JP2000178279A - Gas storing organometallic complex, its production and gas storing device - Google Patents

Gas storing organometallic complex, its production and gas storing device

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Publication number
JP2000178279A
JP2000178279A JP10360174A JP36017498A JP2000178279A JP 2000178279 A JP2000178279 A JP 2000178279A JP 10360174 A JP10360174 A JP 10360174A JP 36017498 A JP36017498 A JP 36017498A JP 2000178279 A JP2000178279 A JP 2000178279A
Authority
JP
Japan
Prior art keywords
gas
organometallic complex
gas storage
metal ion
storage device
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.)
Pending
Application number
JP10360174A
Other languages
Japanese (ja)
Inventor
Kenji Seki
建司 関
Naoki Inoue
直樹 井上
Susumu Kitagawa
進 北川
Mitsuru Kondo
満 近藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Osaka Gas Co Ltd
Original Assignee
Osaka Gas Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Osaka Gas Co Ltd filed Critical Osaka Gas Co Ltd
Priority to JP10360174A priority Critical patent/JP2000178279A/en
Publication of JP2000178279A publication Critical patent/JP2000178279A/en
Pending legal-status Critical Current

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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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/30—Use of alternative fuels, e.g. biofuels

Abstract

PROBLEM TO BE SOLVED: To obtain an organometallic complex useful as a gas occluding material by mixing a solution of an organic ligand capable of coordinating to a specific metal ion with a solution of the said metal salt. SOLUTION: An organometallic complex having a three dimensional structure constituted of a two valent metal ion and an organic ligand having a bidentate amide bond containing atoms capable of coordinating to the said metal ion in the molecule, e.g. a complex expressed by the formula [Cd(pcia)2 (NO3)2]n [pcia is N-(4-picoryl)-isonicotinamide], is obtained by mixing a solution of a bidentate organic ligand capable of coordinating to be bidentate to a two valent metal (e.g. magnesium, etc.), e.g. a ligand expressed by the formula (R and R' are each an alkylene, alkenyl or an arylene) with a solution of the bivalent metal salt. The crystal of the organometallic complex is obtained by standing the obtained mixture solution for, e.g. at normal temperature -60 deg.C for several hours to several days, filtering the precipitated solid by suction and drying at 100 deg.C for 5 hours in vacuum.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【０００１】[0001]

【発明の属する技術分野】本発明は、新規な有機金属錯
体及びその製造方法に関し、詳しくは、メタンを主成分
とするガスの吸蔵材として好適な有機金属錯体及びその
製造方法に関する。本発明は、ガス吸蔵材、ガス貯蔵方
法及びガス貯蔵装置に関し、詳しくは、メタンを主成分
とするガスを貯蔵するために好適なガス吸蔵材、ガス貯
蔵方法及びガス貯蔵装置に関する。さらに、本発明は、
ガス自動車に関し、詳しくは、メタンを主成分とするガ
スから駆動力を得るガス自動車に関する。The present invention relates to a novel organometallic complex and a method for producing the same, and more particularly, to an organometallic complex suitable as a storage material for a gas containing methane as a main component and a method for producing the same. The present invention relates to a gas storage material, a gas storage method, and a gas storage device, and more particularly, to a gas storage material, a gas storage method, and a gas storage device suitable for storing a gas containing methane as a main component. Further, the present invention provides
More particularly, the present invention relates to a gas vehicle that obtains driving power from a gas containing methane as a main component.

【０００２】さらに、本発明は、吸着式ガス貯蔵タンク
及びＬＮＧ貯蔵装置に関する。[0002] Furthermore, the present invention relates to an adsorption type gas storage tank and an LNG storage device.

【０００３】[0003]

【従来の技術】従来、メタンを主成分とするガスの貯蔵
にあたっては、吸蔵材として主に活性炭を使用すること
が提案されている。しかしながら、活性炭を使用する場
合は、体積当たりのガスの吸着量が少ない。体積当たり
のガスの吸着量を上げるために、活性炭を成型して吸蔵
材とした場合においても、その吸着量の向上には限界が
あった。比表面積が大きく、比較的体積当たりのガス吸
着能が高いもの（高比表面積活性炭）もあるが、これら
は、その価格が高い。ガスの吸着、脱離状況について考
察すると、活性炭の場合は、細孔径が様々であるため、
ガスの吸着、脱離を繰り返すと、吸着、脱離性能が一定
せず、繰り返し特性が悪いという問題があった。2. Description of the Related Art Hitherto, it has been proposed to use mainly activated carbon as an occluding material when storing a gas containing methane as a main component. However, when activated carbon is used, the amount of gas adsorbed per volume is small. Even when activated carbon is molded and used as an occlusion material in order to increase the amount of gas adsorbed per volume, there is a limit in improving the amount of adsorbed gas. Some of them have a large specific surface area and a relatively high gas adsorption capacity per volume (high specific surface area activated carbon), but these are expensive. Considering the state of gas adsorption and desorption, activated carbon has various pore diameters,
When gas adsorption and desorption are repeated, the adsorption and desorption performance is not constant, and there is a problem that the repetition characteristics are poor.

