JP2013111563A - Composition and ammonia production method using the same - Google Patents

Composition and ammonia production method using the same Download PDF

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JP2013111563A
JP2013111563A JP2011262903A JP2011262903A JP2013111563A JP 2013111563 A JP2013111563 A JP 2013111563A JP 2011262903 A JP2011262903 A JP 2011262903A JP 2011262903 A JP2011262903 A JP 2011262903A JP 2013111563 A JP2013111563 A JP 2013111563A
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composition
metal
ammonia
component
ruthenium
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Inventor
Susumu Kitagawa
進 北川
Hiroshi Kitagawa
宏 北川
Masakazu Higuchi
雅一 樋口
Katsutoshi Nagaoka
勝俊 永岡
Manami Kono
まなみ 河野
Takashi Kajiwara
隆史 梶原
Hideyuki Higashimura
秀之 東村
Yoshiko Mitsuya
由子 三津家
Kazuo Nagashima
和郎 永島
Daisuke Watabe
大輔 渡部
Shinji Oshima
伸司 大島
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Sumitomo Chemical Co Ltd
住友化学株式会社
Shoei Chem Ind Co
昭栄化学工業株式会社
Jx Nippon Oil & Energy Corp
Jx日鉱日石エネルギー株式会社
Kyoto Univ
国立大学法人京都大学
Oita Univ
国立大学法人 大分大学
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Priority to JP2011262903A priority Critical patent/JP2013111563A/en
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

PROBLEM TO BE SOLVED: To provide a composition which is excellent in stability, and which is obtained by compounding a specific metal atom and a porous metal complex, and an ammonia production method using the composition.SOLUTION: The composition is provided which is obtained by compounding the following (1) and (2), and the ammonia production method is provided for producing ammonia by causing nitrogen and hydrogen to react with each other using the composition as a catalyst. (1) At least one metal selected from a group comprising scandium, titanium, vanadium, chromium, manganese, cobalt, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium and iridium, alloy including the metal or a compound including the metal. (2) A porous metal complex which does not cause structural collapse at 200°C in the presence of ammonia of 1 atm.

Description

  The present invention relates to a composition comprising a metal and a porous metal complex, and an ammonia production method using the composition.

In recent years, porous metal complexes have attracted attention as new porous materials. The porous metal complex has a structure in which a pore structure is formed by accumulating organometallic complex skeletons. According to the porous metal complex, the micropores can be designed and controlled more precisely as compared with porous materials such as zeolite and activated carbon.
On the other hand, transition metals are widely used industrially as catalysts. For example, in recent years, it is known that ruthenium functions effectively as an ammonia synthesis catalyst (Non-Patent Document 1).

There are few examples where the above transition metal is supported on a porous metal complex. For example, in Non-Patent Document 2, ruthenium is MOF-5 ([Zn 4 O (bdc) 3 ]; bdc = 1,4-benzenedicarboxylate). The catalyst supported on the catalyst (hereinafter sometimes referred to as Ru / MOF-5) has hydrogen adsorption properties, has CO adsorption properties, can oxidize benzyl alcohol to benzaldehyde in the presence of oxygen, It describes that benzene can be reduced to cyclohexane in the presence.

Kenichi Akika, "Catalyst", 2003, Vol. 45, No. 1, p17-19 Schroder et al., "Journal of American Chemical Society", 2008, 130, p. 6119-6130 Low et al., "Journal of American Chemical Society", 2009, 131, p. 15834-15842

  However, as for MOF-5 used in Non-Patent Document 2, Non-Patent Document 3 describes that it decomposes at 1 mol% water vapor at 40 ° C. As described above, MOF-5 is susceptible to hydrolysis and has low heat resistance, so that the application range as a catalyst is limited. In particular, since ammonia has higher nucleophilicity than water and MOF-5 is more easily decomposed, application to ammonia synthesis and ammonia decomposition was difficult.

  This invention is made | formed in view of the said subject, Comprising: The composition which mix | blended the specific metal atom and porous metal complex excellent in stability, and the ammonia manufacturing method using this composition are provided. This is the issue.

The present invention provides the following compositions [1] to [3] and an ammonia production method [4].
[1] A composition comprising the following (1) and (2).
(1) selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, cobalt, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium and iridium At least one metal, an alloy containing the metal, or a compound containing the metal.
(2) A porous metal complex that does not cause structural collapse at 200 ° C. in the presence of 1 atm of ammonia.
[2] (1) includes ruthenium, ruthenium-containing alloy, ruthenium-containing compound, rhodium, rhodium-containing alloy, rhodium-containing compound, osmium, osmium-containing alloy, osmium-containing compound, iridium, and iridium. The composition according to [1], which is at least one selected from the group consisting of an alloy and a compound containing iridium.
[3] The above (2) is a porous metal complex having at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel, [1] or [2 ] The composition of description.
[4] A method for producing ammonia by reacting nitrogen and hydrogen using the composition according to any one of [1] to [3] as a catalyst.

