WO2016088896A1 - 複合体、複合体の製造方法、アンモニア合成触媒及びアンモニア合成方法 - Google Patents
複合体、複合体の製造方法、アンモニア合成触媒及びアンモニア合成方法 Download PDFInfo
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- WO2016088896A1 WO2016088896A1 PCT/JP2015/084207 JP2015084207W WO2016088896A1 WO 2016088896 A1 WO2016088896 A1 WO 2016088896A1 JP 2015084207 W JP2015084207 W JP 2015084207W WO 2016088896 A1 WO2016088896 A1 WO 2016088896A1
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- Prior art keywords
- metal
- ammonia
- catalyst
- carrier
- supported
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 430
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 204
- 239000003054 catalyst Substances 0.000 title claims abstract description 162
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- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 106
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- 238000004519 manufacturing process Methods 0.000 title claims description 57
- 238000001308 synthesis method Methods 0.000 title claims description 10
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- 239000002184 metal Substances 0.000 claims abstract description 237
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 91
- 150000003624 transition metals Chemical class 0.000 claims abstract description 86
- -1 amide compound Chemical class 0.000 claims abstract description 64
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- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
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- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 88
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 56
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 23
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- 125000004429 atom Chemical group 0.000 description 29
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
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- BWKDLDWUVLGWFC-UHFFFAOYSA-N calcium;azanide Chemical compound [NH2-].[NH2-].[Ca+2] BWKDLDWUVLGWFC-UHFFFAOYSA-N 0.000 description 10
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
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- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
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- 238000004255 ion exchange chromatography Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
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- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 208000005156 Dehydration Diseases 0.000 description 1
- 241000975394 Evechinus chloroticus Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- JAZNSOPOXXXZQO-UHFFFAOYSA-N [N].CCO Chemical compound [N].CCO JAZNSOPOXXXZQO-UHFFFAOYSA-N 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- VUBLMKVEIPBYME-UHFFFAOYSA-N carbon monoxide;osmium Chemical group [Os].[Os].[Os].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] VUBLMKVEIPBYME-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
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- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
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Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/04—Preparation of ammonia by synthesis in the gas phase
- C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
- C01C1/0411—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst characterised by the catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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Definitions
- the present invention relates to a composite containing a transition metal, a carrier and a metal amide, a supported metal catalyst using the composite, an ammonia synthesis catalyst, and an ammonia synthesis method.
- Alkaline earth metal nitrides such as Ca 3 N 2 , Sr 3 N 2 , Ba 3 N 2 are raw materials for aluminum nitride used in semiconductor devices, ceramic particles for metal sliding members, battery electrode constituent materials, conductive fine particles It is a compound used for etc.
- Patent Document 1 discloses a method for producing an alkaline earth metal nitride by thermally decomposing a corresponding alkaline earth metal amide.
- Patent Document 2 discloses a method for producing a high-purity metal nitride by reacting alkaline earth metal with ammonia to form a liquid phase, and thermally decomposing the obtained metal amide compound.
- Patent Document 3 discloses a method for producing a metal amide compound by adding a metal simple substance or alloy to a metal hydride or metal hydride and reacting with liquid ammonia as a method for producing the metal amide compound.
- a metal such as Li or Ca or a compound thereof is sealed in a reaction vessel, and under cooling, ammonia having a volume ratio to metal of 10 times or more is introduced and liquefied, followed by stirring reaction, LiNH 2 .
- a method for producing a metal amide such as Ca (NH 2 ) 2 is disclosed (Patent Document 4).
- Calcium nitride which is a typical alkaline earth metal nitride has so far been known as ⁇ -Ca 3 N 2 , ⁇ -Ca 3 N 2 , ⁇ -Ca 3 N 2 , Ca 11 N 8 , Ca 2 N and the like. ing. Also known are Ca 2 NH, CaNH, Ca (NH 2 ) 2, etc., which are hydrides of calcium nitride (hereinafter sometimes referred to as “Ca—N—H compounds”).
- Ca 2 N is known to be a very chemically unstable substance such as being easily oxidized, and the range in which Ca 2 N can stably exist is 1000 ° C. or lower in Ar, or nitrogen. Among them, it is reported that it is between 250 ° C. and 800 ° C. (Non-patent Document 1).
- a nitride represented by AE 2 N (AE represents at least one element selected from Ca, Sr, and Ba) has a high conductivity “two-dimensional electride compound” (Patent Document 5).
- This two-dimensional electride compound AE 2 N is a layered compound in which electrons (e ⁇ ) are bonded as anions between layers composed of [AE 2 N] + . That is, it can also be expressed as AE 2 N + : e ⁇ in the ionic formula.
- Ca 2 N which is a typical two-dimensional electride compound
- Ca 3 N 2 and metal Ca in a vacuum.
- the conduction electron concentration of Ca 2 N is 1.4 ⁇ 10 22 / cm 3 and is reported to have a work function of 2.6 eV (Non-patent Document 2).
- Non-patent Document 3 an example in which this two-dimensional electride is used as a reducing agent for pinacol coupling has been reported.
- Non-patent Document 4 acts as a base catalyst and exhibits catalytic activity for isomerization of olefins such as 2-methyl-1-butene
- Non-patent Document 5 Reported is an example (Non-Patent Document 5) where a catalyst in which an amide compound of Na, K, Eu, or Yb is supported on an oxide carrier exhibits catalytic activity for isomerization of olefins such as 2-methyl-1-butene Has been. Both examples have been reported to function as base catalysts.
- ammonia synthesis uses a method (Haber-Bosch method) in which a catalyst containing several mass% of Al 2 O 3 and K 2 O in Fe 3 O 4 is used.
- iron-based catalysts and Ru-based catalysts for example, Ru / MgO, Ru / CaO, Ru-Cs / MgO
- Ru-based catalysts have been studied as synthesis methods other than the Harbor Bosch method (Non-Patent Documents 6 and 7).
- These catalysts are catalysts in which a transition metal having ammonia synthesis activity is supported on a carrier, and are generally referred to as “supported metal catalysts”.
- supported metal catalysts for ammonia synthesis include nitrides of Group 8 or Group 9 transition metals such as Fe, Ru, Os, Co, Group 8 or Group 6B transition metals, and Co / Mo composite nitridation. A thing etc. are used (patent documents 6-9). Further, there is known an ammonia synthesis catalyst in which Ru is supported on silicon nitride or boron nitride supported on Al 2 O 3 , SiO 2 , Mg 2 O or magnesium aluminum spinel as a sub-carrier (Patent Document). 10).