【０００４】[0004]

【発明が解決しようとする課題】本発明の目的は、安価
であるとともに体積当たりのガス吸着能が高く、繰り返
し特性の良好なガスの貯蔵技術を提供するとともに、ガ
スの貯蔵を簡便に行えるガス貯蔵装置、さらには、こう
いった特性を備えたガス自動車、吸着式ガス貯蔵タンク
及びＬＮＧ貯蔵装置を得ることにある。SUMMARY OF THE INVENTION It is an object of the present invention to provide a gas storage technique which is inexpensive, has a high gas adsorption capacity per volume, has good repetition characteristics, and can easily store gas. An object of the present invention is to provide a storage device, a gas vehicle, an adsorption type gas storage tank, and an LNG storage device having such characteristics.

【０００５】[0005]

【課題を解決するための手段】本発明者は、上記のよう
な課題を解決するために鋭意研究を遂行し、特定の有機
金属錯体がガス吸蔵材、特にメタンを主成分とするガス
の吸蔵材として好適であることを見出し、本発明を完成
した。本発明は、以下の有機金属錯体及びその製造方
法、ガス吸蔵材、ガス貯蔵方法及びガス貯蔵装置、ガス
自動車、吸着式ガス貯蔵タンク及びＬＮＧ貯蔵装置に係
る。Means for Solving the Problems The present inventor has conducted intensive studies in order to solve the above-mentioned problems, and has found that a specific organometallic complex is a gas occluding material, particularly a gas occluding material mainly composed of methane. The present invention was found to be suitable as a material, and the present invention was completed. The present invention relates to the following organometallic complexes and their production methods, gas storage materials, gas storage methods and gas storage devices, gas vehicles, adsorption-type gas storage tanks and LNG storage devices.

【０００６】本発明は、下記の項１〜項１２に関する。 項１． ２価の金属イオン、前記金属イオンに配位可能
な原子を有する２座配位可能なアミド結合を分子内に有
する有機配位子より構成される三次元構造を有する有機
金属錯体。 項２． 有機配位子が下記式（１）The present invention relates to the following items 1 to 12. Item 1. An organometallic complex having a three-dimensional structure comprising a divalent metal ion and an organic ligand having in its molecule a bidentate amide bond having an atom capable of coordinating with the metal ion. Item 2. The organic ligand has the following formula (1)

【０００７】[0007]

【化２】 Embedded image

【０００８】〔式中、ＲおよびＲ’は同一又は異なって
アルキレン基、アルケニレン基またはアリーレン基を示
す。〕で表される項１に記載の有機金属錯体。 項３． 化学式（２） ［Ｍ2+（Ligand)2］(NO3 -)2 （２） 〔式中、Ｍ2+は２価の金属イオンを示し、Ligandは２価
の金属イオンに２座配位可能なアミド結合を分子内に有
する前記有機配位子である。〕で表される項１に記載の
有機金属錯体。 項４． Ｍが銅、カドミウム、コバルト、ニッケル及び
鉄からなる群から選ばれる項３に記載の有機金属錯体。 項５． ２価の金属イオン塩及び前記金属イオンに配位
可能な原子を有する２座配位可能なアミド結合を分子内
に有する有機配位子を溶媒中に所定比率で混合し、反応
させることを特徴とする三次元構造を有する有機金属錯
体の製造方法。 項６． 項１〜４のいずれかに記載の有機金属錯体から
なるガス吸蔵材。 項７． ガスが出入口を備えた耐圧容器の内部に形成さ
れた空間に、項５に記載のガス吸蔵材を収納したガス貯
蔵装置。 項８． 項６に記載のガス吸蔵材に加圧条件下でメタン
を主成分とするガスを吸着して貯蔵するガス貯蔵方法。 項９． 貯蔵対象のガスが出入り可能な出入口(5a)、(5
b)と容器内のガスを加圧状態で保持可能な保持機構
（６）とを備え、且つ常温に温度維持可能な圧力容器
（４）を備えたガス貯蔵装置であって、前記圧力容器
（４）内に項６に記載のガス吸蔵材（８）を備え、メタ
ンを主成分とするガスを貯蔵対象とするガス貯蔵装置。 項１０． 項９に記載のガス貯蔵装置（１）を備え、ガ
ス貯蔵装置（１）から供給されるメタンを主成分とする
ガスから駆動力を得る内燃機関（３）を備えたガス自動
車。 項１１． 項６に記載のガス吸蔵材を含む吸着式ガス貯
蔵タンク。 項１２． ＬＮＧタンクと項６に記載のガス吸蔵材が充
填された吸着式充填タンクを安全弁を介して連設し、Ｌ
ＮＧタンクの圧力が所定値以上に高くなった場合に、一
定量の蒸発ガス（ＢＯＧ）を吸着式充填タンクに充填さ
れるようにしてなるＬＮＧ貯蔵装置。Wherein R and R ′ are the same or different and each represents an alkylene group, alkenylene group or arylene group. ] The organometallic complex according to item 1, which is represented by the formula: Item 3. Chemical formula (2) [M 2+ (Ligand) 2 ] (NO 3 − ) 2 (2) [wherein, M 2+ represents a divalent metal ion, and Ligand is a bidentate coordination to a divalent metal ion. Said organic ligand having a possible amide bond in the molecule. ] The organometallic complex according to item 1, which is represented by the formula: Item 4. Item 4. The organometallic complex according to item 3, wherein M is selected from the group consisting of copper, cadmium, cobalt, nickel and iron. Item 5. A bivalent metal ion salt and an organic ligand having in its molecule a bidentate amide bond having an atom capable of coordinating to the metal ion are mixed and reacted in a solvent at a predetermined ratio. A method for producing an organometallic complex having a three-dimensional structure. Item 6. Item 5. A gas occluding material comprising the organometallic complex according to any one of Items 1 to 4. Item 7. Item 6. A gas storage device in which the gas occlusion material according to Item 5 is stored in a space formed inside a pressure-resistant container provided with a gas inlet / outlet. Item 8. Item 7. A gas storage method, wherein a gas containing methane as a main component is adsorbed and stored on the gas occluding material according to Item 6 under pressurized conditions. Item 9. Entrance (5a), (5
b) and a holding mechanism (6) capable of holding the gas in the container in a pressurized state and a pressure container (4) capable of maintaining the temperature at room temperature, wherein the pressure container (4) 4) A gas storage device including the gas storage material (8) according to item 6 therein and storing a gas containing methane as a main component. Item 10. Item 10. A gas vehicle comprising: the gas storage device (1) according to Item 9; and an internal combustion engine (3) that obtains driving power from a gas containing methane as a main component supplied from the gas storage device (1). Item 11. Item 7. An adsorption type gas storage tank containing the gas occluding material according to Item 6. Item 12. An LNG tank and an adsorption-type filling tank filled with the gas occluding material described in Item 6 are connected to each other via a safety valve.
An LNG storage device in which a fixed amount of evaporative gas (BOG) is filled in an adsorption type filling tank when the pressure of the NG tank becomes higher than a predetermined value.