ADVANTAGE OF THE INVENTION According to this invention, the composition which mix | blended the specific metal atom and porous metal complex excellent in stability can be provided. Since the composition is excellent in chemical stability and thermal stability, it becomes possible to produce, adsorb and separate basic gases such as ammonia, and the application range is expanded.
Moreover, ammonia can be manufactured satisfactorily by using the composition of the present invention.

It is a schematic diagram which shows the ammonia gas tolerance evaluation apparatus used in the Example. It is an XRD spectrum of Cu 2 (bpdc) 2 (bpy). It is an XRD spectrum of Zn 2 (bpdc) 2 (bpy). It is an XRD spectrum of HKUST-1. It is a XRD spectrum of MOF-5. It is a XRD spectrum of MG (HCOO) 2 . It is a XRD spectrum of MIL-68 (In). It is an XRD spectrum of MIL-125. It is a XRD spectrum of UiO-66. It is an XRD spectrum of MIL-101 (Cr). It is a XRD spectrum of MOF-74 (Mg). It is a XRD spectrum of MOF-76 (Y). It is a XRD spectrum of Al-BTB. It is an XRD spectrum of ZIF-8. It is a schematic diagram which shows the ammonia synthesis reaction apparatus used in the Example.

[Composition]
The composition which is the first aspect of the present invention comprises:
(1) selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, cobalt, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium and iridium At least one metal, an alloy containing the metal or a compound containing the metal, and
(2) A porous metal complex that does not cause structural collapse at 200 ° C. in the presence of 1 atm of ammonia is blended.
In the composition of the present invention, the porous metal complex to be blended as the component (2) has a regular pore structure, so that gas can be taken into the pores at a high concentration. Therefore, for example, since the reaction rate of the catalytic reaction that proceeds on the porous metal complex can be increased, the entire composition can be used as a good catalyst. The catalyst can be applied to a reduction reaction by storing hydrogen.

The composition of the present invention can also be used as a gas storage material.
The porous metal complex has an ordered pore structure. By the presence of the metal component derived from component (1), gas adsorption ability that cannot be achieved by the porous metal complex alone can be exhibited. For example, the metal component of component (1) can be used to adsorb impurities in the gas, store the gas, and release the gas with increased purity.
Examples of the gas that can be stored by the composition of the present invention include hydrogen, methane, carbon monoxide, carbon dioxide, and the like. By appropriately selecting the components (1) and (2) according to the target gas, it can be used favorably as a gas storage material.

  Hereinafter, each component of the composition of this invention is demonstrated in order. Hereinafter, the blending components are referred to as “component (1)” and “component (2)”, respectively.

(1) Metal, an alloy containing the metal, or a compound containing the metal In the composition of the present invention, the component (1) can function as a catalyst in ammonia production.
As the metal of component (1), scandium, titanium, vanadium, chromium, manganese, cobalt, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium and iridium At least one selected from the metal element group consisting of may be used in combination of two or more. The metal to be used can be appropriately selected according to the applied catalyst.
Among them, at least one selected from the group consisting of ruthenium, rhodium, osmium, and iridium is preferable because the ionization tendency is small and the ionization is difficult.
Since hydrogen is easily added and application as a hydrogen storage material can be expected, at least one selected from the group consisting of ruthenium and rhodium is more preferable,
Ruthenium is more preferable because it can be applied to high-temperature reactions such as ammonia synthesis and ammonia decomposition reaction and to ring-opening metathesis reactions.

As an alloy containing the metal of component (1), two types selected from the metal element group described above may be a eutectic or a solid solution, and one or two types selected from the metal element group described above. The above and metal elements other than the above may be eutectic or solid solutions.
Preferred metal elements are the same as those mentioned as preferred metals in the description of the metal.
The metal element other than the above is not particularly limited as long as it can form an alloy with the above metal element. However, since it has ammonia synthesis reactivity and can improve the catalytic ability, iron, molybdenum and nickel. At least one selected from the group consisting of: is preferred, and iron is more preferred because it is industrially used for ammonia synthesis.

As a compound containing the metal of a component (1), the compound which consists of a metal element mentioned above and a ligand is mentioned.
Preferred metal elements are the same as those mentioned as preferred metals in the description of the metal.
The ligand is not particularly limited, and may be a neutral ligand or an ionic ligand.
Specific examples of the compound containing a metal include ruthenium chloride, ruthenium acetylacetonate, potassium ruthenium cyanate, sodium ruthenate, potassium ruthenate, ruthenium oxide, dodecacarbonyl triruthenium, and ruthenium nitrate.

