JP2000210559A - Gas storable organic metal complex, manufacture thereof and gas storage device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To achieve high gas storage showing a high gas storing amount per volume as a low cost storing method for various kinds of gas by using a specific organic metal complex as an adsorbent, taking advantage of the best suitability of the complex for gas adsorption. SOLUTION: An adsorbent of a gaseous or a liquid organic compound excepting methane at normal temperatures and under normal pressure, is formed of an organic metal complex. In this case, the adsorbent using the organic metal complex selects at least one kind from the group of hydrogen, oxygen and nitrogen. In addition, an acetylene adsorbent is formed using the organic metal complex. Further, the adsorbent using the organic metal complex selects at least one kind from the group of arsine and phosphine. The organic metal complex is at least one kind selected from the group of a metal complex of dicarboxylic acid, an organic metal complex with a three dimensional structure, a halogenated metal complex of dicarboxylic acid, a metal complex of dicarboxylic acid comprising an organic ligand which can be coordinated at two seats in a specified metal and the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas adsorbent using an organometallic complex and an adsorption gas storage method using the same.

[0002]

2. Description of the Related Art As a method of storing a gas at a high density, there are generally known a method of cooling, compressing and liquefying a gas to a temperature lower than a critical temperature of the gas, and a method of storing as a compressed gas at normal temperature and high pressure. Have been.

However, the method of liquefied storage requires large-scale cooling and compression equipment, and thus the equipment cost is high. In addition, it is difficult to use it in a field requiring movement such as an automobile. On the other hand, the method of storing as a compressed gas has a lower energy density than a liquefied gas,
Even a compressed gas with a pressure of about kgf / cm ² ,
Its energy is only about one-third of the same volume of gasoline. In addition, since a high-pressure cylinder is used, a large-sized and heavy pressure vessel and pressure regulating valve are required.

As a method of storing gas at a relatively low pressure without requiring the above-mentioned large-scale equipment, a method of storing gas by adsorbing the gas under pressure into an adsorbent in a pressure vessel such as a cylinder has been proposed. I have. According to this method, the intermolecular distance is smaller in the pores of the adsorbent than in the gas phase bulk, so that the same amount of gas as the high pressure compressed gas can be stored even at a relatively low pressure. As a result, the pressure vessel and the pressure regulating valve can be reduced in weight.

[0005] For example, when storing methane gas, activated alumina, silica, zeolite and activated carbon have been evaluated as adsorbents to be filled into cylinders and the like, and it has been reported that activated carbon has the best storage capacity. (A. Golovoy, Compress. Nat. Gas, 36 (1983)).

[0006] However, even with the adsorption amount indicated above, the energy density is much lower than the energy density of liquefied gas or gasoline.

[0007]

An object of the present invention is to provide a gas storage technique which is inexpensive and has a high gas storage amount per volume as a method for storing various gases.

[0008]

Means for Solving the Problems The present inventor has conducted intensive studies in order to solve the above problems, and found that a specific organometallic complex is suitable as a gas adsorbent.
By using this complex as an adsorbent, a gas storage technology that is inexpensive and has a high gas storage amount per volume has been completed as various gas storage methods.

The present invention relates to the following items 1 to 8. Item 1. Adsorbent for gaseous or liquid organic compounds at normal temperature and normal pressure except for methane using an organometallic complex. Item 2. At least one adsorbent selected from the group consisting of hydrogen, oxygen and nitrogen using an organometallic complex. Item 3. Acetylene adsorbent using organometallic complex. Item 4. At least one adsorbent selected from the group consisting of arsine and phosphine using an organometallic complex. Item 5. Item 5. The adsorbent according to any one of Items 1 to 4, wherein the organometallic complex is at least one selected from the group consisting of the following complexes I to VII. Complex I. Metal complex of dicarboxylic acid consisting of dicarboxylic acid and at least one metal selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium and zinc; Complex II. A divalent metal ion, a bidentate organic ligand having an atom capable of coordinating to the metal ion, and SiF _{6
^{2-, GeF 6 2-, ZrF 6}} 2-, TiF 6 2-, SnF 6 2-, NbOF 6 2-, MoO 2 F
Organometallic complex having a three-dimensional structure composed of at least one selected from the group consisting of ₄ ^2-;. Complex III Formula _{(1) Ru 2 (OOC-} R 1 -COO) 2 · X (1) [Formula In the formula, R ¹ represents an alkylene group, alkenylene group, alkynylene group, or an optionally substituted arylene group. X is a halogen ion or BF ₄ ^- shows a. ] The dicarboxylic acid metal halide complex represented by these. Complex IV. Chemical formula (2)

[0010]