【０００９】[0009]

【発明の実施の形態】＜金属錯体の製造＞２価の金属イ
オンに２座配位可能な有機配位子の溶液と２価の金属塩
の溶液を混合することにより、本発明の有機金属錯体を
得ることができる。得られた混合液を例えば常温から６
０℃で数時間から数日放置し、沈殿した固体を吸引濾過
し、１００℃で５時間真空乾燥することにより有機金属
錯体の結晶を製造することができる。BEST MODE FOR CARRYING OUT THE INVENTION <Production of Metal Complex> The organic metal of the present invention is prepared by mixing a solution of an organic ligand capable of bidentate coordination with a divalent metal ion and a solution of a divalent metal salt. A complex can be obtained. The obtained mixture is cooled, for example, from room temperature to 6
The mixture is allowed to stand at 0 ° C. for several hours to several days, and the precipitated solid is subjected to suction filtration and vacuum-dried at 100 ° C. for 5 hours to produce an organometallic complex crystal.

【００１０】２価の金属イオンの塩としては、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２価の金属イオン
の硫酸塩、硝酸塩、過塩素酸塩、テトラフルオロホウ酸
塩、ヘキサフルオロリン酸塩、ハロゲン化塩、炭酸塩、
ギ酸塩、酢酸塩を使用することができる。この金属塩の
溶液と二座配位可能な有機配位子を反応させることによ
り、目的のガス吸蔵材である有機金属錯体を得ることが
できる。Examples of the salts of divalent metal ions 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 the like.
Sulfate, nitrate, perchlorate, tetrafluoroborate, hexafluorophosphate, halide, carbonate of divalent metal ions such as cadmium, mercury, lead, and manganese;
Formates and acetates can be used. By reacting the solution of the metal salt with an organic ligand capable of bidentate coordination, an organometallic complex as a target gas storage material can be obtained.

【００１１】前記２座配位可能な有機配位子は、例えば
前記一般式（１）で表される化合物が使用できる。As the organic ligand capable of bidentate coordination, for example, a compound represented by the general formula (1) can be used.

【００１２】濃度としては、金属塩の２モル当量であ
り、０．０１〜０．５ｍｏｌ／Ｌである。The concentration is 2 molar equivalents of the metal salt, and is 0.01 to 0.5 mol / L.

【００１３】前記合成の反応温度は−２０〜１００℃程
度であり、常温で反応する。The reaction temperature of the above synthesis is about -20 to 100 ° C., and the reaction is carried out at room temperature.

【００１４】本反応の溶媒としては、水、アセトン、メ
タノール、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、ベンゼン、トルエン、
ヘキサン等の有機溶媒を単独又は混合して使用できる。Examples of the solvent for this reaction include water, alcohols such as acetone, methanol and ethanol, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, benzene, toluene,
Organic solvents such as hexane can be used alone or in combination.