As the component (1), only one of the metal, the alloy containing the metal, and the compound containing the metal may be used, or two or more kinds may be used in combination.
When the component (1) is an alloy containing the metal or a compound containing the metal, the content of the metal in the alloy or the compound is preferably 1% by mass to 99% by mass, and ensures reactivity. Since it is easy to do, it is more preferable that it is 50 mass%-95 mass%.

The blending ratio of the component (1) in the composition is not particularly limited as long as it is a ratio that can exhibit good catalytic ability, but is preferably 1 to 99% by mass, and 3 to 97% by mass. More preferably, it is more preferably 5 to 95% by mass.
Moreover, it is preferable that the compounding ratio of the metal component of the component (1) in a composition is 0.001-0.15 mass% in conversion of a metal, and it is more preferable that it is 0.010-0.10 mass%. preferable. By setting it to 0.001% by mass or more, good catalytic activity can be obtained. Moreover, it can balance a catalyst activity and cost by setting it as 0.15 mass% or less. Furthermore, by setting it as 0.15 mass% or less, the functional inhibition of the component (2) resulting from the excessive component (1) blocking the pores of the component (2) described later does not occur.

(2) Porous metal complex that does not cause structural collapse at 200 ° C. in the presence of 1 atm of ammonia In the composition of the present invention, since component (2) has a porous structure, Gas can be taken in. Therefore, the component (2) not only functions as a gas storage material, but can improve the catalyst efficiency by the component (1) blended together.

In the present invention, the porous metal complex means “no structural collapse at 200 ° C. in the presence of 1 atm ammonia” means that the porous metal complex is heated to 200 ° C. in the presence of 1 atm ammonia. Even in this case, it means that the porous metal complex does not undergo structural collapse and can maintain the same structure as in the case of atmospheric conditions and normal temperature (18 to 25 ° C.).
Whether or not an equivalent structure can be maintained is determined by, for example, using a porous metal complex after heating to 200 ° C. in the presence of 1 atm of ammonia as a powder, and the structure (crystallinity, phase structure, etc.) by XRD (X-ray diffraction). ) And the result of analyzing the structure of the porous metal complex under atmospheric conditions and room temperature in the same manner can be confirmed.
Since the component (2) has the thermal stability and chemical stability as described above, the composition of the present invention can be used under high temperature conditions and in the presence of a nucleophilic reaction with a basic compound. For example, it can be used for ammonia production.
The porous metal complex is not particularly limited, and those usually used as a functional material such as a carrier can be appropriately selected. By using a porous metal complex as the component (2), the gas taken into the porous metal complex can improve the catalyst efficiency of the component (1).

  Examples of the porous metal complex include Reference 1 (Low et al., “Journal of American Chemical Society”, 2009, 131, p.15834-15842) and Reference 2 (Schroder et al., “Journal of American Chemical Chemistry,” 2008, No. 130, p.6119-6130), those which do not cause structural collapse at 200 ° C. in the presence of 1 atm of ammonia can be used.

As the porous metal complex of the present invention, one having at least one metal element selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel as a central atom is preferable. In the case of a porous metal complex having these metal elements as central atoms, a good porous structure is formed by coordination bonds and ionic bonds by having two or more sites where ligands can coordinate. be able to.
Further, the ligand constituting the porous metal complex is not particularly limited as long as the thermal stability and water vapor stability of the porous metal complex can be ensured. For example, benzene tricarboxylate anion, Examples thereof include benzene dicarboxylate anion, dioxide benzene dicarboxylate anion, methyl imidazolate anion, formate anion, imidazolate-2-carboxaldehyde anion and the like.

Among these, as component (2), ZIF-8, Al-PhBTB, Al-BTB, MIL-53 (Al), DUT-5, MOF-76 (Yb), MOF-76 (Y), MOF-76 ( Tb), MOF-76 (Co), MOF-74 (Co), MOF-74 (Zn), MOF-74 (Mg), MIL-101 (Cr), MIL-103 (Tb), UiO-67, UiO -66, UiO-66-1,4-Naph, MIL-125, MIL-68 (Ga) and Al-bpdc are preferred;
Since structural collapse does not occur even at 300 ° C., ZIF-8, Al-PhBTB, Al-BTB, MIL-53 (Al), MOF-76 (Yb), MOF-76 (Y), MOF-76 (Tb ), MOF-76 (Co), MOF-74 (Co), MOF-74 (Zn), MOF-74 (Mg), MIL-101 (Cr) and Al-bpdc are more preferred;
Since no structural collapse occurs even at 350 ° C., ZIF-8, Al-BTB, MIL-53 (Al), MOF-76 (Yb), MOF-76 (Y), or MOF-74 (Mg) and MIL -101 (Cr) is more preferable.

