzdc was found to be b.
It is presumed that they are connected by py to form a multi-layered structure to form a crystal, and a space capable of storing gas is formed between the layers. FIG. 1 schematically shows this layer structure.
【0023】(ガス貯蔵能力の測定1)錯体合成例1に
て得られた、(Measurement of Gas Storage Capacity 1) Obtained in Complex Synthesis Example 1,
【化4】Cu2(bpy)(pyzdc)2 なる組成の錯体について、メタンの吸着能力を測定し
た。実験条件は、 使用ガス:メタン(純度 99.99%) 温度 :25℃ 時間 :平衡に達するまで(数秒間) にて行った。結果を図1に示した。この結果より、化3
にて示される組成を有する金属錯体は、メタンの吸着に
対して選択性を有していることが判る。## STR00004 ## The methane adsorption capacity of the complex having the composition Cu 2 (bpy) (pyzdc) 2 was measured. The experimental conditions were as follows: gas used: methane (purity 99.99%) temperature: 25 ° C. time: until equilibrium was reached (several seconds). The results are shown in FIG. From this result,
It can be seen that the metal complex having the composition shown in 1) has selectivity for the adsorption of methane.
【0024】[0024]
【図1】Cu2(bpy)(pyzdc)2組成の錯体の
結晶構造模式図。FIG. 1 is a schematic diagram of a crystal structure of a complex having a Cu 2 (bpy) (pyzdc) 2 composition.
【図2】Cuを使用した金属錯体の、メタンガス吸着特
性測定性能を測定したグラフ。FIG. 2 is a graph showing measurement performance of methane gas adsorption characteristics of a metal complex using Cu.
【図3】ガス貯蔵装置の概略図。FIG. 3 is a schematic diagram of a gas storage device.
【図4】ガス自動車のモデル図。FIG. 4 is a model diagram of a gas vehicle.
1 ガス貯蔵装置 2 圧力容器 3 金属錯体 4a ガス出口 4b ガス入口 5 区画 6 棚部材 7 空間 9 自動車 10 内燃機関 1 Gas Storage Device 2 Pressure Vessel 3 Metal Complex 4a Gas Outlet 4b Gas Inlet 5 Section 6 Shelf Member 7 Space 9 Automotive 10 Internal Combustion Engine
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 FI 技術表示箇所 C10L 3/06 6958−4H C10L 3/00 D F01K 27/00 6958−4H A ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification number Office reference number FI technical display location C10L 3/06 6958-4H C10L 3/00 D F01K 27/00 6958-4H A
Claims (10)
前記金属イオンに配位可能な原子を有する2座配位可能
な有機配位子、及び2,3−ピラジンジカルボン酸より
構成される、ガス貯蔵可能な有機金属錯体。1. A divalent metal ion, a bidentate-coordinating organic ligand having an atom capable of coordinating with the metal ion at both ends of a rigid skeleton, and 2,3-pyrazinedicarboxylic acid. A gas-storable organometallic complex.
ン、4,4’−ビピリジル、トランス−1,2−ビス
(4−ピリジル)エチレン、1,4−ジシアノベンゼ
ン、4,4’−ジシアノビフェニル、1,2−ジシアノ
エチレン、1,4−ビス(4−ピリジル)ベンゼンより
選択される有機配位子である、請求項1記載の、ガス貯
蔵可能な有機金属錯体。2. The organic ligand capable of bidentate coordination is pyrazine, 4,4′-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4, The gas-storable organometallic complex according to claim 1, which is an organic ligand selected from 4'-dicyanobiphenyl, 1,2-dicyanoethylene, and 1,4-bis (4-pyridyl) benzene.
−ピラジンジカルボン酸を表す。)にて表されるもので
ある、請求項1記載のガス貯蔵性有機金属錯体。3. Cu 2 (bpy) (pyzdc) 2 (bpy is 4,4′-bipyridyl, pyzdc is 2,3)
-Represents pyrazine dicarboxylic acid. The gas-storing organometallic complex according to claim 1, which is represented by the formula (1).