【００１５】なお、本発明の有機金属錯体は、例えば下
記組成式（Ａ）または（Ｂ） ｛［Ｍ2+（Ligand)2］(Ｘ-)2｝ｎ （Ａ） ［Ｍ2+（Ligand)2］(Ｘ-)2 （Ｂ） 〔式中、Ｍ、Ligandは前記に同じ。ｎは任意の正の整数
を示す。Ｘ-は硝酸イオン、過塩素酸イオン、テトラフ
ルオロホウ酸イオン、ヘキサフルオロリン酸イオン、塩
素イオン、臭素イオン、ヨウ素イオン、フッ素イオン、
１／２炭酸イオン、ギ酸イオン、酢酸イオン、１／２硫
酸イオンなどの１価のアニオンを示す〕で表すことがで
きる。上記において、組成式（Ｂ）はＭ2+、Ligand、Ｘ
-の比率を示し、組成式（Ａ）は該組成の有機金属錯体
が３次元的に広がった構造を有することを”ｎ”を用い
て示すものである。従って、ｎは任意の正の整数を示
す。ガス吸蔵材 有機金属錯体はガス（例えば、メタンを主成分とするガ
ス）を吸着することができるので、ガス吸蔵材として使
用することができる。有機金属錯体の結晶における細孔
径は、構造上一定しているため、特定のガス（例えば、
メタン）以外のガス成分を吸着したまま脱着しにくくな
り、繰り返し性能が劣化するといった問題も発生しにく
い。The organometallic complex of the present invention can be prepared, for example, by the following composition formula (A) or (B) {[M 2+ (Ligand) 2 ] (X − ) 2 } n (A) [M 2+ (Ligand ) 2 ] (X − ) 2 (B) wherein M and Ligand are the same as above. n represents an arbitrary positive integer. X - is nitrate ion, perchlorate ion, tetrafluoroborate ion, hexafluorophosphate ion, chloride ion, bromine ion, iodine ion, fluorine ion,
Monovalent anions such as 1/2 carbonate ion, formate ion, acetate ion and 1/2 sulfate ion]. In the above, the composition formula (B) is represented by M 2+ , Ligand, X
The composition formula (A) indicates that the organometallic complex of the composition has a three-dimensionally spread structure using “n”. Therefore, n indicates any positive integer. The gas occluding material organometallic complex can adsorb a gas (for example, a gas containing methane as a main component), and thus can be used as a gas occluding material. Since the pore size in the crystal of the organometallic complex is structurally constant, a specific gas (for example,
It becomes difficult to desorb while adsorbing gas components other than (methane), and the problem that the performance is repeatedly deteriorated is also unlikely to occur.

【００１６】有機金属錯体の結晶を成型（特に、圧縮成
型）することにより、比較的嵩密度の高いガス吸蔵材と
することができる。ガス吸蔵材の嵩密度を高くすること
により、体積当たりのガスの吸着量を大きく増大するこ
とができ、ガス貯蔵性能の点からも好ましい。有機金属
錯体の結晶を成型することにより、その成型密度を高く
するとともに、その吸着能を高くすることができ、単位
体積当たりのガス吸蔵能を、例えば、活性炭より格段に
高いものとすることができる。ガス貯蔵方法 本発明のガス吸蔵材を、加圧条件下で、貯蔵の対象とな
るガス（例えば、メタンを主成分とするガス）を接触さ
せることにより、吸着し、貯蔵することができる。この
貯蔵は、常温以上（例えば、５℃以上）でも可能であ
る。ガスを吸着したガス吸蔵材のガス圧（貯蔵容器内の
圧力）を減圧することにより又は吸蔵材を加熱すること
により、吸着したガスを脱着（放出）させることができ
る。By molding (particularly, compression molding) the crystal of the organometallic complex, a gas occluding material having a relatively high bulk density can be obtained. By increasing the bulk density of the gas occluding material, the amount of gas adsorbed per volume can be greatly increased, which is preferable from the viewpoint of gas storage performance. By molding the crystal of the organometallic complex, it is possible to increase its molding density and its adsorption ability, and to make the gas storage capacity per unit volume much higher than, for example, activated carbon. it can. Gas Storage Method The gas occluding material of the present invention can be adsorbed and stored by contacting a gas to be stored (for example, a gas containing methane as a main component) under a pressurized condition. This storage is possible at room temperature or higher (for example, at 5 ° C. or higher). The adsorbed gas can be desorbed (released) by reducing the gas pressure (pressure in the storage container) of the gas occluding material that has adsorbed the gas or by heating the occluding material.