The abbreviations have the following meanings.
ZIF-8 = Zn (min) 2 .
min = methyl-imidazolate.
Al-PhBTB = Al (PhBTB).
PhBTB = benzo-1,3,5-tris (biphenylcarboxylate).
Al-BTB = Al (btb).
btb = benzene-1,3,5-tris (phenylcarboxylate).
MIL-53 (Al) = Al (OH) (bdc).
bdc = benzen-1,4-dicboxylate.
DUT-5 = Al (OH) (bpdc).
bpdc = biphenyl-4,4′-dicboxylate.
MOF-76 (M) = M (btc); M = Yb, Y, Tb or Co.
btc = benzene-1,3,5-triscarboxylate.
MOF-74 (M) = M 2 (dobdc); M = Co, Zn or Mg.
dodbc = 2,5-dioxido-benzene-1,4-dicboxylate.
MIL-101 (Cr) = Cr 3 O (OH) (bdc) 3.
MIL-103 (Tb) = Tb (btb).
UiO-67 = Zr 6 O 4 (OH) 4 (bpdc) 6.
UiO-66 = Zr 6 O 4 (OH) 4 (bdc) 6.
UiO-66-1,4-Naph = Zr 6 O 4 (OH) 4 (ndc) 6.
ndc = naphthalene-1,4-dicboxylate.
MIL-125 = Ti 8 O 8 (OH) 4 (bdc) 6 .
MIL-68 (Ga) = Ga (OH) (bdc).
Al-bpdc = Al (OH) (bpdc).
bpy = 4,4′-bipyridine.

  The blending ratio of component (2) in the composition is preferably 0.10 to 10000% by mass, more preferably 1.0 to 1000% by mass, based on the metal equivalent of component (1). -500 mass% is further more preferable.

  The composition of the present invention may contain other components other than components (1) and (2). Other components are not particularly limited as long as the effects of the present invention are not impaired.

  In the present invention, the method of preparing the composition by blending the components (1) and (2) is not particularly limited, but the components (1) and (2) are mixed by some method, and at least the components are mixed. It is preferable to form a composite having the partial structure (1) and the partial structure (2). In the composite, the partial structure of the component (1) having catalytic ability may be fixed to the surface of the structure of the component (2), or may be included in the porous structure.

Examples of the preparation method include the following methods (A) to (C).
(A) A method in which component (1) and component (2) are physically mixed and then heated.
(B) After reducing the precursor solution of component (1) to zero-valent component (1), component (2) is added, and the zero-valent component (1) is added to component (2). Impregnation method.
(C) A method of mixing component (1) and component (2) previously supported on a carrier.
Hereinafter, the methods (A) to (C) will be described.

(Method (A))
In the method (A), the component (1) and the component (2) are physically mixed and then heated to prepare a composition.
In the method (A), as the component (1), those composed only of the above-mentioned specific metal or a specific metal alloy may be used, or a compound containing a specific metal may be used. In the method (A), by performing heating after physical mixing, an anion or a ligand in a compound containing a metal can be removed, and a zero-valent metal having catalytic ability can be obtained. Examples of the compound include metal chlorides and carbonyl complexes. Among these, an iron carbonyl complex, a cobalt carbonyl complex, a ruthenium carbonyl complex, and a rhodium carbonyl complex are preferable, and Ru 3 (CO) 12 is more preferable because it is stable even at normal temperature and pressure.
As a component (2), you may synthesize | combine by a well-known method and may use a commercial item. For example, in the case of ZIF-8, J.M. Cravillon et al., Chem. Mater. 2009, 21, 1410-1412. It can be synthesized by the method described in 1. Commercial products such as Basolite Z1200 (sold by Aldrich) can also be used.

The method of physically mixing the component (1) and the component (2) is not particularly limited, and can be performed by a usual method such as mixing with a mortar or ball mill.
The heat treatment can be performed by heat treatment under vacuum conditions or in the presence of an inert gas such as He. Heating is preferably performed at 80 to 500 ° C., preferably 100 to 500 ° C., more preferably 200 to 500 ° C., and further preferably 200 to 300 ° C., for 0.5 to 20 hours.

(Method (B))
In the method (B), the precursor of the component (1) is reduced in a solvent to obtain a zero-valent component (1), then the component (2) is added, and the zero-valent component is added to the component (2). The composition is prepared by impregnating (1) and then heating, distilling off, etc. as necessary.