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[In the formula, R ² represents an alkylene group, alkenylene group, alkynylene group, or an arylene group which may have a substituent. And at least one metal selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium, and tungsten, and an organic coordination capable of bidentate coordination with the metal. Metal carboxylate complex; complex V. Chemical formula (3) HOOC—R ³ —COOH (3) wherein R ³ represents an alkylene group, alkenylene group, alkynylene group, or an arylene group which may have a substituent. And at least one metal selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium, zinc and tungsten, and an organic compound capable of bidentate coordination with the metal. A dicarboxylic acid metal complex comprising a ligand. Complex VI. Chemical formula (4) Cu ₂ (constituting a divalent metal ion, an organic ligand capable of coordinating bidentate having an atom capable of coordinating with the metal ion (Ligand) and 2,3-pyrazinedicarboxylic acid (pyzdc) Ligand) (pyzdc) ₂ An organometallic complex having a three-dimensional structure represented by (4): Complex VII. Divalent metal ion and chemical formula (5)

[0012]

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Wherein R ⁴ and R ⁵ are the same or different,
It represents an alkylene group, an alkenylene group, an alkynylene group, an optionally substituted arylene group or a single bond. However, R ⁴ and R ⁵ do not simultaneously form a single bond. 5. An organometallic complex comprising an organic ligand represented by the formula: Item 7. A gas storage device in which the adsorbent according to any one of Items 1 to 5 is stored in a space formed inside a pressure-resistant container provided with a gas inlet / outlet. Item 7. A gas, a vapor or a liquid compound having 2 or more carbon atoms under pressurized conditions as necessary for the gas storage device according to item 6,
A storage method characterized by adsorbing at least one selected from the group consisting of hydrogen, oxygen, nitrogen, arsine and phosphine. Item 8. Item 5 relates to a gas storage method and a gas storage device for adsorbing and storing acetylene on a gas adsorbent comprising an organometallic complex according to item 5.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. Is mentioned.

Examples of the haloalkyl group include those having 1 carbon atom such as trifluoromethyl, pentafluoroethyl, monochloromethyl, trichloromethyl and heptafluoropropyl.
To 4 haloalkyl groups.

As the alkylene group,-(CH ₂ ) _n-
And groups represented by (n = 1 to 6).

As the alkenylene group,-(CH ₂ ) _n1
—CH ＝ CH— (CH ₂ ) _n2 — (n1 + n2 = 0, 1, 2, or 3; n1 ≧ 0; n2 ≧ 0).

The alkynylene group includes-(CH ₂ ) _n3
—CH≡CH— (CH ₂ ) _n4 — (n1 + n2 = 0, 1, 2, or 3; n1 ≧ 0; n2 ≧ 0).

[0019] As the arylene group, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthylene, biphenylene _{(-C 6 H 4 -C 6 H} 4 -), triphenylene (-C ₆ H _{4 -C 6 H 4 -C 6 H 4} -), - C 6 H 4 -CH = CH-C 6 H 4 -, - C 6 H 4 -CON
_{HC 6 H 4 -, - C} 6 H 4 -OC 6 H 4 - , and the like.

Examples of the aryl group include a phenyl group and a naphthyl group. Examples of the substituent of the aryl group include an alkyl group and an alkoxy group (alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, propoxy and butoxy). , A halogen atom (F, Cl, Br, I) and the like.

Examples of the aralkyl group include benzyl, phenethyl and the like.

The organic ligand capable of bidentate coordination includes:
Pyrazine, 4,4'-bipyridyl, trans-1,2-
Bis (4-pyridyl) ethylene, 4,4'-azopyridine, 4,4'-bipyridylethane, 4,4'-bisbipyridylphenylene, N- (4-pyridyl) isonicotinamide and the like can be used. <Production of metal complex> Method for producing organometallic complex I By mixing a solution containing a metal salt with a dicarboxylic acid dissolved in an organic solvent, a dicarboxylic acid metal complex I is prepared.
Can be manufactured. The resulting mixture, for example,
After leaving for several hours to several days, the precipitated solid is filtered off with suction,
By drying at 120 ° C. for 5 hours, a crystal of a metal dicarboxylate (particularly, a crystal having a one-dimensional channel structure) can be produced.

The type of dicarboxylic acid used as a raw material is selected to control the pore size of the resulting dicarboxylic acid metal complex crystal, that is, to control the channel of the dicarboxylic acid metal complex crystal having a one-dimensional channel structure. The size can be adjusted. Dicarboxylic acids of general formulas (1) to (9), fumaric acid, trans-cyclohexanedicarboxylic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, stilbenedicarboxylic acid, transdicarboxylic acid, By using at least one selected from triphenyldicarboxylic acid, it is possible to produce a crystal of a metal dicarboxylate having a large specific surface area and a large amount of adsorption.