【００１７】メタン以外の貯蔵可能な成分としては、一
酸化炭素、水素、エタン、プロパン、等が挙げられる。
なお、メタンのみを吸蔵することも可能である。ガス貯蔵装置 本発明のガス貯蔵装置においては、圧力容器内に本発明
のガス吸蔵材を備えるので、吸蔵材が収納されている圧
力容器内に、その出入口からメタンを主成分とするガス
を圧入することにより、ガス吸蔵材に吸着させた状態で
貯蔵することができる。本発明のガス貯蔵装置において
は、例えば、出口側に備えられる弁を開放し、圧力容器
内の内圧を低下させることにより、ガスをガス吸蔵材か
ら脱着させ、貯蔵装置から放出させることができる。ガス自動車 図４に、本発明のガス貯蔵装置を備えたガス自動車２の
概略構成を示す。ガス自動車２は、燃料タンク１として
本発明のガス貯蔵装置を備えるとともに、燃料タンク１
から、タンク内に貯蔵される天然ガスを得て、燃焼用酸
素含有ガス（例えば空気）と混合して、その燃焼により
走行駆動力を得る内燃機関としてのエンジン３を備えて
いる。The storable components other than methane include carbon monoxide, hydrogen, ethane, propane, and the like.
It is also possible to store only methane. Gas storage device In the gas storage device of the present invention, since the gas storage material of the present invention is provided in the pressure vessel, a gas containing methane as a main component is injected into the pressure vessel containing the storage material from the inlet and outlet. By doing so, it can be stored in a state of being adsorbed by the gas occlusion material. In the gas storage device of the present invention, for example, by opening the valve provided on the outlet side and reducing the internal pressure in the pressure vessel, the gas can be desorbed from the gas occluding material and released from the storage device. Gas Vehicle FIG. 4 shows a schematic configuration of a gas vehicle 2 provided with the gas storage device of the present invention. The gas vehicle 2 includes the gas storage device of the present invention as the fuel tank 1 and the fuel tank 1
Thus, the engine 3 is provided as an internal combustion engine that obtains natural gas stored in a tank, mixes it with an oxygen-containing gas for combustion (for example, air), and obtains a driving force by the combustion.

【００１８】燃料タンク１は、いわゆる圧力容器４を備
えて構成されるとともに、貯蔵対象のガスが出入り可能
な出入口として一対の出口５ａと入口５ｂとを備え、容
器４内のガスを加圧状態に維持可能な気密保持機構を構
成する一対の弁６を、出口５ａ及び入口５ｂそれぞれに
備えている。燃料である天然ガスは、ガスステーション
７において、加圧状態で、燃料タンク１に充填される。
燃料タンク１には、本発明のガス吸蔵材８が内装されて
おり、ガス吸蔵材８が天然ガス（メタンを主成分とする
ガスの一例）を常温、加圧状態で吸着する。The fuel tank 1 is provided with a so-called pressure vessel 4 and is provided with a pair of outlets 5a and 5b as an entrance through which gas to be stored can enter and exit. A pair of valves 6 constituting an airtight holding mechanism that can be maintained at the outlet 5a and the inlet 5b are provided. Natural gas, which is a fuel, is charged into the fuel tank 1 in a gas station 7 in a pressurized state.
The gas occluding material 8 of the present invention is provided in the fuel tank 1, and the gas occluding material 8 adsorbs natural gas (an example of a gas containing methane as a main component) at normal temperature and under pressure.

【００１９】燃料タンク１は、通常、常温状態であり、
特に冷却されたりすることはなく、気温が上昇する例え
ば夏場においては、比較的温度が高くなる。本発明のガ
ス吸蔵材（カルボン酸金属錯体の結晶）は、このような
条件下において、即ち、比較的高温（２５〜６０℃程
度）の温度域においても、その吸着能が高く、有効な使
用が図れる。The fuel tank 1 is normally in a normal temperature state,
There is no particular cooling, and the temperature is relatively high, for example, in summer when the temperature rises. The gas occluding material (crystal of the metal carboxylate) of the present invention has a high adsorptivity under such conditions, that is, even in a relatively high temperature range (about 25 to 60 ° C.), and is effectively used. Can be achieved.

【００２０】出口側の弁６を開放することにより、吸着
状態にあるガスをガス吸蔵材８から脱着させることがで
きる。脱着したガスをエンジン３側に送って燃焼させる
ことにより、走行駆動力を得ることができる。吸着式ガス貯蔵タンク 従来のガス貯蔵タンク内に、本発明のガス吸蔵材を入れ
ることにより、タンクの単位体積当たりのガス貯蔵量を
増大することができる。ＬＮＧ貯蔵装置 従来のＬＮＧタンクに、本発明の吸着材を備えた吸着式
充填タンクを接続し、これらのタンクの間に安全弁を設
けることにより、ＬＮＧタンクの圧力が所定圧力（例え
ば１〜９kg/cm2）以上になった場合に、安全弁を介して
蒸発ガス（ＢＯＧ）が吸着式充填タンクに流れ込み、Ｌ
ＮＧタンクの内圧を設定値以内に保つことができる。By opening the valve 6 on the outlet side, the gas in the adsorbed state can be desorbed from the gas occluding material 8. The driving force can be obtained by sending the desorbed gas to the engine 3 and burning it. Adsorption type gas storage tank By putting the gas occluding material of the present invention in a conventional gas storage tank, the gas storage amount per unit volume of the tank can be increased. LNG storage device A conventional LNG tank is connected to an adsorption-type filling tank equipped with the adsorbent of the present invention, and a safety valve is provided between these tanks so that the pressure of the LNG tank becomes a predetermined pressure (for example, 1 to 9 kg / l). cm 2 ) or more, the evaporative gas (BOG) flows into the adsorption type filling tank via the safety valve,
The internal pressure of the NG tank can be kept within a set value.

【００２１】[0021]

【発明の効果】本発明の有機金属錯体はガス吸蔵材とし
て有用である。本発明の錯体は製造が容易で安価である
ため、経済的なメリットが大きい。The organometallic complex of the present invention is useful as a gas storage material. Since the complex of the present invention is easy to produce and inexpensive, it has great economical advantages.