- the present inventors have found that by supporting a transition metal on a two-dimensional electride compound, it becomes an ammonia synthesis catalyst having high activity.
- the two-dimensional electride compound itself is unstable, There is a problem that the stability of is low.
- a two-dimensional electride compound is used as a catalyst carrier, there is a problem that the processability is poor and it is difficult to mold the catalyst according to the reaction.
- the BET specific surface area when Ca 2 N was used as a support was measured, it was about 1 m 2 / g.
- the particles of the supported transition metal became large and supported with high dispersion. There was also a problem that it was not possible.
- the gist of the present invention is [1] a composite comprising a transition metal, a carrier, and a metal amide compound represented by the following general formula (1), wherein the carrier is a metal oxide or a carbonaceous carrier.
- the metal amide compound is a metal amide compound represented by the following general formula (1): M (NH 2 ) x (1) (the general formula (1) M represents at least one metal atom selected from Li, Na, K, Be, Mg, Ca, Sr, Ba, and Eu, and x represents the valence of M.)
- the composite of the present invention can be produced without requiring a reaction at a high temperature and for a long time, and can more easily enjoy the properties of the two-dimensional electride compound. Since the composite of the present invention can be obtained in the production process without undergoing a reaction at a high temperature and for a long time, it is a composite in which a transition metal is supported with high dispersibility. Therefore, the composite of the present invention has high performance as a supported metal catalyst, particularly an ammonia synthesis catalyst. *
- the composite of the present invention When the composite of the present invention is used as a supported metal catalyst, it has the possibility of being usable as a catalyst in various reactions, and is advantageous in that, for example, an ammonia decomposition reaction can be promoted.
- Ca is a TEM photograph of (NH 2) 2 was carried ZrO 2 on the carrier Ca (NH 2) 2 / ZrO 2 composites. Different amounts of Ca and (NH 2) 2 supported on ZrO 2 on the support, further carrying a Ru complex, which is a graph showing the catalytic activity when used as an ammonia synthesis catalyst. Ca and (NH 2) 2 supported on ZrO 2 on the carrier, a further different amounts complexes carrying Ru of a graph showing the catalytic activity when used as an ammonia synthesis catalyst.
- the composite of the present invention contains a transition metal, a carrier, and a metal amide compound.
- the composite of the present invention contains a carrier described later, a metal amide compound described later, and a transition metal, and more specifically, the metal amide compound is supported on the carrier, and further the metal A transition metal is supported on an amide compound, and preferably has a structure in which the metal amide and the transition metal are laminated in this order on the support.
- the structure of the composite is not particularly limited. Even if the metal amide and transition metal are stacked and supported on a planar support in this order, the metal amide and transition metal are stacked and supported on a substantially spherical support. It may be a so-called core-shell type structure. *
- Support used in the present invention is a metal oxide or a carbonaceous support. Although it does not specifically limit as a metal oxide, The metal used for a metal oxide may be a typical metal or a transition metal. *
- the carrier of the present invention carries a metal amide compound described later, and in this case, the treatment is usually performed in a liquid ammonia atmosphere. Therefore, a basic, neutral, or weakly acidic metal oxide is preferable in terms of affinity with ammonia or a generated metal amide compound.
- metal oxide that satisfies the above definition
- specific basic, neutral, or weakly acidic metal oxides include ZrO 2 , TiO 2 , CeO 2 , Al 2 O 3 , At least one metal oxide selected from Nb 2 O 5 , Ta 2 O 5 , and MgO has high reaction activity when used as a supported metal catalyst, specifically, ammonia generation when used as an ammonia synthesis catalyst It is preferable in terms of high speed, and at least one metal oxide selected from ZrO 2 , TiO 2 , CeO 2 , Al 2 O 3 , and MgO can be generally used, and more excellent in workability.
- ZrO 2 , TiO 2 , and Al 2 O 3 are more preferable from the viewpoint of cost.
- a carbonaceous carrier can also be used as the carrier used in the present invention.
- the carbonaceous carrier means a carrier mainly composed of carbon, and specifically includes graphite, carbon black, activated carbon, carbon nanotube, graphene, etc., but those having no oxygen-containing functional group are metal amide compounds. From the viewpoint of affinity, graphite is usually preferred. One type or two or more types of the carriers may be contained. *
- the carrier is preferably a metal oxide. This is because the reaction activity when used as a supported metal catalyst to be described later is high, and it is assumed that the interaction given by the support is larger than that of the carbonaceous support.
- the metal oxide has a higher stability than the carbonaceous support when the composite of the present invention is used as a supported metal catalyst.
- the carbonaceous support is preferably a metal oxide because it can generate methane by decomposition.
- the form of the carrier in the present invention is not particularly limited, and can be changed according to the purpose and application of use, and is usually in the form of powder, its molded body, porous body, solid sintered body, thin film, solid A single crystal or the like can be used. In particular, a porous molded body is preferable. *
- the particle size of the carrier used in the present invention is not particularly limited.
- the BET specific surface area of the carrier used in the present invention is not particularly limited, but is usually 10 m 2 / g or more and 1000 m 2 / g or less, preferably 500 m 2 / g or less.
- metal oxides and carbonaceous supports have many types of powders and molded products having different surface areas and pore structures, for example, by using a support having a large surface area with a developed pore structure, the basic structure of the support can be improved. Since the transition metal and the metal amide compound are highly dispersed on the carrier while maintaining, high activity can be obtained. *
- reaction temperature for synthesizing metal amide compounds is considerably lower than the reaction temperature for synthesizing ammonia, if a transition metal is supported on the metal amide compound, shrinkage or aggregation may occur during the reaction. High nature. As a result, the transition metal supported on the metal amide aggregates, and when the composite of the present invention is used as a supported metal catalyst, its activity may be reduced. On the other hand, by using the composite of the present invention, it is possible to prevent aggregation of the metal amide compound itself and to obtain a stable catalytic activity over a long period of time. *
- the metal amide compound used in the present invention is a metal amide compound represented by the following general formula (1).
- M represents a metal atom that forms a metal amide compound, and is at least one metal atom selected from Li, Na, K, Be, Mg, Ca, Sr, Ba, and Eu, in terms of thermal stability. Ca, Sr, and Ba are preferable, and Ca is more preferable in terms of reactivity and operability.
- the x represents the valence of the metal atom M. *
- the metal amide compound in the present invention is considered to be one of the two-dimensional electride compounds.