[0024]

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Easy to dissolve dicarboxylic acid and metal salt,
By using an organic solvent that hardly dissolves the dicarboxylic acid metal complex, the dicarboxylic acid and the metal salt (metal ion) can be efficiently reacted, and the crystals of the dicarboxylic acid metal complex can be efficiently collected. Examples of the organic solvent include alcohols such as methanol, ethanol, and propanol,
Benzene, toluene, acetonitrile, tetrahydrofuran, dimethylsulfoxide, dimethylformamide (DMF), hexane, acetone or a mixed solvent thereof can be used. Organic solvents that do not coordinate with the dicarboxylic acid metal complex (eg, methanol, ethanol, DM
By using F, alcohol or a mixed solvent thereof, generation of impurities (metal complex of organic solvent) can be prevented.

0.005 to 0.1 mol /
1, preferably a metal salt (metal ions: Cu ²⁺ , Mo ²⁺ , Cr ²⁺ , Rh ²⁺ , Pd) by using a dicarboxylic acid dissolved in a concentration of 0.02 to 0.08 mol / l.
²⁺ and W ²⁺ salts).

By using one or more metal salts selected from copper salts, molybdenum salts, chromium salts, rhodium salts, palladium salts and tungsten salts, the corresponding metal complexes of dicarboxylic acids can be produced. As the metal salt, organic acid salts such as formate and acetate, and inorganic acid salts such as sulfate, nitrate and carbonate can be used. In general, copper salts are inexpensive and easy to handle. Therefore, by using at least one copper salt selected from copper formate, copper acetate, copper sulfate, copper nitrate and copper carbonate as a metal salt, The acid copper complex can be easily and inexpensively mass-produced.

0.5 to 2 mol based on dicarboxylic acid
By using a solution containing an equal amount of a metal salt, a dicarboxylic acid and a metal ion can be efficiently reacted. By using a metal salt in an amount of 0.5 mol equivalent or more with respect to dicarboxylic acid, a metal complex of dicarboxylic acid can be produced in a high yield. By setting the use amount of the metal salt to 2 mol equivalent or less with respect to the dicarboxylic acid, a side reaction can be suppressed in relation to the coordination number of the metal (for example, copper coordinates two).

By adding a specific additive to the dicarboxylic acid solution, the crystal structure of the resulting dicarboxylic acid metal complex can be stabilized, and the gas adsorbing ability when used as a gas storage material can be substantially reduced. Can be controlled.
Organic acids can be used as additives. As the organic acid, formic acid, acetic acid, trifluoroacetic acid, and propionic acid (preferably formic acid and acetic acid) can be used.

The dicarboxylic acid metal complex (crystal) can be efficiently produced by dissolving the dicarboxylic acid in the organic solvent and adding the metal salt solution dropwise to the solution whose pH has been adjusted by adding the organic acid. . By adding 0.1 to 20% by weight, preferably 0.5 to 10% by weight of the organic acid to the dicarboxylic acid, the gas storage capacity of the obtained metal complex of dicarboxylic acid can be improved. If the amount of the organic acid is too small, the gas storage capacity of the obtained dicarboxylic acid metal complex does not increase, and if it is too large, the dicarboxylic acid metal complex is hardly generated.

As the additive, a compound that acts as a template for the crystal structure, that is, a compound that does not react with the dicarboxylic acid and can be taken into the crystal when the dicarboxylic acid metal complex crystal is formed and precipitated. Can be used. Since the size of the voids (pores) of the dicarboxylic acid metal complex crystal of the present invention is about 7 to 12 °, the compound having a molecular size of about 12 ° or less, particularly about 8 to 12 °, has a dicarboxylic acid metal complex crystal precipitated. In doing so, it can be incorporated into the crystal.

As the compound acting as a template, for example, a compound having a 6-membered ring, especially a benzene ring,
Specifically, aromatic compounds having a methyl group such as toluene, xylene, and mesitylene can be used. 1-100 cc, preferably 10-50 cc, of the compound acting as a template for the crystal structure is added to 1 g of dicarboxylic acid.
By using cc, the crystal structure of the resulting metal dicarboxylate complex can be stabilized.

By reacting a dicarboxylic acid with a metal salt (metal ion) at about -20 ° C. to 80 ° C., a dicarboxylic acid metal complex (crystal) can be produced. Preparation of organometallic complex II Preparation of organometallic complex II by mixing a solution of hexafluorosilicate metal salt obtained by reaction of ammonium hexafluorosilicate and metal salt with a solution of organic ligand capable of bidentate coordination can do. Specifically, the obtained mixed solution is allowed to stand, for example, for several hours to several days,
The precipitated solid is subjected to suction filtration and vacuum-dried at 100 ° C. for 5 hours to produce organometallic complex II as crystals.