末端に前記金属イオンに配位可能な原子を有する2座配
位可能な有機配位子の溶液、及び2,3−ピラジンジカ
ルボン酸の溶液を所定比率で混合し、反応させることを
特徴とする、2価の金属イオン、2座配位可能な有機配
位子及び2,3−ピラジンジカルボン酸より構成され、
層状構造を有し、ガス貯蔵可能な有機金属錯体の製造方
法。4. A solution of a divalent metal ion, a solution of a bidentate-coordinating organic ligand having atoms capable of coordinating with the metal ion at both ends of a rigid skeleton, and 2,3-pyrazine. A solution of a dicarboxylic acid is mixed at a predetermined ratio and reacted, which is composed of a divalent metal ion, a bidentate-coordinable organic ligand, and 2,3-pyrazinedicarboxylic acid,
A method for producing an organometallic complex having a layered structure and capable of storing gas.
ン、4,4’−ビピリジル、トランス−1,2−ビス
(4−ピリジル)エチレン、1,4−ジシアノベンゼ
ン、4,4’−ジシアノビフェニル、1,2−ジシアノ
エチレン、1,4−ビス(4−ピリジル)ベンゼンより
選択される有機配位子を使用する、請求項4記載の、層
状構造を有するガス貯蔵可能な金属錯体の製造方法。5. An organic ligand capable of bidentate coordination is pyrazine, 4,4′-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4. A gas-storable metal having a layered structure according to claim 4, which uses an organic ligand selected from'-dicyanobiphenyl, 1,2-dicyanoethylene, 1,4-bis (4-pyridyl) benzene. Method for producing complex.
液、2座配位可能な有機配位子として4,4’−ビピリ
ジルの溶液、及び2,3−ピラジンジカルボン酸の溶液
を所定比率で混合し、反応させることを特徴とする請求
項4記載の、層状構造を有するガス貯蔵可能な有機金属
錯体の製造方法。6. A solution of Cu ions as divalent metal ions, a solution of 4,4′-bipyridyl as an organic ligand capable of bidentate coordination, and a solution of 2,3-pyrazinedicarboxylic acid at a predetermined ratio. 5. The method for producing a gas-storable organometallic complex having a layered structure according to claim 4, wherein the method is carried out by mixing.
形成された空間に、2価の金属イオン、剛直な骨格の両
末端に前記金属イオンに配位可能な原子を有する2座配
位可能な有機配位子、及び2,3−ピラジンジカルボン
酸より構成され、層状構造を有し、ガス貯蔵可能な有機
金属錯体を収納した、ガス貯蔵装置。7. A bidentate coordination having a divalent metal ion and an atom capable of coordinating with the metal ion at both ends of a rigid skeleton in a space formed inside a pressure-resistant container having a gas inlet / outlet port. A gas storage device, which is composed of a possible organic ligand and 2,3-pyrazinedicarboxylic acid, has a layered structure, and stores a gas-storable organometallic complex.
な有機配位子として、ピラジン、4,4’−ビピリジ
ル、トランス−1,2−ビス(4−ピリジル)エチレ
ン、1,4−ジシアノベンゼン、4,4’−ジシアノビ
フェニル、1,2−ジシアノエチレン、1,4−ビス
(4−ピリジル)ベンゼンより選択される有機配位子を
使用したものである、請求項7記載のガス貯蔵装置。8. A gas storable metal complex, wherein the organic ligand capable of bidentate coordination is pyrazine, 4,4′-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 1, 8. An organic ligand selected from 4-dicyanobenzene, 4,4'-dicyanobiphenyl, 1,2-dicyanoethylene, 1,4-bis (4-pyridyl) benzene is used. Gas storage device.
−ピラジンジカルボン酸を表す。)にて表されるもので
ある、請求項7記載のガス貯蔵装置。9. The gas storable metal complex is represented by the following formula: Cu 2 (bpy) (pyzzdc) 2 (bpy is 4,4′-bipyridyl, pyzdc is 2,3
-Represents pyrazine dicarboxylic acid. 8. The gas storage device according to claim 7, which is represented by
置を搭載し、前記ガス貯蔵装置より供給されるガスをエ
ネルギー源として動く自動車。10. An automobile equipped with the gas storage device according to claim 7, 8 or 9, and moving by using gas supplied from the gas storage device as an energy source.
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