- the metal amide compound By supporting the metal amide compound on the carrier, the metal amide compound also functions as an active species and cooperates with the transition metal particles supported on the composite. It is estimated that the function as an active species is enhanced.
- the amount of the metal amide compound supported is not particularly limited, but is usually 1% by mass or more, preferably 10% by mass or more, and usually 90% by mass or less, and 40% by mass with respect to the total mass with the carrier. The following is preferred.
- the amount of support per 1 m 2 of BET specific surface area of the carrier is not particularly limited, but is 0.01% by mass or more, preferably 0.1% by mass or more, and usually 1.0% by mass or less, 0.5% The mass% or less is preferable.
- transition metal used in the present invention is not particularly limited, but is usually a Group 4 element metal of the periodic table such as Ti, Zr, Hf, etc .; Group 5 element of the periodic table such as V, Nb, etc. Metal; metal of Group 6 element of the periodic table such as Cr, Mo, W; metal of Group 7 element of the periodic table such as Mn, Tc, Re; metal of Group 8 element of the periodic table such as Fe, Ru, Os; Co, Rh, Ir etc. periodic table group 9 element metal; Ni, Pd, Pt etc. periodic table group 10 element metal; etc. are used, and these metals can be used alone or in combination of two or more metals. Can also be used. *
- the transition metal is usually a reaction active component, so that the metal species can be appropriately selected according to the reaction using the supported metal catalyst, although not particularly limited, Mo, Mn, Fe, Ru, Rh, Ni, Pt, Pd, Rh, or the like can be preferably used.
- the transition metal can be appropriately selected from metals that can be converted into ammonia using a gas containing nitrogen and hydrogen as raw materials.
- Ru, Co, and Fe are usually used, and Ru is preferable because of its high reaction activity.
- the composite of the present invention may contain components other than the transition metal, the carrier, and the metal amide compound depending on the purpose of use.
- the BET specific surface area of the composite of the present invention is not particularly limited, but is usually 10 m 2 / g or more, preferably 30 m 2 / g or more, and usually 200 m 2 / g or less.
- the average particle diameter of the transition metal particles supported on the surface of the composite of the present invention is not particularly limited, but is usually several nm to several tens of nm as measured by a CO adsorption method.
- the transition metal particles are usually supported as nanoparticles having a degree of dispersion of about 10 to 50%.
- the method for producing a composite of the present invention comprises a carrier used in the present invention, a metal atom source containing the metal atom M in the general formula (1) (hereinafter sometimes simply referred to as a metal atom source), and a liquid.
- a step of mixing ammonia hereinafter referred to as a mixing step
- a step of reacting the metal atom source with liquid ammonia to produce the metal amide compound on the carrier to obtain a metal amide-supported carrier (hereinafter referred to as a reaction step). It is characterized by including.
- FIG. 1 shows an outline of a process for supporting Ca (NH 2 ) 2 on a carrier as an example of a composite.
- the metal atom source containing the metal atom M refers to a raw material of the metal atom M in the metal amide compound, and is not particularly limited as long as it is a raw material. M) is used. Specifically, it is at least one metal selected from metal Li, metal Na, metal K, metal Be, metal Mg, metal Ca, metal Sr, metal Ba, and metal Eu. Further, a hydride of each metal such as CaH 2 can also be used. Preferably, metal M is used in terms of reactivity. As the metal M, metal Li, metal Na, metal K, and metal Ca are preferable, and metal Ca is more preferable in terms of operability and reactivity.
- the form of the metal atom source is not particularly limited, but in order to facilitate dissolution in liquid ammonia, it is preferably powdered or particulate, the particle diameter is not particularly limited, and is usually preferably 1 mm or more and 2 mm or more. Usually, 5 mm or less and 3 mm or less are preferable. *
- the carrier used in the present invention is not particularly limited before being subjected to the mixing step, but a treatment for removing impurities such as surface hydroxyl groups and carbon dioxide generated by chemical adsorption of water on the carrier surface (hereinafter, removal treatment). Can be done.)
- the method for the removal treatment is not particularly limited and can be performed by a commonly used method. Specifically, a method of heating at a high temperature, a method by vacuum evacuation, or a combination thereof is used. It is preferable to perform treatment using both high-temperature heating and evacuation. Conditions for the high-temperature heating are not particularly limited as long as the purpose of the removal treatment is achieved, and can be performed by a commonly used method, but is usually heated at 500 ° C. or higher. Similarly, the method and conditions of evacuation are not particularly limited as long as the purpose of the removal treatment is achieved, and can be performed by a commonly used method. *
- reaction container which performs the said mixing process and reaction process is not specifically limited, Usually, it carries out using a pressure-resistant container.
- the mixing step and the reaction step may be performed individually or consistently, but usually both steps are performed as a consistent step.
- the carrier, the metal atom source, and liquid ammonia are mixed in a reaction vessel.
- the order of mixing is not particularly limited, but usually, ammonia gas is introduced into a reaction vessel in which the carrier and the metal atom source are sealed, the reaction vessel is cooled, the ammonia is liquefied, and then mixed.
- the metal atom source used is usually uniformly dissolved in liquid ammonia.
- the mixing time is not particularly limited, and can be appropriately set as long as the purpose of uniformly dissolving the metal atom source can be achieved.
- the mixing method is not particularly limited, but it can be performed by a commonly used method such as stirring. In the case of mixing by stirring, the means is not particularly limited, and can be performed by a commonly used method. *
- the cooling temperature is not particularly limited as long as the ammonia gas is liquefied, but it is usually higher than the melting point ( ⁇ 77 ° C.) of ammonia under normal pressure.
- the temperature is preferably ⁇ 50 ° C. or higher, and usually the boiling point ( ⁇ 35 ° C.) or lower and ⁇ 40 ° C. or lower is preferable.
- the amount of ammonia added is not particularly limited, but usually ammonia is used in a mass ratio of 3 to 30 times the amount of the metal atom source used. *
- a metal amide compound is produced by a reaction represented by the following reaction formula. M + xNH 3 ⁇ M (NH 2 ) x + (x / 2) H 2 (x represents the valence of metal M)
- the produced metal amide compound M (NH 2 ) x is supported on the carrier mixed in the mixing step, and a metal amide carrier is obtained.
- the reaction temperature is not particularly limited, but is usually ⁇ 20 ° C. or higher and 100 ° C. or lower, and can be appropriately set according to the ease of loading the metal amide compound on the support.
- the reaction time is not particularly limited, and can be appropriately set similarly to the reaction temperature.