In the method (B), the precursor of the component (1) can be reduced to a zero-valent component (1), that is, a zero-valent metal. Metal salts in which a ligand or an anion is coordinated as the metal element (zero valence) of the above.
More specifically, chlorides such as ruthenium chloride, rhodium chloride, osmium chloride, iridium chloride; acetylacetonate complexes such as ruthenium acetylacetonate, rhodium acetylacetonate, osmium acetylacetonate, iridium acetylacetonate; ruthenium cyanide Examples include potassium cyanate complexes such as potassium oxalate, potassium rhodium cyanate, potassium osmium cyanate, potassium iridium cyanate; and potassium salts such as potassium ruthenate, potassium rhodate, potassium osmate, potassium iridate. By reducing these precursors in a solvent, a zero-valent component (1) is obtained.

  The solvent is not particularly limited as long as it can dissolve the precursor, but water is preferable because solubility is easily secured. The solvent may be a single solvent or a mixed solvent. The solvent may have a function as a reducing agent.

Examples of the reducing agent include hydrazine, sodium borohydride, citric acid, oxalic acid, 1,2-benzenediol, 1,3-benzenediol, 1,4-benzenediol, and hydrogen gas, 2-ethanediol (ethylene glycol), 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol , Pentanediol, hexanediol, heptanediol, octanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, hexylene glycol, 2-butene-1,4-diol, glycerol, 1,1,1-tris Hydroxymethylethane, 2-ethyl-2- Dorokishimechiru-1,3-propanediol, 1,2,3-hexanetriol, it includes alcohol reducing solvent such as benzyl alcohol,
Since it preferably has properties as a solvent, it is an alcohol-based reducing solvent, more preferably 1,2-ethanediol, 1,2-propanediol and 1,3-propanediol, and particularly preferably 1,2-ethanediol.
A reducing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  The addition amount of the reducing agent may be more than the amount that can sufficiently reduce the precursor, and in the case other than the alcohol-based reducing solvent, 0.5 mol or more is preferable with respect to 1 mol of the precursor, and 1 mol or more is more. preferable.

In the method (B), the same component (2) as that used in the method (A) can be used.
After the addition of component (2), the mixture can be stirred, heated, the solvent or water distilled off, and the resulting product can be dried, if necessary. The heating temperature is preferably 80 ° C to 300 ° C, more preferably 100 ° C to 250 ° C, and further preferably 150 ° C to 230 ° C.

Further, during the reduction reaction or during the addition of component (2), an acid derived from the anion of the precursor may be generated. Therefore, it is preferable to add a base so that it can be neutralized. In particular, when ruthenium is used as the component (1), it is preferable that the ruthenium aggregation can be reduced by setting the reaction solution under basic conditions.
The base used for neutralization is not particularly limited, and sodium hydroxide, potassium hydroxide and the like can be used.

(Method (C))
In the method (C), a composition is prepared by mixing the component (1) and the component (2) previously supported on a carrier.

There are no particular restrictions on the carrier, preferably a metal oxide, Al 2 O 3, MgO, a metal oxide such as TiO 2, CeO 2, La 2 O 3, Pr 6 O 11 is preferable, CeO More preferred are lanthanoid oxides such as 2 , La 2 O 3 , and Pr 6 O 11 .

The component (1) can be supported on the carrier by, for example, a method (impregnation method) in which the component (1) is dispersed in a solvent or water and then supported by adding the carrier.
Although it does not specifically limit as a solvent, Alcohol solvents, such as polar solvents, such as acetone and tetrahydrofuran, methanol, ethanol, etc. are mentioned.
The addition amount of the carrier is not particularly limited, but it is preferably added so that the ratio of the component (1) to the total of the component (1) and the carrier is 0.1 to 15% by mass.
After the addition of the carrier, the mixture can be stirred, the solvent or water can be distilled off, and the resulting product can be dried as necessary.

  When component (1) is a non-zero compound, the anion or ligand contained in the compound is preferably removed after loading. The anion or the ligand can be removed by, for example, heat treatment under vacuum conditions or in the presence of an inert gas such as He. Heating is preferably performed at 50 to 600 ° C, preferably 150 to 550 ° C for 0.5 to 20 hours.

  The method of mixing the supported component (1) obtained as described above and the same component (2) is not particularly limited. For example, physical mixing may be used, and impregnation by adding the component (2) to the supported component (1) in the solvent may be used. Physical mixing and impregnation can be performed by the same methods as the method (A) and the method (B), respectively.

[Ammonia production method]
The ammonia production method according to the second aspect of the present invention uses the composition according to the first aspect as a catalyst.

The method for producing ammonia is not particularly limited. For example, ammonia is produced by supplying a raw material gas composed of hydrogen gas and nitrogen gas into a reaction vessel filled with the composition of the first aspect. can do.
The composition of the first aspect may be used for the production of ammonia after previously pulverizing, molding, sizing and the like.