Examples of the metal salt 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, cadmium, mercury, and lead. Sulfate, nitrate, perchlorate, tetrafluoroborate, hexafluorophosphate, halide, carbonate, formate and acetate of metal ions such as manganese can be used. By reacting ammonium hexafluorosilicate with these metal salts, a hexafluorosilicate metal salt can be obtained.

As the organic ligand, pyrazine, 4,
4'-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 4,4'-azopyridine, 4,4'-
Bipyridylethane, 4,4'-bisbipyridylphenylene, N- (4-pyridyl) isonicotinamide and the like can be used.

The concentration is 2 equivalents of hexafluorosilicate, and is 0.01 to 0.5 mol / L.

The reaction temperature of the above synthesis is about -20 to 100 ° C., and the reaction is carried out at ordinary temperature.

As the solvent for this reaction, 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. Method for producing organometallic complex III Dicarboxylic acid and Ru ₂ (CH ₃ COO) ₄ .X (X = C
1, BF ₄ , Br), a carboxylate complex III as a target gas adsorbent can be produced by mixing a solution containing one or more metal salts and a halide. Specifically, the obtained liquid mixture is allowed to stand, for example, for several hours to several days, the precipitate is collected by centrifugation, washed with methanol, and then dried in vacuum at 100 ° C. for 5 hours to obtain a three-dimensional organometallic complex III. Can be produced.

The dicarboxylic acid is preferably a saturated fatty acid such as succinic acid or adipic acid, an unsaturated fatty acid such as fumaric acid or acetylenedicarboxylic acid, cyclohexanedicarboxylic acid, terephthalic acid, biphenylamidedicarboxylic acid, stilbenedicarboxylic acid or trandicarboxylic acid. Acids and aryl dicarboxylic acids such as biphenylethylene dicarboxylic acid can be used. The concentration of dicarboxylic acid is
0.003 to 0.1 mol / L, preferably 0.005
０．０５0.05 mol / L.

As the metal salt, Ru ₂ (CH ₃ COO) ₄
· X ruthenium metal salt selected from _{(X = Cl, BF 4,} Br) can be used. The concentration of the metal salt is
1 equivalent of the dicarboxylic acid, 0.003 to 0.1
mol / L, preferably 0.005-0.05 mol /
L.

As the metal halide, lithium chloride, lithium bromide, sodium chloride and the like can be used.

The concentration is 0.5 to 0.6 equivalent to the metal complex formed from the dicarboxylic acid and the metal salt.
Preferably it is 0.5 equivalent.

As the solvent, an organic solvent which can easily dissolve the dicarboxylic acid, the metal salt and the metal halide and hardly dissolve the target carboxylic acid metal complex can be used. Specifically, alcohols such as methanol, ethanol, and propanol, and organic solvents such as benzene, toluene, acetonitrile, tetrahydrofuran, dimethylformamide, hexane, and acetone can be used alone or in combination.

The reaction temperature of the synthesis is about -20 to 100 ° C., and the reaction is carried out at ordinary temperature. Production method of organometallic complex IV By mixing an organic solution of a metal complex formed from a benzoic acid amide compound and a metal salt with a solution containing an organic ligand capable of bidentate coordination, it is an intended gas adsorbent Carboxylic acid complexes can be produced. Specifically, the obtained mixture is stirred, for example, for several hours to several days, the precipitate is collected by centrifugation, washed with methanol, and then washed at 100 ° C for 5 hours.
The crystals of organometallic complex IV can be produced by vacuum drying for a time.

The benzoic acid amide compound is represented by the following chemical formula (2)

[0046]

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[In the formula, R ² represents an alkyl group, a haloalkyl group, an aryl group which may have a substituent, or an aralkyl group. Preferred benzoic acid amide compounds include t-butylbenzoic acid amide and phenylbenzoic acid amide.

The concentration of the benzoic acid amide compound is 0.00
3 to 0.1 mol / L, preferably 0.005 to 0.0
5 mol / L.

As the organic ligand, pyrazine, 4,4
4'-bipyridyl, trans-1,2-bis (4-pyridyl) ethylene, 4,4'-azopyridine, 4,4'-
Bipyridylethane, 4,4'-bisbipyridylphenylene, N- (4-pyridyl) isonicotinamide and the like can be used.

The concentration of the organic ligand capable of bidentate coordination is 1 to 2 equivalents, preferably 1.3 to 1.1 equivalent to the metal complex formed from the benzoic acid amide compound and the metal salt.
7 equivalents.