- the metal amide compound is usually supported by removing the ammonia gas and hydrogen gas remaining in the reaction vessel from the reaction vessel after returning the temperature of the reaction vessel to room temperature.
- a metal amide-supported carrier supported thereon is obtained.
- the obtained metal amide-supported carrier is not particularly limited, but is usually obtained in a state where the shape of the used carrier is maintained and the surface thereof is coated with the metal amide compound.
- FIG. 1 shows an outline of a process for supporting Ca (NH 2 ) 2 on a carrier.
- metal Ca is used as the metal atom source
- calcium amide is generated as shown in the following formula. Ca + 2NH 3 ⁇ Ca (NH 2 ) 2 + H 2
- the outside of the stainless steel pressure vessel enclosing the metal Ca and the carrier is usually cooled in the range of ⁇ 40 to ⁇ 50 ° C. with liquid nitrogen-ethanol.
- ammonia gas is introduced into the container to form liquefied ammonia, and metallic Ca is uniformly dissolved in the liquid ammonia.
- Stirring is usually performed for about 1 hour with a magnetic stirrer or the like.
- the inside of the pressure vessel is maintained at ⁇ 20 ° C. to 100 ° C., and the reaction is usually stirred for about 1 to 3 hours.
- a carrier in which Ca (NH 2 ) 2 is immobilized on the surface of the carrier is obtained.
- the BET specific surface area of the metal amide-supported carrier is not particularly limited, but is usually 10 m 2 / g or more, preferably 30 m 2 / g or more, usually 1000 m 2 / g or less, preferably 500 m 2 / g or less.
- the method for producing a composite of the present invention includes a step (hereinafter referred to as a raw material supporting step) of supporting the transition metal raw material compound (hereinafter sometimes referred to as a transition metal raw material) on the metal amide supporting carrier. Also good.
- the transition metal raw material may be pyrolyzed to precipitate the transition metal.
- the raw material supporting step and the step of precipitating the transition metal may be performed separately or independently, but it is preferable to perform both steps consistently, and following the raw material supporting step, More preferably, the step of depositing the transition metal is performed. These steps are preferably performed subsequent to the mixing step and the reaction step. *
- the transition metal raw material compound is not particularly limited as long as it is a compound that can support the transition metal used in the composite of the present invention on the composite, but usually the transition metal salt or the transition metal These organometallic complexes are used.
- the transition metal raw material can be supported on the composite through the step of precipitating the transition metal by subsequently pyrolyzing the transition metal raw material, so that the transition metal raw material can be easily pyrolyzed by heating. Is preferred.
- transition metal is Ru
- triruthenium dodecacarbonyl [Ru 3 (CO) 12 ] dichlorotetrakis (triphenylphosphine) ruthenium (II) [RuCl 2 (PPh 3 ) 4 ], dichlorotris (triphenylphosphine) Ruthenium (II) [RuCl 2 (PPh 3 ) 3 ], tris (acetylacetonato) ruthenium (III) [Ru (acac) 3 ], ruthenocene [Ru (C 5 H 5 )], ruthenium chloride [RuCl 3 ], etc. Is mentioned.
- transition metal is Fe
- pentacarbonyl iron [Fe (CO) 5 ] tetracarbonyl iron iodide [Fe (CO) 4 I 2 )]
- iron chloride [FeCl 3 ] iron chloride [FeCl 3 ]
- ferrocene [Fe (C 5 H 5). ) 2 tris (acetylacetonato) iron (III) [Fe (acac) 3 ], dodecacarbonyltriiron [Fe 3 (CO) 12 ] and the like.
- transition metal is Co
- cobalt chloride [CoCl 3 ] tris (acetylacetonato) cobalt (III) [Co (acac) 3 ], cobalt (II) acetylacetonato [Co (acac) 2 ], cobalt octa
- Examples include carbonyl [Co 2 (CO) 8 ], cobaltcene [Co (C 5 H 5 ) 2 ] and the like.
- transition metal carbonyl complexes are more preferred in terms of easy thermal decomposition and easy handling.
- the surface of the metal amide compound may change when immersed in a solvent such as alcohol.
- a carbonyl compound capable of supporting a transition metal by vapor deposition without using a solvent does not use a metal source while maintaining the surface structure. This is because it can be supported.
- Examples of carbonyl compounds other than the above include triosmium dodecacarbonyl [Os 3 (CO) 12 ] and molybdenum hexacarbonyl [Mo (CO) 6 ].
- a method for supporting the transition metal raw material on the metal amide supporting carrier is not particularly limited, but a method such as a vapor deposition method such as an impregnation method, a physical mixing method, and vapor deposition can be used. . *
- the metal amide-supporting carrier and the transition metal raw material are mixed.
- a specific mixing method is not particularly limited, but an impregnation method or a physical mixing method is used.
- the metal amide-supported carrier and the transition metal raw material are both solid, they are mixed by a physical mixing method. Can take the way.
- a method of mixing by impregnation as in the case of a powder or a porous body, or a CVD method (chemical vapor deposition method) on the surface of the transition metal raw material Further, they can be mixed by a vapor deposition method such as sputtering.
- the physical mixing method it can mix by the method performed normally, and what is called solid phase mixing can be performed, for example, it can mix using a mortar, a ball mill, etc.
- Specific examples of the mixing method in the impregnation method include a method in which the metal amide-supported carrier is dispersed and stirred in a solution obtained by dissolving the transition metal raw material in a solvent.
- the solvent for dissolving the transition metal raw material is not particularly limited as long as the transition metal raw material can be uniformly dissolved.
- a solvent such as n-hexane, benzene, toluene, THF, ethanol, liquid ammonia, dimethylformamide or the like is used. Can be mentioned. *
- the ratio of the transition metal raw material to the metal amide carrier in the raw material carrier step is not particularly limited, but the transition metal raw material is usually 0.01% by mass or more, preferably 0.02% by mass with respect to the metal amide carrier. % Or more, more preferably 0.05% by mass or more, and usually 40% by mass or less, preferably 30% by mass, more preferably 20% by mass or less. *
- the metal amide-supported carrier supporting the transition metal raw material can deposit the transition metal by thermal decomposition.
- the method of thermal decomposition is not particularly limited, and a commonly performed method can be used. Usually, thermal decomposition is performed in an inert gas stream such as nitrogen, argon, helium, or under vacuum.
- the metal amide-carrying carrier carrying the transition metal raw material is first evaporated to dryness by heating. And by continuing a heating, a transition metal raw material is reduce
- the temperature at the time of thermal decomposition is not particularly limited, but is usually 50 ° C. or higher and 200 ° C. or lower.