  The reaction temperature is preferably 200 ° C to 600 ° C, more preferably 250 ° C to 500 ° C, and further preferably 300 ° C to 450 ° C.

  In the ammonia production method of the present invention, by using the composition of the first aspect as a catalyst, the inside of the reaction vessel becomes 200 ° C. or higher, and the structure of the catalyst collapses even in a situation where there is a nucleophilic reaction by ammonia. In this way, ammonia can be preferably produced. Moreover, according to this invention, ammonia can be manufactured with a high yield.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

The ammonia gas resistance evaluation of the component (2) in this example was performed using the apparatus shown in FIG.
Specifically, the porous metal complex of component (2) was placed in a microtube, and the microtube was placed in a desiccator. After evacuating the desiccator, ammonia gas was flowed for 2 hours. After purging with nitrogen gas, the microtube was taken out, XRD measurement of the porous metal complex after ammonia exposure was performed, and the resistance against ammonia gas was evaluated by comparing the obtained XRD chart with the XRD chart before ammonia exposure. .
Evaluation experiments at high temperatures (200 ° C., 300 ° C., 350 ° C.) were performed in the same procedure by using a Schlenk tube instead of a desiccator and heating with a mantle heater.

<Reference Example 1>
Table 1 shows the results of evaluation of ammonia gas resistance and high temperature resistance in various porous metals. In Table 1, chemical formula abbreviations are the same as above. “-” In Table 1 means that no examination was made.

Further, an XRD chart of Cu 2 (bpdc) 2 (bpy) is shown in FIG. 2, an XRD chart of Zn 2 (bpdc) 2 (bpy) is shown in FIG. 3, an XRD chart of HKUST-1 is shown in FIG. 4, and MOF-5 5 is an XRD chart of MgFo 2 , FIG. 7 is an XRD chart of MIL-68 (In), FIG. 8 is an XRD chart of MIL-125, and FIG. 8 is an XRD chart of UiO-66. FIG. 9 shows an XRD chart of MIL-101 (Cr), FIG. 11 shows an XRD chart of MOF-74 (Mg), FIG. 11 shows an XRD chart of MOF-76 (Y), and FIG. An XRD chart is shown in FIG. 13, and an XRD chart of ZIF-8 is shown in FIG. 2 to 14, (a) is an XRD chart predicted by simulation, (b) is an XRD chart before exposure to ammonia (at room temperature), and (c) to (f) are room temperatures after exposure to ammonia, respectively. It is a XRD chart of (23 degreeC), 200 degreeC, 300 degreeC, and 350 degreeC.

From the results shown in Table 1 and FIGS. 2 to 14, Cu 2 (bpdc) 2 (bpy), Zn 2 (bpdc) 2 (bpy), HKUST-1, MOF-5, MgFo 2 and MIL-68 (In) were evaluated. A significant decrease in XRD intensity and a change in peak pattern were observed before and after the experiment. On the other hand, in other porous metal complexes, it was confirmed that the XRD chart did not change and was not decomposed by ammonia gas at 200 ° C.

<Preparation Example 1>
5% by mass Ru / Pr 6 O 11 (a composition in which 5% by mass of Ru is supported on Pr 6 O 11 was represented as follows) was prepared as follows.
Ru 3 (CO) 12 (Wako Pure Chemical Industries, Ltd.) 0.55 mg (2.6 mmol) was placed in an eggplant flask and dissolved in 200 ml of tetrahydrofuran, followed by 5.0 g (11.5 mmol) of support Pr 6 O 11. ) And stirred with a magnetic stirrer at room temperature for 12 hours. Thereafter, the solvent was removed by heating using a rotary evaporator. At this time, the temperature of the warm bath was gradually raised to 70 ° C. The obtained solid was transferred from the eggplant flask to a baking dish and dried with a dryer at 70 ° C. for one day. Thereafter, it is placed in a boat made of Pyrex (registered trademark) glass (manufactured by Corning) and subjected to heat treatment at 350 ° C. for 5 hours under a flow of He in a horizontal tubular furnace to remove the ligand of the ruthenium compound, and the product 4. 7 g was obtained.