As the solvent, an organic solvent which easily dissolves a metal complex formed from a benzoic acid amide compound and a metal salt and an organic ligand capable of bidentate coordination and hardly dissolves a target metal carboxylate complex is used. Can be used. Specifically, alcohols such as methanol, ethanol, and propanol, and organic solvents such as benzene, toluene, acetonitrile, tetrahydrofuran, dimethylformamide, hexane, and acetone can be used alone or in combination.

The reaction temperature of the above synthesis is about -20 to 100 ° C., and the reaction is carried out at ordinary temperature. Method for producing organometallic complex V By mixing an organic solution of a metal complex formed from a dicarboxylic acid and a metal salt with a solution containing an organic ligand capable of bidentate coordination, a carboxylic acid as a target gas adsorbent is mixed. Complexes can be produced. Alternatively, by mixing an organic solution of a metal complex formed from an organic ligand capable of bidentate coordination and a metal salt with a solution containing a dicarboxylic acid of the chemical formula (3), a carboxylic acid as a target gas adsorbent is mixed. Complexes can be produced. Specifically, the obtained mixed solution is stirred, for example, for several hours to several days, a precipitate is collected by centrifugation, washed with methanol, and then dried in vacuum at 100 ° C. for 5 hours to form crystals of the organometallic complex V. Can be manufactured.

The dicarboxylic acids include saturated fatty acids such as succinic acid and adipic acid, unsaturated fatty acids such as fumaric acid and acetylenedicarboxylic acid, cyclohexanedicarboxylic acid,
Aryl dicarboxylic acids such as terephthalic acid, biphenylamide dicarboxylic acid, stilbene dicarboxylic acid, transdicarboxylic acid, and biphenylethylene dicarboxylic acid can be used. The concentration of dicarboxylic acid is from 0.003 to
0.1 mol / L, preferably 0.005 to 0.05 m
ol / L.

As the metal salt, a metal salt selected from rhodium salts, copper salts, molybdenum salts, chromium salts, palladium salts, zinc salts and tungsten salts can be used. In addition, as these metal salts, organic acid salts such as formate and acetate, and inorganic acid salts such as sulfate, nitrate and carbonate can be used. The concentration of the metal salt is 1/2 equivalent of the dicarboxylic acid, and is 0.001 to 0.05 mol /.
L, preferably 0.003 to 0.03 mol / L.

The concentration of the organic ligand capable of bidentate coordination is 0.5 to 0.6 equivalent, preferably 0.5 equivalent, to the metal complex formed from the dicarboxylic acid and the metal salt. Quantity.

As the solvent, an organic solvent which easily dissolves the metal complex formed from the dicarboxylic acid and the metal salt and the organic ligand capable of bidentate coordination and hardly dissolves the target dicarboxylic acid metal complex is used. can do. Specifically, alcohols such as methanol, ethanol, and propanol, and organic solvents such as benzene, toluene, acetonitrile, tetrahydrofuran, dimethylformamide, hexane, and acetone can be used alone or in combination.

The reaction temperature of the above synthesis is about -20 to 100 ° C., and the reaction is carried out at ordinary temperature. Method for Producing Organometallic Complex VI The bidentate organic ligand constituting the metal complex of the present invention may be pyrazine, 4,4′-bipyridyl, trans-
1,2-bis (4-pyridyl) ethylene, 1,4-dicyanobenzene, 4,4′-dicyanobiphenyl, 1,2
-Dicyanoethylene, 1,4-bis (4-pyridyl) benzene, 4,4'-azopyridine, 4,4'-bipyridylethane, 4,4'-bisbipyridylphenylene, N-
(4-pyridyl) isonicotinamide and the like can be used.

Such a ligand has an atom capable of coordinating with a metal ion, preferably a nitrogen atom, at both ends of the molecule and has rigidity in the molecule. The nitrogen atoms present at symmetrical positions coordinate to different metal ions, and a repeating structure of the (metal ion-ligand) is formed in the crystal lattice of the complex. It is considered that a layered structure capable of storing gas is formed by forming the stacked structure. Since the distance between the atoms coordinated to the metal in the ligand, here the nitrogen atom, is determined by this ligand, the choice of the ligand can change the size of the molecule to be adsorbed, In addition, it is possible to select a gas component that can be stored.
In addition, it may vary depending on the anion of the metal salt as the raw material compound.

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;
Metal ions such as copper, zinc, cadmium, mercury, lead and manganese can be used, and sulfates, nitrates, perchlorates, tetrafluoroborates, hexafluorophosphates, halide salts of these metal ions, Carbonates, formates, and acetates can be used as raw materials for the metal ions.
As the metal ions, copper ions are preferable, and as the metal salts, inorganic salts such as copper sulfate, copper nitrate, and copper carbonate, and organic salts such as copper formate and copper acetate can be preferably used.