- the time for thermal decomposition is not particularly limited, but is usually 30 minutes or longer and 5 hours or shorter. *
- the BET specific surface area of the supported metal catalyst is not particularly limited, but is usually 10 m 2 / g or more, preferably 30 m 2 / g or more, usually 1000 m 2 / g or less, preferably 500 m 2 / g or less.
- the BET specific surface area is the same even when used as an ammonia synthesis catalyst.
- the supported metal catalyst containing the composite of the present invention can be used as a catalyst in various reactions. Specifically, it can be used for hydrogenation of unsaturated bonds such as olefins, acetylenes, aromatic rings, aldehyde groups, ⁇ and ⁇ unsaturated aldehydes, hydrocracking of hydrocarbons, hydrogen transfer reactions, and the like.
- the transition metal supported in this case is not particularly limited, but Ni, Pd, Pt, Rh, etc. are usually used. It can also be used as a catalyst for ammonia decomposition reaction.
- the transition metal supported in this case is not particularly limited, but usually, Ru, Fe, Co, Ni, Mo, Mn, Rh, etc. are exemplified, and Ru is preferable. *
- the supported metal catalyst containing the composite of the present invention is suitable for ammonia synthesis reaction. That is, the complex of the present invention can be used as an ammonia synthesis catalyst, and can also be used as an ammonia synthesis catalyst containing the complex as a reaction active component and components other than the complex. Specifically, ammonia can be produced by bringing a gas containing nitrogen and hydrogen into contact with the composite of the present invention. *
- the metal amide compound supported in the composite also functions as an active species, and the function as an active species is enhanced in cooperation with the transition metal particles supported in the composite.
- the function of the active species is further enhanced by the function of the carrier to increase the active component, and it is suitable as a supported metal catalyst.
- the composite of the present invention when used as an ammonia synthesis catalyst, it shows higher catalytic activity than a catalyst using a conventional two-dimensional electride compound as a carrier, and further stable catalytic activity can be obtained for a long time. And is suitable as an ammonia synthesis catalyst.
- ammonia Synthesis> a gas containing nitrogen and a gas containing hydrogen are brought into contact with an ammonia synthesis catalyst containing the complex of the present invention (hereinafter simply referred to as the ammonia synthesis catalyst of the present invention). It is characterized by synthesizing ammonia.
- the reaction form is not particularly limited as long as the above characteristics are satisfied, and a commonly used method can be adopted.
- ammonia produced by a method similar to the conventional Harbor Bosch method that is, by directly reacting a mixed gas of nitrogen and hydrogen under heating and pressurization and N 2 + 3H 2 ⁇ 2NH 3
- a method of separating by absorbing with cooling or water will be described.
- the reaction pressure of the mixed gas of nitrogen and hydrogen is not particularly limited, but is usually 10 kPa or more, preferably 100 kPa or more, and is usually 20 MPa or less, preferably 10 MPa or less, more preferably 1 MPa or less.
- the reaction efficiency is higher when the reaction is performed under a pressurized condition. Therefore, considering the practical use, the reaction pressure is preferably higher.
- the reaction pressure is high, a dedicated high-pressure reaction facility is required.
- the ammonia synthesis catalyst of the present invention is advantageous in that it can sufficiently synthesize ammonia even under a low pressure. Of the nitrogen and hydrogen gas subjected to the reaction, unreacted nitrogen and hydrogen gas can be recycled and used in the reactor after removing the produced ammonia. *
- the ammonia synthesis catalyst of the present invention when a catalyst is used in combination, the ammonia synthesis catalyst of the present invention is preferably used in the last reactor because of its high activity at low temperatures. That is, a high ammonia yield can be obtained by performing the final reaction at a low temperature which is balanced and advantageous.
- Evaluation of the complex of the present invention as an ammonia synthesis catalyst is obtained by dissolving the amount of NH 3 produced using the ammonia synthesis catalyst of the present invention into a gas chromatograph or NH 3 produced in an aqueous sulfuric acid solution, was determined by ion chromatography to determine the ammonia production rate, and the ammonia synthesis activity was evaluated based on the production rate.
- the obtained Ca (NH 2 ) 2 / ZrO 2 powder was about 1 g, and the BET specific surface area measured by the nitrogen adsorption method (NOVA 4200e, manufactured by Quantachrome) was 60 m 2 / g.
- N 2 nitrogen gas
- H 2 hydrogen gas
- NH 3 ammonia gas
- 0.1 g of the composite powder obtained above was packed in a glass tube as an ammonia synthesis catalyst and reacted in a fixed bed flow reactor.
- the gas flow rates were set to N 2 : 15 mL / min, H 2 : 45 mL / min, and a total of 60 mL / min, and the reaction was performed at a pressure of atmospheric pressure and a reaction temperature of 340 ° C.
- the gas coming out from the flow reactor was bubbled into a 0.005 M sulfuric acid aqueous solution, the produced ammonia was dissolved in the solution, and the resulting ammonium ions were quantified by ion chromatography.
- the production rate of ammonia at 340 ° C. was 7383 ⁇ mol / g ⁇ h as shown in FIG.
- the TOF was 16.7 ⁇ 10 ⁇ 3 / s.
- the activation energy from 340 ° C. to 250 ° C. was 65 kJ / mol.
- Example 3 Ru / Ca (NH) as in Example 1 except that the amount of Ca (NH 2 ) 2 supported in Example 1 was set to 30% by mass and the amount of metal Ca added was 0.177 g. 2 ) 2 / ZrO 2 was synthesized.
- the specific surface area of the obtained Ca (NH 2 ) 2 / ZrO 2 was 92.2 m 2 / g.
- the specific surface area of the obtained composite Ru / Ca (NH 2 ) 2 / ZrO 2 powder was 72 m 2 / g.
- an ammonia synthesis reaction was carried out in the same manner as in Example 1.
- the production rate of ammonia at 340 ° C. was 4229 ⁇ mol / g ⁇ h.
- Example 4 A composite Ru / Ca similar to Example 1 except that the amount of Ca (NH 2 ) 2 supported in Example 1 was set to 50% by mass and the amount of metal Ca added was 0.295 g. (NH 2 ) 2 / ZrO 2 was synthesized. The specific surface area of the obtained Ca (NH 2 ) 2 / ZrO 2 was 55 m 2 / g. Further, the specific surface area of the obtained composite Ru / Ca (NH 2 ) 2 / ZrO 2 was 42 m 2 / g. Using the obtained composite as an ammonia synthesis catalyst, an ammonia synthesis reaction was carried out in the same manner as in Example 1. The production rate of ammonia at 340 ° C. was 5082 ⁇ mol / g ⁇ h.