【００２２】本発明のガス吸蔵材は、メタンを主成分と
するガスの貯蔵において、体積当たりの吸着量が多く、
繰り返し特性が良い。本発明のガス吸蔵材によれば、常
温条件下の加圧状態でガス（特に、メタンを主成分とす
るガス）を貯蔵することができる。本発明のガスの貯蔵
方法によれば、メタンを主成分とするガスを、効率よく
吸蔵することができる。The gas occluding material of the present invention has a large amount of adsorption per volume in the storage of gas containing methane as a main component.
Good repetition characteristics. ADVANTAGE OF THE INVENTION According to the gas occlusion material of this invention, gas (especially gas containing methane as a main component) can be stored in a pressurized state under normal temperature conditions. According to the gas storage method of the present invention, a gas containing methane as a main component can be efficiently stored.

【００２３】本発明のガス貯蔵装置は、容積当たりのガ
ス貯蔵能が高い。本発明のガス貯蔵装置によれば、本発
明の吸蔵材の常温、加圧下におけるメタン吸着能を利用
して、比較的小さい容積中に有効にガスを貯蔵すること
ができる。The gas storage device of the present invention has a high gas storage capacity per volume. ADVANTAGE OF THE INVENTION According to the gas storage apparatus of this invention, a gas can be effectively stored in a comparatively small volume using the methane adsorption | suction ability of normal temperature and pressurization of the storage material of this invention.

【００２４】本発明のガス自動車は、容積当たりのガス
貯蔵能が高いガス貯蔵装置を備えているので、構造上使
用しやすい。The gas vehicle according to the present invention is provided with a gas storage device having a high gas storage capacity per volume, so that it is easy to use structurally.

【００２５】本発明のガス貯蔵タンクは、単位体積当た
りのガス貯蔵量が大きい。The gas storage tank of the present invention has a large gas storage amount per unit volume.

【００２６】本発明のＬＮＧ貯蔵装置は、ＬＮＧタンク
の温度が上昇した場合にも、ＬＮＧが吸着式充填タンク
に貯蔵され、ＬＮＧタンクの圧力を許容範囲内に収める
ことができる。In the LNG storage device of the present invention, even when the temperature of the LNG tank rises, LNG is stored in the adsorption type filling tank, and the pressure of the LNG tank can be kept within an allowable range.

【００２７】[0027]

【実施例】（１）有機金属錯体の合成実施例１ N-(4-ヒ゜コリル)-イソニコチンアミト゛(pcia, R=CH2)(420mg, 2mmol)
のエタノール溶液４０ｍｌをCd(NO3)2・4H2O (308mg、1m
mol）のメタノール溶液４０ｍｌに滴下し、５０℃に加
熱しながら１時間攪拌した。得られた白色沈殿を濾過し
て集め、減圧乾燥したところ、目的物である錯体が０．
５８ｇ得られた。得られた錯体の比表面積をＢＥＴ法に
より調べたところ、１６０ｍ2／ｇであり、細孔径は約
４Åであった。EXAMPLES (1) Synthesis of Organometallic Complex Example 1 N- (4-Picocholyl) -isonicotinamide (pcia, R = CH2) (420 mg, 2 mmol)
Of ethanol solution of Cd (NO 3 ) 2 .4H 2 O (308 mg, 1 m
mol) of methanol solution, and the mixture was stirred for 1 hour while heating to 50 ° C. The resulting white precipitate was collected by filtration and dried under reduced pressure to give a target compound of 0.1%.
58 g were obtained. When the specific surface area of the obtained complex was measured by the BET method, it was 160 m 2 / g and the pore diameter was about 4 °.

【００２８】得られた錯体を元素分析することにより、
組成式が｛Cd(pcia)2(NO3)2｝nで表されるものであるこ
とが判明した。By subjecting the obtained complex to elemental analysis,
It was found that the composition formula was represented by {Cd (pcia) 2 (NO 3 ) 2 ｝ n .

【００２９】この結晶についてＸ線測定を行い構造を解
析した結果、Ｃｄイオン配位子であるｐｃｉａが４配位
することにより生成した二次元格子構造を水素結合によ
り、三次元に積層した構造を形成している。この分子内
空間にガスを貯蔵することが可能となる。この構造を模
式的に示したのが図１及び図２である。実施例２ N-(4-ヒ゜コリル)-イソニコチンアミト゛(pcia, R=CH2)(210mg, 1mmol)
のメタノール溶液１０ｍｌをFe(SCN)2・6H2O (0.5mmol）
のメタノール溶液１０ｍｌに滴下し、５０℃に加熱しな
がら１時間攪拌し、その後１週間静置した。得られた赤
色沈殿を濾過して集め、減圧乾燥したところ、目的物で
ある錯体が０．２８ｇ得られた。得られた錯体の比表面
積をＢＥＴ法により調べたところ、２５０ｍ2／ｇであ
り、細孔径は約５Åであった。The crystal was subjected to X-ray measurement and the structure was analyzed. As a result, a two-dimensional lattice structure formed by the coordination of pcia, which is a Cd ion ligand, was three-dimensionally stacked by hydrogen bonding. Has formed. Gas can be stored in this intramolecular space. FIGS. 1 and 2 schematically show this structure. Example 2 N- (4-Picocolyl) -isonicotinamide (pcia, R = CH2) (210 mg, 1 mmol)
The methanol solution 10ml Fe (SCN) 2 · 6H 2 O (0.5mmol)
Was added dropwise to a methanol solution (10 ml), and the mixture was stirred for 1 hour while heating to 50 ° C., and then allowed to stand for one week. The obtained red precipitate was collected by filtration, and dried under reduced pressure to obtain 0.28 g of the target complex. When the specific surface area of the obtained complex was examined by the BET method, it was 250 m 2 / g, and the pore diameter was about 5 °.