The metal complex is obtained by mixing and reacting a solution of a metal salt, a solution of an organic ligand, and a solution of 2,3-pyrazinedicarboxylic acid to form a complex. The mixture is mixed so that the ratio becomes a predetermined ratio, uniformly stirred, and then reacted under predetermined conditions to generate a complex crystal. The reaction conditions vary depending on the combination of the metal ion and the ligand.For example, the obtained mixture is stirred for several hours to several days, for example, and the precipitate is collected by centrifugation.
After washing with methanol and vacuum drying at 100 ° C. for 5 hours, crystals of organometallic complex VI can be produced. The reaction temperature is about −20 to 100 ° C., preferably 10
Reacts at about 60 ° C.

Examples of the solvent for this reaction include water, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, alcohols such as methanol and ethanol, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, benzene, toluene, hexane, and the like. Organic solvents such as esters such as ethyl acetate and butyl acetate can be used alone or in combination. Production method of organometallic complex VII Chemical formula (5)

[0062]

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Wherein R ⁴ and R ⁵ are as defined above. By mixing a solution of an organic ligand having an amide bond capable of bidentate coordination in a molecule thereof and a solution of a metal salt, an organometallic complex VII can be produced. Specifically, the obtained mixed solution is, for example, several hours to
The mixture is allowed to stand for several days, and the precipitated solid is suction-filtered and vacuum-dried at 100 ° C. for 5 hours, whereby the organometallic complex VII can be produced as crystals.

Examples of the metal salt 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, cadmium, mercury, and lead. Sulfate, nitrate, perchlorate, tetrafluoroborate, hexafluorophosphate, halide, carbonate, formate and acetate of metal ions such as manganese can be used. By reacting this metal salt with an organic ligand capable of bidentate coordination, organometallic complex VII can be obtained.

The concentration of the organic ligand is 2 molar equivalents of the metal salt, and is 0.01 to 0.5 mol / L.

The reaction temperature of the above synthesis is about -20 to 100 ° C., and the reaction is carried out at ordinary temperature.

Examples of the solvent for this reaction include water, alcohols such as acetone, methanol, and ethanol, acetonitrile, tetrahydrofuran, dioxane, dimethylformamide, dimethylacetamide, benzene, toluene, and the like.
Organic solvents such as hexane can be used alone or in combination. Gas adsorbent Since the organometallic complex can adsorb gas, it can be used as a gas occluding material. Since the pore diameter of the crystal of the organometallic complex is constant in structure, it becomes difficult to desorb while adsorbing gas components other than the specific gas,
Problems such as repeated performance degradation are unlikely to occur.

By molding (particularly, compression molding) the crystal of the organometallic complex, a gas occlusion 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.

The storable gas components include organic compounds which are gaseous or liquid at normal temperature and pressure except for methane, such as acetylene, ethylene, ethane, propylene, propyne, propane, 1-butene, 2-butene and 1-butyne. , 2-butyne, pentene, pentane, cyclopentane, cyclopentene, methanol, ethanol, butanol, dimethyl ether; hydrogen, oxygen, nitrogen, arsine, phosphine and the like, and preferably a gas having 2 to 4 carbon atoms (acetylene, ethylene, Ethane, propylene, propyne, propane, 1-butene, 2-butene, 1-butyne, 2-butyne), and especially acetylene. Gas Storage Method The gas occluding material of the present invention can be adsorbed and stored by contacting a gas to be stored under a pressurized condition. This storage is at normal temperature or higher (for example, 5 ° C or higher)
But it is possible. 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. Gas storage device In the gas storage device of the present invention, since the gas occlusion material of the present invention is provided in the pressure vessel, the gas is adsorbed by pressurizing the gas from the inlet / outlet into the pressure vessel in which the occlusion material is stored. It can be stored in a state of being adsorbed on the 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.

[0070]

As described above, the gas adsorbent of the present invention is inexpensive as a gas storage method, and therefore has a great economical advantage and an improved gas storage performance per volume.

[0071]

EXAMPLES (1) Synthesis of organometallic complex Production example 1 In a mixed solvent of 100 cc of methanol and 14 cc of formic acid,
1,4-trans-cyclohexanedicarboxylic acid 2.5
Dissolve 3 g. A solution prepared by dissolving 3.3 g of copper formate in 100 cc of methanol was added dropwise to the obtained 1,4-trans-cyclohexanedicarboxylic acid solution with stirring, and the resulting solution was allowed to stand at room temperature for several days. The obtained blue-green precipitate was collected by filtration, and dried under reduced pressure to obtain 2.68 g of the target complex.