- Example 5 A composite Ru / Ca (NH 2 ) 2 / ZrO 2 was synthesized in the same manner as in Example 1 except that the amount of Ru supported in Example 1 was changed to 2% by mass. Using the obtained composite as an ammonia synthesis catalyst, an ammonia synthesis reaction was carried out in the same manner as in Example 1. The production rate of ammonia at 340 ° C. was 2930 ⁇ mol / g ⁇ h.
- Example 6 A composite Ru / Ca (NH 2 ) 2 / ZrO 2 was synthesized in the same manner as in Example 1 except that the amount of Ru supported in Example 1 was changed to 8% by mass. Using the obtained composite as an ammonia synthesis catalyst, an ammonia synthesis reaction was carried out in the same manner as in Example 1. The production rate of ammonia at 340 ° C. was 7420 ⁇ mol / g ⁇ h.
- Example 7 Except that CeO 2 (specific surface area 81.4 m 2 / g, JRC-CEO-3) was used as a carrier, CeO 2 (hereinafter referred to as Ca (NH 2 ) on which calcium amide was supported was carried out in the same manner as in Example 1. ) 2 / CeO 2 .
- the specific surface area of this Ca (NH 2 ) 2 / CeO 2 was 109 m 2 / g.
- a metal Ru was supported on Ca (NH 2 ) 2 / CeO 2 in the same manner as in Example 1 to obtain a powder of a composite (hereinafter referred to as Ru / Ca (NH 2 ) 2 / CeO 2 ). .
- the specific surface area of Ru / Ca (NH 2 ) 2 / CeO 2 was 76 m 2 / g.
- the Ru dispersion of Ru / Ca (NH 2 ) 2 / CeO 2 was 20.5%, and the Ru average particle size was 18.3 nm.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the complex used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / CeO 2 .
- the production rate of ammonia at 340 ° C. was 5255 ⁇ mol / g ⁇ h.
- the TOF was 15.2 ⁇ 10 ⁇ 3 s ⁇ 1 .
- the activation energy from 340 ° C. to 250 ° C. was 59 kJ / mol.
- Example 8 except for using TiO 2 (specific surface area 50 m 2 / g, Degussa Corporation P-25) as a carrier, in the same manner as in Example 1, TiO 2 (hereinafter calcium amide is carried, Ca (NH 2 ) 2 / TiO 2 was obtained.
- the specific surface area of this Ca (NH 2 ) 2 / TiO 2 was 105 m 2 / g.
- Metal Ru was supported on Ca (NH 2 ) 2 / TiO 2 in the same manner as in Example 1 to obtain a powder of a composite (hereinafter referred to as Ru / Ca (NH 2 ) 2 / TiO 2 ). .
- the specific surface area of Ru / Ca (NH 2 ) 2 / TiO 2 was 71 m 2 / g. Further, the Ru dispersion degree of this composite was 21.6%, and the Ru average particle diameter was 6.2 nm.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the composite used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / TiO 2 .
- the production rate of ammonia at 340 ° C. was 5557 ⁇ mol / g ⁇ h.
- the TOF was 14.4 ⁇ 10 ⁇ 3 s ⁇ 1 ).
- the activation energy from 340 ° C. to 250 ° C. was 61 kJ / mol.
- Example 9 Except for using MgO (specific surface area 30 m 2 / g, Ube Industries, Ltd., 500A) as a carrier, MgO loaded with calcium amide (hereinafter referred to as Ca (NH 2 ) Represented as 2 / MgO).
- the specific surface area of Ca (NH 2 ) 2 / MgO was 91 m 2 / g.
- a metal Ru was supported on Ca (NH 2 ) 2 / MgO in the same manner as in Example 1 to obtain a composite (hereinafter referred to as Ru / Ca (NH 2 ) 2 / MgO) powder.
- the specific surface area of Ru / Ca (NH 2 ) 2 / MgO was 44 m 2 / g. Further, the Ru dispersion degree of this composite was 28.6%, and the Ru average particle diameter was 4.6 nm.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the composite used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / MgO.
- the production rate of ammonia at 340 ° C. was 6904 ⁇ mol / g ⁇ h.
- the TOF was 13.8 ⁇ 10 ⁇ 3 s ⁇ 1 .
- the activation energy from 340 ° C. to 250 ° C. was 67 kJ / mol.
- Ta 2 O 5 (Example 10) carrier (specific surface area 20 m 2 / g), in the same manner as in Example 1, Ta 2 O 5 in which the calcium amide is carried (hereinafter, Ca (NH 2) expressed as 2 / Ta 2 O 5.) was obtained.
- Ca in (NH 2) 2 / Ta 2 O 5, metal Ru supported in the same manner as in Example 1, powder of a complex (hereinafter referred to as Ru / Ca (NH 2) 2 / Ta 2 O 5) Got the body.
- the specific surface area of Ru / Ca (NH 2 ) 2 / Ta 2 O 5 was 18 m 2 / g.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the composite used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / Ta 2 O 5 .
- the production rate of ammonia at 340 ° C. was 6370 ⁇ mol ⁇ 1 h ⁇ 1 .
- Nb 2 O 5 Example 11
- Ca (NH 2 ) expressed as 2 / Nb 2 O 5
- a metal Ru is supported on Ca (NH 2 ) 2 / Nb 2 O 5 in the same manner as in Example 1, and a composite powder (hereinafter referred to as Ru / Ca (NH 2 ) 2 / Nb 2 O 5 ) Got the body.
- the specific surface area of Ru / Ca (NH 2 ) 2 / Nb 2 O 5 was 60 m 2 / g.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the complex used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / Nb 2 O 5 .
- the production rate of ammonia at 340 ° C. was 4995 ⁇ molg ⁇ 1 h ⁇ 1 .
- Example 12 Al 2 O 3 as support (specific surface area 80 m 2 / g, Alfa Aesar Co.) except for using, in the same manner as in Example 1, Al 2 O 3 calcium amide is carried (Hereinafter referred to as Ca (NH 2 ) 2 / Al 2 O 3 ).
- the specific surface area of Ca (NH 2 ) 2 / Al 2 O 3 was 50 m 2 / g.
- Powder of composite hereinafter referred to as Ru / Ca (NH 2 ) 2 / Al 2 O 3 ) by supporting metal Ru on Ca (NH 2 ) 2 / Al 2 O 3 by the same method as in Example 1. Got the body.