<Example 1>
Al-BTB and 5 mass% Ru / Pr 6 O 11 were physically mixed in a mortar at a mass ratio of 1: 9 to obtain a composition 1 represented by Al-BTB + Ru / Pr 6 O 11 . Thereafter, the obtained composition 1 (catalyst) was sufficiently pulverized and mixed in a mortar, formed into a disk, pulverized again, and sized to 250 to 500 μm, and used for the reaction.
The following reaction was performed using an atmospheric pressure fixed bed flow reactor shown in FIG. A quartz reaction tube having an inner diameter of 7 mm was filled with 0.20 g of composition 1 (catalyst), N 2 + 3H 2 (10 mL / min, 0.1 MPa) was circulated, and measurement was performed at a reaction temperature of 350 ° C. The space velocity (GHSV) was 18000 mL / hour · g under the above conditions. Ion chromatography was used for gas analysis. Sampling was performed through a sampling loop with a known volume, the amounts of H 2 and N 2 were measured at the reaction tube inlet and the reaction tube outlet, and the amount of ammonia was determined by calculation.

<Ion chromatography analysis conditions>
Column: Shodex IC YK-421
Column size: ID 4.6 mm, length 125 mm
Filler: Weakly acidic cation exchanger with silica gel coated with polymer having carboxyl group Eluent: 4 mmol / l phosphoric acid solution

A nitrogen atom was used as an internal standard for the calculation of the ammonia yield. The calculation formula is as follows.

<Comparative Example 1>
The ammonia yield was measured in the same procedure as in Example 1 using 5% by mass Ru / Pr 6 O 11 as the catalyst. The results are summarized below.

  From the above results, it was confirmed that the ammonia yield was improved by using the composition 1 of the present invention as a catalyst.

<Example 2>
In a mortar, 10.8 mg of Ru 3 (CO) 12 and 103.3 mg of ZIF-8 (Basolite 1200) were physically mixed for 30 minutes. Thereafter, 84.4 mg of the mixture was heated to 200 ° C. at a rate of 3 K / min in a tube furnace under a nitrogen stream of 200 mL / min and held for 2 hours. Then, it stood to cool to room temperature, and obtained 81.2 mg of the composition 2 of Ru and ZIF-8.
When the obtained composition 2 of Ru and ZIF-8 was measured by X'Pert Pro MPD (manufactured by XRD Spectris Co., Ltd.), it was confirmed that the ZIF-8 skeleton could be maintained.

<Example 3>
After 23.4 mg (113 μmol) of RuCl 3 was dissolved in 2.0 ml of ethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.), 211 mg of ZIF-8 was dispersed. Subsequently, 0.050 mL (400 μmol) of an 8M aqueous sodium hydroxide solution was added and heated at 200 ° C. for 3 hours. The obtained reaction mixture was filtered to obtain 184 mg of the intended Ru and ZIF-8 composition 3.

<Example 4>
0.041 g (0.138 mmol) of zinc nitrate hexahydrate, which is the raw material of ZIF-8 to be prepared, and 0.0225 g (0.274 mmol) of 2-methylimidazole are each completely dissolved in 10 ml of dimethylformamide as a solvent. Mixed. Furthermore, 0.5 g of 5 mass% Ru / Pr 6 O 11 obtained in Preparation Example 1 was added to obtain a raw material solution. The composition of the raw material was such that zinc nitrate hexahydrate: 2-methylimidazole was 1: 2, and the prepared ZIF-8 was based on a Ru / Pr 6 O 11 catalyst (Ru content is 5% by mass). It mix | blended so that it might become 10 mass%. The raw material solution was prepared at room temperature.
The above raw material solution was placed in a 25 ml autoclave and heated at a reaction temperature of 140 ° C. for 24 hours. The resulting precipitate was collected by filtration, washed with alcohol, and then vacuum dried at room temperature to obtain a composition 4 of 5% by mass Ru / Pr 6 O 11 and ZIF-8. The obtained composition 4 was confirmed by XRD for confirmation of crystal phase, confirmation of coordination bond formation by FT-IR measurement, confirmation of shape by SEM observation, and confirmation of element distribution by TEM-EDX.
A new fully automatic multipurpose X-ray diffractometer D8 ADVANCE manufactured by Bruker AXS was used for XRD measurement, and a field emission scanning electron microscope JSM-7000F manufactured by JEOL Ltd. was used for SEM image observation. The infrared absorption spectrum was measured by the ATR method using a Fourier transform infrared spectroscopic analyzer Spectrum 100 manufactured by PerkinElmer. TEM-EDX was measured using a field emission electron microscope JEM-2200FS manufactured by JEOL.
The presence of 5 mass% Ru / Pr 6 O 11 was confirmed by X-ray diffraction measurement, and the presence of ZIF-8 was confirmed by FT-IR. From SEM image observation, it was confirmed that no large difference was observed in the surface state of the particles before and after the reaction. In addition, analysis by TEM-EDX confirmed that the constituent elements of 5 mass% Ru / Pr 6 O 11 and ZIF-8 were uniformly distributed without segregation.