When the specific surface area of the obtained complex was measured by the BET method, it was 480 m ² / g, and the pore diameter was about 4.
It was 7Å. Production Example 2 1.20 g of fumaric acid is dissolved in a mixed solvent of 100 cc of methanol and 12 cc of formic acid. To the obtained fumaric acid solution, 3.38 g of copper formate was added with stirring to 100 cc of methanol.
Was added dropwise, and the resulting solution was allowed to stand at room temperature for several days. The resulting blue precipitate was collected by filtration and dried under reduced pressure to give 1.37 g of the desired complex.

When the specific surface area of the obtained complex was measured by the BET method, it was 450 m ² / g, and the pore size was about 5.
It was 4Å. Production Example 3 In a mixed solvent of 90 cc of DMF and 0.5 cc of formic acid, 0.25 g of biphenyldicarboxylic acid was dissolved. A solution prepared by dissolving 0.5 g of copper formate in 25 cc of methanol was added dropwise to the obtained biphenyldicarboxylic acid solution with stirring, and the resulting solution was allowed to stand at room temperature for several days. The obtained blue-green precipitate was collected by filtration and dried under reduced pressure to obtain 0.17 g of the target complex.

When the specific surface area of the obtained complex was measured by the BET method, it was 1200 m ² / g, and the pore diameter was about 7.8 °. Production Example 4 copper perchlorate hexahydrate _{(Cu (ClO 4) 2 ·} 6H 2 0,378mg, 1.02mm
ol) and ammonium hexafluorosilicate ((NH ₄ ) ₂ Si
F _6, 200mg, 1.12mmol) was dissolved in water 20ml. To this, an aqueous solution of 4,4′-bipyridyl (349 mg, 2.24 mmol) (20 m
l) was added slowly. The resulting blue precipitate was collected by filtration and dried under reduced pressure to give 0.53 g of the desired complex. When the specific surface area of the obtained complex was examined by the BET method, it was 1193 m ² / g, and the pore diameter was about 7.8.
Was Å. Production Example 5 <Synthesis of Cu (OOCC = CCOO) ₂ .pyridine> C
u (CH ₃ COO) ₂ .H ₂ O (199 mg), 116 mg of fumaric acid, 80 mg of pyridine and 1 cc of formic acid
The mixture was placed in a ml eggplant flask, dissolved in about 20 ml of methanol, stirred at room temperature, and allowed to stand for 4 days. Thereafter, the precipitate is filtered off with suction, washed three times with methanol and reduced in vacuo to 100
The mixture was dried by heating at ℃ for about 2 hours to obtain 118 mg of the desired product. Production Example 6 <Synthesis of Ru ₂ (OOCC = CCOO) ₂ .Cl> Ru ₂
(CH ₃ COO) ₄ .Cl (477 mg), fumaric acid 23
2 mg and lithium chloride 42 mg were put in a 200 ml eggplant flask and dissolved in about 100 ml of methanol.
The mixture was stirred at room temperature and allowed to stand for 4 days. Thereafter, the precipitate was filtered by suction, washed with methanol three times, and dried by heating at 100 ° C. under vacuum for about 2 hours to obtain 532 mg of the desired product. Production Example 7 <Synthesis of Rh ₂ (p-OOCC ₆ H ₄ NHCO ^t Bu) ₄ .pyrazine> Rh ₂ (CH ₃ COO) ₄ (100 mg) and p
- ^t BuCONHC ₆ H ₄ COOH and (400 mg) 10
The mixture was placed in a 0 ml eggplant flask, dissolved in about 10 ml of diglyme, stirred at 200 ° C. for 2 hours, and then the solvent was distilled off. About 5 ml of diglyme was added again, and the mixture was stirred at 200 ° C. for 30 minutes, and then the solvent was distilled off. Methanol was added to the obtained green crude crystals, and the crystals were collected by a centrifuge. Further, it is washed with methanol three times, dried by heating at 100 ° C. under vacuum for about 2 hours, and Rh ₂ (p-OOCC ₆ H ₄ NHCO ^t Bu) ₄
168 mg was obtained.