- the specific surface area of Ru / Ca (NH 2 ) 2 / Al 2 O 3 was 35 m 2 / g.
- the ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the composite used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / Al 2 O 3 .
- the production rate of ammonia at 340 ° C. was 5094 ⁇ molg ⁇ 1 h ⁇ 1 .
- Example 13 Except that graphite (HSAG) (specific surface area 300 m 2 / g) was used as a support, graphite (hereinafter referred to as Ca (NH 2 ) 2 on which calcium amide was supported was obtained in the same manner as in Example 1. / Denoted as Gra). Metal Ru was supported on Ca (NH 2 ) 2 / Gra by the same method as in Example 1 to obtain a composite powder (hereinafter referred to as Ru / Ca (NH 2 ) 2 / Gra). The specific surface area of Ru / Ca (NH 2 ) 2 / Gra was 250 m 2 / g.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that the complex used as the ammonia synthesis catalyst was Ru / Ca (NH 2 ) 2 / Gra.
- the production rate of ammonia at 340 ° C. was 2909 ⁇ molg ⁇ 1 h ⁇ 1 .
- ammonia synthesis reaction was carried out in the same manner as in Example 1 except that Ru / ZrO 2 was used as the ammonia synthesis catalyst.
- the production rate of ammonia at 340 ° C. was 506 ⁇ mol / g ⁇ h as shown in FIG.
- Example 2 (Comparative Example 2) was placed a metal Ca powder 0.236g stainless steel pressure vessel in the first embodiment performs the same operation as in Example 1, was recovered powder Ca (NH 2) 2.
- An ammonia synthesis reaction was carried out in the same manner as in Example 1 except that Ru / Ca (NH 2 ) 2 was used as the ammonia synthesis catalyst.
- the production rate of ammonia at 340 ° C. was 2481 ⁇ mol / g ⁇ h as shown in FIG.
- the specific surface area of the metal amide powder represented by Ca (NH 2 ) 2 was 127 m 2 / g.
- C12A7 e - Ru / except that the carrier was 2 wt% on the Ru under the same conditions as in Example 1 a C12A7: e - to produce a supported metal catalyst powder represented by.
- the Ru dispersion degree measured by the CO adsorption method was 4.7%, and the Ru average particle diameter measured by the CO adsorption method was 28.7 nm.
- an ammonia synthesis reaction was carried out in the same manner as in Example 1.
- the production rate of ammonia at 340 ° C. was 2221 ⁇ mol / g ⁇ h.
- the TOF was 73.7 ⁇ 10 ⁇ 3 s ⁇ 1 .
- the activation energy from 340 ° C. to 250 ° C. was 91 kJ / mol.
- Comparative Example 5 A supported metal catalyst powder represented by Ru / Ca 3 N 2 supporting 2% by mass of Ru under the same conditions as in Example 1 except that Ca 3 N 2 was used as a support was produced.
- the Ru dispersion degree measured by the CO adsorption method was 3.0%, and the Ru average particle diameter measured by the CO adsorption method was 44 nm.
- an ammonia synthesis reaction was carried out in the same manner as in Example 1.
- the production rate of ammonia at 40 ° C. was 3164 ⁇ mol / g ⁇ h as shown in FIG.
- the TOF was 167 ⁇ 10 ⁇ 3 s ⁇ 1 .
- the activation energy from 340 ° C. to 250 ° C. was 66 kJ / mol.
- Example 6 An ammonia synthesis reaction was performed under the same conditions as in Example 1 except that Ru-Cs / MgO (Ru supported amount: 6 mass%) as the supported metal catalyst powder was used. As shown in FIG. 5, the production rate of ammonia at 340 ° C. was 4303 ⁇ mol / g ⁇ h. *
- FIG. 3 shows the Ca (NH 2) 2 supported amount different Ru / Ca (NH 2) 2 / ZrO 2 results in ammonia synthesis catalytic. It was found that the catalytic activity greatly improved with an increase in the amount of Ca (NH 2 ) 2 supported, and the highest activity was exhibited when 40% by mass was supported.
- Example 1 since the BET specific surface area of ZrO 2 as the support is 100 m 2 / g and the supported amount of the metal amide is 40% by mass with respect to the total amount with the support, the surface area of the support is 1 m 2.
- the amount that Ca (NH 2 ) 2 covers / g is 0.4% by mass.
- the minimum amount required for Ca (NH 2 ) 2 to coat a support with a surface area of 1 m 2 / g is 0.07% by mass, and the loading in each example is much higher than that amount. It is presumed that the metal amide can sufficiently cover the surface of the support, and the catalytic activity is improved by being a certain amount or more per 1 m 2 / g of the surface area of the support. On the other hand, if the loading amount increases too much, it is suggested that the effect of using the carrier cannot be obtained.
- FIG. 4 shows the results of ammonia synthesis when the supported amount of Ru is 2% by mass, 5% by mass, and 8% by mass with respect to the total amount of Ca (NH 2 ) 2 / ZrO 2 and Ru. As shown in FIG. 4, 5% by mass shows considerably higher activity than 2% by mass, but 8% by mass is not significantly different from 5% by mass, and the supported amount is 5% by mass. It was found to show sufficient activity.
- FIG. 5 shows a comparison of ammonia production rates depending on the carrier.
- C12A7 compared with a catalyst in which Ru is supported on e ⁇ or Ca 3 N 2 , a metal oxide carrier such as ZrO 2 , CeO 2 , TiO 2 , or MgO has Ca (NH 2 ) 2 and It was found that the composite of the present invention supporting Ru exhibited very excellent catalytic performance due to the synergistic action of the support, the metal amide compound, and the transition metal Ru particles.
- the one using graphite as a carrier also showed a high ammonia production rate.
- a supported metal catalyst in which a metal Ru is supported on a carbonaceous support such as graphite, ammonia is hardly produced and no catalytic activity is exhibited.
- the composite of the present invention it can be applied to ammonia production even if a carbonaceous carrier is used.
- the catalyst of the present invention exhibited higher ammonia synthesis activity than Ru—Cs / MgO of Comparative Example 6, which was conventionally said to have high activity.
- the ammonia synthesis reaction was continued for a long time at a reaction temperature of 340 ° C., and the stability of the catalyst was evaluated. 6, using a Ru / Ca (NH 2) 2 / amide reinforced supported metal catalyst represented by ZrO 2 and of Comparative Example 2 Ru / Ca (NH 2) 2 in Example 1 as a catalyst, subjected to ammonia synthesis The results are shown.