<Example 5>
0.05 g (0.108 mmol) of aluminum nitrate nonahydrate which is a raw material of Al-BTB to be prepared, 0.0489 g (0.108 mmol) of 1,3,5-tris (4-carboxyphenyl) benzene (H 3 BTB) ) Were completely dissolved in 5 ml of diethylformamide as a solvent and mixed. Furthermore, 0.5 g of 5 mass% Ru / Pr 6 O 11 obtained in Preparation Example 1 was added to obtain a raw material solution. The compounding composition of the raw materials is aluminum nitrate nonahydrate: H 3 BTB is 1: 1, and blended so that the prepared Al-BTB is 10% by mass with respect to 5% by mass Ru / Pr 6 O 11 . did. Preparation at the time of raw material mixing was performed at room temperature.
The raw material solution was placed in a 25 ml autoclave and heated at a reaction temperature of 150 ° C. for 72 hours. The resulting precipitate was collected by filtration, washed with alcohol and then vacuum dried at room temperature to obtain a composition 5 of 5% by mass Ru / Pr 6 O 11 and Al-BTB.
The presence of the 5 mass% Ru / Pr 6 O 11 was confirmed by X-ray diffraction measurement, and the presence of Al-BTB was confirmed by FT-IR. From SEM image observation, it was confirmed that there was no significant difference in particles before and after the reaction. Moreover, it was confirmed by the analysis by TEM-EDX that the constituent elements of 5 mass% Ru / Pr 6 O 11 and Al-BTB were uniformly distributed without segregation.

  Since the composition of the present invention has a wide application temperature range and can withstand strong basicity, it can be suitably used as a catalyst, adsorbent or separation material for the production of basic gas such as ammonia gas.

Claims (4)

  1. The composition which mix | blended following (1) and (2).
    (1) selected from the group consisting of scandium, titanium, vanadium, chromium, manganese, cobalt, copper, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, silver, hafnium, tantalum, tungsten, rhenium, osmium and iridium At least one metal, an alloy containing the metal, or a compound containing the metal.
    (2) A porous metal complex that does not cause structural collapse at 200 ° C. in the presence of 1 atm of ammonia.
  2. Said (1) is
    Ruthenium, ruthenium containing alloys, ruthenium containing compounds, rhodium, rhodium containing alloys, rhodium containing compounds, osmium, osmium containing alloys, osmium containing compounds, iridium, iridium containing alloys and iridium containing compounds The composition of Claim 1 which is at least 1 sort (s) chosen from.
  3. (2)
    The composition according to claim 1 or 2, which is a porous metal complex having at least one metal selected from the group consisting of zinc, copper, magnesium, aluminum, manganese, iron, cobalt and nickel.
  4.   A method for producing ammonia by reacting nitrogen and hydrogen using the composition according to any one of claims 1 to 3 as a catalyst.
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Publication number Priority date Publication date Assignee Title
WO2016133213A1 (en) * 2015-02-20 2016-08-25 国立大学法人大分大学 Ammonia synthesis catalyst and method for producing same
WO2016133134A1 (en) * 2015-02-17 2016-08-25 味の素株式会社 Production system and production method for organic compounds or microbes
CN107530686A (en) * 2015-02-20 2018-01-02 国立研究开发法人科学技术振兴机构 ammonia synthesis catalyst and preparation method thereof

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JP2010510881A (en) * 2006-11-27 2010-04-08 コリア リサーチ インスティテュート オブ ケミカル テクノロジー Method for producing porous organic-inorganic hybrid, organic-inorganic hybrid obtained by the method, and catalytic use thereof
JP2010527890A (en) * 2007-05-21 2010-08-19 財団法人韓国化学研究院 Preparation of surface-functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinately unsaturated metal sites and their catalytic application
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JP2010510881A (en) * 2006-11-27 2010-04-08 コリア リサーチ インスティテュート オブ ケミカル テクノロジー Method for producing porous organic-inorganic hybrid, organic-inorganic hybrid obtained by the method, and catalytic use thereof
JP2010527890A (en) * 2007-05-21 2010-08-19 財団法人韓国化学研究院 Preparation of surface-functionalized porous organic-inorganic hybrid materials or mesoporous materials with coordinately unsaturated metal sites and their catalytic application
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WO2016133134A1 (en) * 2015-02-17 2016-08-25 味の素株式会社 Production system and production method for organic compounds or microbes
WO2016133213A1 (en) * 2015-02-20 2016-08-25 国立大学法人大分大学 Ammonia synthesis catalyst and method for producing same
CN107530686A (en) * 2015-02-20 2018-01-02 国立研究开发法人科学技术振兴机构 ammonia synthesis catalyst and preparation method thereof
EP3260198A4 (en) * 2015-02-20 2018-12-05 Japan Science and Technology Agency Ammonia synthesis catalyst and method for producing same

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