【００３０】得られた錯体を元素分析することにより、
組成式が｛Fe(pcia)2(NCS)2｝nで表されるものであるこ
とが判明した。By subjecting the obtained complex to elemental analysis,
It has been found composition formula is represented by {Fe (pcia) 2 (NCS ) 2} n.

【００３１】この結晶についてＸ線測定を行い構造を解
析した結果、実施例１と同じ構造を形成していることが
分かった。 （２）ガス貯蔵能力の測定 実施例１及び２で得られた｛Cd(pcia)2(NO3)2｝n又は
｛Fe(pcia)2(NCS)2｝nなる組成の錯体についてメタンの
吸着能力を測定した。X-ray measurement of this crystal and analysis of the structure revealed that the same structure as in Example 1 was formed. (2) Measurement of gas storage capacity The complex of 組成 Cd (pcia) 2 (NO 3 ) 2 ｝ n or ｛Fe (pcia) 2 (NCS) 2 ｝ n obtained in Examples 1 and 2 was treated with methane. The adsorption capacity was measured.

【００３２】実験条件は、 使用ガス：メタン（純度９９．９９％） 温度：２５℃ 時間：平行に達するまで（数秒） にて行った。結果を図３に示す。図３に示されるよう
に、本発明の錯体はメタン吸着能を有することが明らか
になった。The experimental conditions were as follows: gas used: methane (purity: 99.99%) temperature: 25 ° C. time: until reaching parallel (several seconds). The results are shown in FIG. As shown in FIG. 3, the complex of the present invention was found to have methane adsorption ability.

【図面の簡単な説明】[Brief description of the drawings]

【図１】 本発明の錯体の三次元構造を模式的に示す概
略図である。FIG. 1 is a schematic diagram schematically showing a three-dimensional structure of a complex of the present invention.

【図２】 本発明の錯体の三次元構造を模式的に示す概
略図である。FIG. 2 is a schematic diagram schematically showing a three-dimensional structure of the complex of the present invention.

【図３】 実施例１の錯体のガス吸着能（吸着等温線）
を示すグラフである。FIG. 3 shows the gas adsorption capacity (adsorption isotherm) of the complex of Example 1.
FIG.

【図４】 ガス自動車の該略図を示す。FIG. 4 shows the schematic diagram of a gas vehicle.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 近藤 満 京都市左京区田中玄京町66 Ｆターム(参考） 3E072 AA03 AA10 DA05 EA10 4H048 AA01 AA02 AA03 AB90 AC90 VA00 VA20 VA30 VA32 VA56 VA68 VB10  ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Mitsuru Kondo 66 F-term (reference) 3F072 AA03 AA10 DA05 EA10 4H048 AA01 AA02 AA03 AB90 AC90 VA00 VA20 VA30 VA32 VA56 VA68 VB10

Claims (12)