- the catalyst represented by Ru / Ca (NH 2 ) 2 of Comparative Example 2 that is not supported on the carrier decreases in catalytic activity with the reaction time, whereas the amide reinforcement of Example 1 supported on ZrO 2. It was found that the supported metal catalyst stably produced ammonia for 24 hours and hardly decreased the reaction activity.
- the amide-reinforced supported metal catalyst of the present invention is a supported metal catalyst Ru / C12A7: e ⁇ which is a mayenite type compound containing a conduction electron of 10 18 cm ⁇ 3 or more previously developed by the present inventors. And ammonia synthesis activity surpassing Ru / Ca 2 N. Further, it exhibits higher activity than the Ru—Cs / MgO catalyst, which is said to exhibit high activity.
- Table 2 shows the results of comparing the physical property evaluation and ammonia synthesis activity of each catalyst.
- the amide-reinforced supported metal catalyst of Example 1 represented by Ru / Ca (NH 2 ) 2 / ZrO 2 is represented by the conventional Ru / C12A7: e ⁇ of Comparative Example 4 or Ru / Ca 3 N 2 of Comparative Example 5. It can be seen that the specific surface area is large and the average particle size of the supported Ru is small compared to the supported metal catalyst. Therefore, it was found that even when the amount of Ru supported was increased, Ru was supported with good dispersibility and exhibited high catalytic activity.
- the activation energy of ammonia synthesis in each example is equivalent to that of the supported metal catalyst represented by Ru / Ca 3 N 2 in Comparative Example 5, and Ca amide synthesizes ammonia by almost the same mechanism as Ca nitride. It became clear that.
- Example 14 Ammonia decomposition reaction
- Ru / Ca (NH 2 ) 2 / ZrO 2 as a supported metal catalyst
- ammonia is decomposed to produce nitrogen and hydrogen. Reaction was performed.
- 0.1 g of the composite powder obtained above was packed in a glass tube as an ammonia decomposition catalyst and reacted in a fixed bed flow reactor.
- the gas flow rate was set to NH 3 : 5 mL / min, and the reaction was performed at a pressure of 0.1 MPa.
- the results are shown in FIG.
- the gas emitted from the flow reactor was quantified by gas chromatography.
- the decomposition efficiency of ammonia at 400 ° C. was 93%.
- the complex of the present invention causes strong electron transfer from the carrier to the metal, it is considered that when the complex of the present invention is used as a supported metal catalyst, it exhibits high catalytic activity for various reactions.
- the composite of the present invention has an effect of improving the stability of the supported metal catalyst, and can be expected to be used as various catalysts as the supported metal catalyst.
- the composite of the present invention can be used as various reaction catalysts in that it has high reaction activity as a supported metal catalyst.
- it can be used as a catalyst for ammonia synthesis, which has a long catalyst life and can be produced even at a low reaction pressure.
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Abstract
Description
(BET比表面積分析)
以下の実施例及び比較例のBET比表面積の測定は、対象物の表面に液体窒素温度で窒素ガスを吸着させ、単分子層吸着した窒素の量を測定した。分析条件は以下の通りである。
測定条件
装置:マイクロトラックベル社製 BELSORP-mini II
吸着ガス:窒素(99.99995%)
吸着温度:液体窒素温度(-196℃)
担体としてCeO2(比表面積81.4m2/g、JRC-CEO-3)を用いた以外は、実施例1と同様の方法により、カルシウムアミドが担持されたCeO2(以下、Ca(NH2)2/CeO2と表わす。)を得た。このCa(NH2)2/CeO2の比表面積は109m2/gであった。
<マイエナイト型化合物粉末の合成>
CaCO3及びAl2O3の各粉末をCaとAlの質量比が11:14となるように混合し、この混合物30gをアルミナ坩堝中にて1300℃加熱し、6時間維持した。得られた粉末をシリカガラス管内に挿入し1×10-4Paの真空中で1100℃、15時間加熱し、原料マイエナイト型化合物の粉末を得た。この段階でのマイエナイト型化合物粉末の比表面積は1m2/g以下であった。
Claims (13)
- 遷移金属と、担体と、下記一般式(1)で表される金属アミド化合物とを含む複合体であり、 前記担体は、金属酸化物又は炭素質担体であり、前記金属アミド化合物が、下記一般式(1)で表される金属アミド化合物であることを
特徴とする複合体。 M(NH2)x ・・・(1)(前記一般式(1)において、Mは、Li、Na、K、Be、Mg、Ca、Sr、Ba及びEuから選ばれる少なくとも1種の金属原子を表わし、xはMの価数を表す。) - 前記担体が、塩基性、中性、又は弱酸性の金属酸化物である請求項1に記載の複合体。
- 前記担体が、ZrO2、TiO2、CeO2、Al2O3、Nb2O5、Ta2O5、又はMgOから選ばれる少なくとも1種の金属酸化物である請求項1又は2に記載の複合体。
- 前記複合体のBET比表面積が、10m2/g以上である請求項1~3のいずれか1項に記載の複合体。
- 前記金属原子MがCaである請求項1~4のいずれか1項に記載の複合体。
- 前記遷移金属がRuである請求項1~5のいずれか1項に記載の複合体。
- 請求項1~6のいずれか1項に記載の複合体を含む担持金属触媒。
- 請求項1~6のいずれか1項に記載の複合体を含むアンモニア合成触媒。
- 請求項1~6のいずれか1項に記載の複合体の製造方法であって、前記金属原子Mを含む金属原子源、前記担体、及び液体アンモニアを混合する工程及び、前記金属原子源と液体アンモニアを反応させ、前記担体に前記金属アミド化合物を生成させ、金属アミド担持担体を得る工程を含むことを特徴とする複合体の製造方法。
- 前記金属アミド担持担体に、前記遷移金属の原料化合物(以下、遷移金属原料)を担持させる工程と、前記遷移金属原料を熱分解して前記遷移金属を析出させる工程を含むことを特徴とする請求項9に記載の複合体の製造方法。
- アンモニアの合成方法であって、窒素を含むガス及び水素を含むガスを、請求項8に記載のアンモニア合成触媒に接触させ、アンモニアを合成することを特徴とするアンモニア合成方法。
- 前記アンモニア合成触媒に接触させる際の温度が、100℃以上600℃以下である請求項11に記載のアンモニア合成方法。
- 前記アンモニア合成触媒に接触させる際の圧力が、10kPa以上20MPa以下である請求項11又は12に記載のアンモニア合成方法。
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