Rh ₂ (p-OOCC ₆ H ₄ NHCO ^t Bu)
₄ (100 mg) was placed in a 50 ml eggplant flask and dissolved in about 20 ml of methanol. To this solution, 11 mg of pyrazine was added and stirred for one day. Thereafter, the precipitate was collected by a centrifugal separator, washed three times with methanol, and vacuumed at 100 ° C. for about 2 hours.
After heating and drying for an hour, 93 mg of the target gas adsorbent was obtained as ocher powder crystals. Production Example 8 N- (4-picolyl) -isonicotinamide (pci
a, R = CH ₂ ) (42 mg, 2 mmol) in ethanol solution 40
of methanol was added dropwise to 40 ml of a methanol solution of Cd (NO ₃ ) ₂ .4H ₂ O (308 mg, 1 mmol).
Stirred for hours. The obtained white precipitate was collected by filtration and dried under reduced pressure to obtain 0.58 g of the target complex.

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 °.

Elemental analysis of this complex revealed that the composition formula was represented by {Cd (pcia) ₂ (NO ₃ ) ₂ } n. (2) Measurement of gas storage capacity The acetylene adsorption capacity of the complexes obtained in Examples 1 to 8 was measured.

The experimental conditions were as follows: gas used: acetylene (purity: 99.99%) temperature: 25 ° C. time: until reaching parallel (several seconds). The results are shown in FIG. As shown in FIG. 1, the complex of the present invention was found to have acetylene adsorption ability.

[Brief description of the drawings]

FIG. 1 is a graph showing the gas adsorption capacity (adsorption isotherm) of the complex of Example 1.

Continuation of the front page F term (reference) 3E072 EA10 GA30 4G066 AA32B AB07B AB24B BA23 BA26 CA21 CA27 CA37 CA38 CA51 FA05

Claims (8)

[Claims] 1. An adsorbent for a gaseous or liquid organic compound at normal temperature and normal pressure except for methane using an organometallic complex. 2. At least one adsorbent selected from the group consisting of hydrogen, oxygen and nitrogen using an organometallic complex. 3. An acetylene adsorbent using an organometallic complex. 4. At least one adsorbent selected from the group consisting of arsine and phosphine using an organometallic complex. 5. The organic metal complex is at least one selected from the group consisting of the following complexes I to VII.
4. The adsorbent according to any one of 4. Complex I. Metal complex of dicarboxylic acid consisting of dicarboxylic acid and at least one metal selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium and zinc; Complex II. A divalent metal ion, a bidentate organic ligand having an atom capable of coordinating to the metal ion, and SiF _{6
^{2-, GeF 6 2-, ZrF 6}} 2-, TiF 6 2-, SnF 6 2-, NbOF 6 2-, MoO 2 F
Organometallic complex having a three-dimensional structure composed of at least one selected from the group consisting of ₄ ^2-;. Complex III Formula _{(1) Ru 2 (OOC-} R 1 -COO) 2 · X (1) [Formula In the formula, R ¹ represents an alkylene group, alkenylene group, alkynylene group, or an optionally substituted arylene group. X is a halogen ion or BF ₄ ^- shows a. ] The dicarboxylic acid metal halide complex represented by these. Complex IV. Chemical formula (2) [In the formula, R ² represents an alkylene group, alkenylene group, alkynylene group, or an arylene group which may have a substituent. And at least one selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium and tungsten
Metal carboxylate complex comprising a metal of a kind and an organic ligand capable of bidentate coordination with the metal; complex V. Chemical formula (3) HOOC—R ³ —COOH (3) wherein R ³ represents an alkylene group, alkenylene group, alkynylene group, or an arylene group which may have a substituent. And at least one metal selected from the group consisting of copper, chromium, molybdenum, rhodium, palladium, zinc and tungsten, and an organic compound capable of bidentate coordination with the metal. A dicarboxylic acid metal complex comprising a ligand. Complex VI. Divalent metal ions, consisting of 2 Zahaii acceptable organic ligands with coordinating an atom to the metal ion (Ligand) and 2,3-pyrazine dicarboxylic acid (pyzdc) Chemical formula (4) Cu ₂ ( Ligand) (pyzdc) ₂ An organometallic complex having a three-dimensional structure represented by (4): Complex VII. Divalent metal ion and chemical formula (5) [In the formula, R ⁴ and R ⁵ are the same or different and each represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group which may have a substituent, or a single bond. Where R
⁴ and R ⁵ do not simultaneously form a single bond. Organometallic complex comprising an organic ligand represented by the formula: 6. A gas storage device in which the adsorbent according to claim 1 is stored in a space formed inside a pressure vessel having a gas inlet / outlet. 7. The gas storage device according to claim 6, wherein the gas storage device according to claim 6 is a gas, vapor or liquid compound having 2 or more carbon atoms, hydrogen, oxygen, nitrogen, arsine and phosphine under a pressurized condition. A storage method comprising adsorbing at least one selected member. 8. A gas storage method and apparatus for adsorbing and storing acetylene on a gas adsorbent comprising the organometallic complex according to claim 5.