【特許請求の範囲】[Claims] 【請求項１】２価の金属イオン、前記金属イオンに配位
可能な原子を有する２座配位可能なアミド結合を分子内
に有する有機配位子より構成される三次元構造を有する
有機金属錯体。An organic metal having a three-dimensional structure comprising a divalent metal ion and an organic ligand having in its molecule a bidentate amide bond having an atom capable of coordinating with the metal ion. Complex. 【請求項２】有機配位子が下記式（１） 【化１】 〔式中、ＲおよびＲ’は同一又は異なってアルキレン
基、アルケニレン基またはアリーレン基を示す。〕で表
される請求項１に記載の有機金属錯体。2. An organic ligand represented by the following formula (1): ## STR1 ## [Wherein, R and R ′ are the same or different and represent an alkylene group, an alkenylene group or an arylene group. The organometallic complex according to claim 1, which is represented by the formula: 【請求項３】化学式（２） ［Ｍ2+（Ligand)2］(NO3 -)2 （２） 〔式中、Ｍ2+は２価の金属イオンを示し、Ligandは２価
の金属イオンに２座配位可能なアミド結合を分子内に有
する前記有機配位子である。〕で表される請求項１に記
載の有機金属錯体。3. The chemical formula (2) [M 2+ (Ligand) 2 ] (NO 3 − ) 2 (2) wherein M 2+ represents a divalent metal ion, and Ligand represents a divalent metal ion. Is an organic ligand having an amide bond capable of bidentate in a molecule. The organometallic complex according to claim 1, which is represented by the formula: 【請求項４】Ｍが銅、カドミウム、コバルト、ニッケル
及び鉄からなる群から選ばれる請求項３に記載の有機金
属錯体。4. The organometallic complex according to claim 3, wherein M is selected from the group consisting of copper, cadmium, cobalt, nickel and iron. 【請求項５】２価の金属イオンの塩及び前記金属イオン
に２座配位可能なアミド結合を分子内に有する有機配位
子を溶媒中に所定比率で混合し、反応させることを特徴
とする三次元構造を有する有機金属錯体の製造方法。5. A mixture of a salt of a divalent metal ion and an organic ligand having an amide bond capable of bidentate coordination with the metal ion in a solvent at a predetermined ratio, and reacting the mixture. For producing an organometallic complex having a three-dimensional structure. 【請求項６】請求項１〜４のいずれかに記載の有機金属
錯体からなるガス吸蔵材。6. A gas occluding material comprising the organometallic complex according to claim 1. 【請求項７】ガスが出入口を備えた耐圧容器の内部に形
成された空間に、請求項５に記載のガス吸蔵材を収納し
たガス貯蔵装置。7. A gas storage device in which a gas storage material according to claim 5 is stored in a space formed inside a pressure vessel having a gas inlet / outlet. 【請求項８】請求項６に記載のガス吸蔵材に加圧条件下
でメタンを主成分とするガスを吸着して貯蔵するガス貯
蔵方法。8. A gas storage method according to claim 6, wherein a gas containing methane as a main component is adsorbed and stored on the gas occluding material under pressure. 【請求項９】貯蔵対象のガスが出入り可能な出入口(5
a)、(5b)と容器内のガスを加圧状態で保持可能な保持機
構（６）とを備え、且つ常温に温度維持可能な圧力容器
（４）を備えたガス貯蔵装置であって、前記圧力容器
（４）内に請求項６に記載のガス吸蔵材（８）を備え、
メタンを主成分とするガスを貯蔵対象とするガス貯蔵装
置。9. An entrance (5) through which a gas to be stored can enter and exit.
a) a gas storage device comprising (a) and (5b) and a holding mechanism (6) capable of holding a gas in a container in a pressurized state, and further comprising a pressure container (4) capable of maintaining a temperature at room temperature, The gas storage material (8) according to claim 6 is provided in the pressure vessel (4),
A gas storage device that stores gas containing methane as a main component. 【請求項１０】請求項９に記載のガス貯蔵装置（１）を
備え、ガス貯蔵装置（１）から供給されるメタンを主成
分とするガスから駆動力を得る内燃機関（３）を備えた
ガス自動車。10. An internal combustion engine (3) comprising the gas storage device (1) according to claim 9 and obtaining a driving force from a methane-based gas supplied from the gas storage device (1). Gas car. 【請求項１１】請求項６に記載のガス吸蔵材を含む吸着
式ガス貯蔵タンク。11. An adsorption type gas storage tank containing the gas occluding material according to claim 6. 【請求項１２】ＬＮＧタンクと請求項６に記載のガス吸
蔵材が充填された吸着式充填タンクを安全弁を介して連
設し、ＬＮＧタンクの圧力が所定値以上に高くなった場
合に、一定量の蒸発ガス（ＢＯＧ）を吸着式充填タンク
に充填されるようにしてなるＬＮＧ貯蔵装置。12. An LNG tank and an adsorption-type filling tank filled with the gas occluding material according to claim 6 are connected via a safety valve, and when the pressure of the LNG tank becomes higher than a predetermined value, the LNG tank becomes constant. An LNG storage device in which an amount of evaporative gas (BOG) is filled in an adsorption type filling tank.
JP10360174A 1998-12-18 1998-12-18 Gas storing organometallic complex, its production and gas storing device Pending JP2000178279A (en)

Priority Applications (1)

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JP2000178279A true JP2000178279A (en) 2000-06-27

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005336129A (en) * 2004-05-28 2005-12-08 Nippon Steel Corp Method for controlling characteristic of polymer complex
US7009066B2 (en) 2002-05-15 2006-03-07 Nippon Shokubai Co., Ltd. Porous coordinatively unsaturated metal complex
US9309264B2 (en) 2013-09-12 2016-04-12 Panasonic Intellectual Property Management Co., Ltd. Method for adsorbing carbon dioxide onto porous metal-organic framework materials, method for cooling porous metal-organic framework materials, method for obtaining aldehyde using porous metal-organic framework materials, and method for warming porous metal-organic framework materials

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7009066B2 (en) 2002-05-15 2006-03-07 Nippon Shokubai Co., Ltd. Porous coordinatively unsaturated metal complex
JP2005336129A (en) * 2004-05-28 2005-12-08 Nippon Steel Corp Method for controlling characteristic of polymer complex
US9309264B2 (en) 2013-09-12 2016-04-12 Panasonic Intellectual Property Management Co., Ltd. Method for adsorbing carbon dioxide onto porous metal-organic framework materials, method for cooling porous metal-organic framework materials, method for obtaining aldehyde using porous metal-organic framework materials, and method for warming porous metal-organic framework materials

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