WO2015136954A1 - アンモニア合成触媒及びアンモニア合成方法 - Google Patents
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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- 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
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to an ammonia synthesis catalyst used for synthesizing ammonia by reacting hydrogen and nitrogen using a gas containing hydrogen and nitrogen as raw materials, and an ammonia synthesis method using the catalyst.
- Ammonia synthesis is one of the fundamental processes in the chemical industry, and the Haber-Bosch method using iron oxide as a catalyst and potassium hydroxide as an accelerator has become widespread. There was not much change.
- nitrogen and hydrogen gas are reacted on the catalyst at a high temperature and high pressure of 300 to 500 ° C. and 20 to 40 MPa.
- the reaction for synthesizing ammonia using a gas containing hydrogen and nitrogen as a raw material is represented by N 2 + 3H 2 ⁇ 2NH 3 , but since this reaction is an exothermic reaction, at low temperatures to move the equilibrium to the right Somehow better, but the number of molecules is reduced by the reaction, so higher pressure is better to move the equilibrium to the right.
- Ru is used as a metal catalyst particle for synthesis of ammonia on a support and used, it is known that the reaction proceeds at a low pressure, and is attracting attention as a second generation ammonia synthesis catalyst.
- the catalytic ability of Ru alone substance is very small, and a material with high electron donating property is used at the same time to exert the ability to break the triple bond of nitrogen molecule and convert it to adsorbed nitrogen atom on Ru metal catalyst particles.
- a catalyst for ammonia synthesis As a catalyst for ammonia synthesis, as a transition metal having ammonia synthesis activity at a low temperature of 300 ° C. or less, a kind of element of Mo, W, Re, Fe, Co, Ru, Os, or Fe, Ru, Ru and A catalyst containing any one of a combination of Re, Fe and Mo, K or Na, alumina, tria, zirconia or silica, wherein the transition metal and alkali metal are substantially in a metal state (Patent Document 1) , A catalyst capable of synthesizing ammonia even at a low temperature such as 200 ° C., in which any one of group 8 or group 9 transition metals such as Fe, Ru, Os, Co and alkali metal is supported on activated carbon or porous carbon.
- Patent Document 2 a catalyst using an alkali metal salt instead of an alkali metal and using graphite-containing carbon having a specific surface area as a catalyst carrier
- Patent Document 3 A catalyst for ammonia production in which a ruthenium compound containing no metal-like ruthenium or chlorine and a rare earth element compound is supported on a hardly-reducible oxide such as alumina or magnesia (Patent Document 4), Ru, Ni and Ce, There is an ammonia synthesis catalyst (Patent Document 5) in which at least a part of cerium is in a trivalent state.
- the electride catalyst made of Ru / CaO—Al 2 O 3 incorporates electrons into the crystal structure of the CaO—Al 2 O 3 compound, and can also incorporate hydrogen atoms from the surrounding gas during the reaction. From these two characteristics, it is reported that the catalyst has high catalytic activity for ammonia synthesis (Non-patent Document 1), and it catalyzes raw material nitrogen and hydrogen under reaction conditions of 100 to 600 ° C. and reaction pressure of 10 kPa to 30 MPa.
- Patent Document 6 A patent application has been filed for an invention relating to the ammonia synthesis method reacted above.
- Perovskite complex oxides have been tried to be applied to various uses such as exhaust gas purification catalysts, superconducting oxides, piezoelectric bodies, sensors, and fuel cell electrolytes.
- Ru catalyst supported on BaCeO 3 nanocrystals is 623 K or less as an ammonia synthesis catalyst compared to Ru / ⁇ -Al 2 O 3 , Ru / MgO, and Ru / CeO 2 catalysts. It has been reported that the catalytic activity at low temperature is excellent (Non-patent Document 2).
- an ammonia synthesis catalyst comprising Ru / BaZrO 3 (Non-patent Document 3, Patent Documents 7 and 8) or an ammonia synthesis comprising a titanium-containing perovskite oxide such as Ru / BaTiO 3 , Ru / SrTiO 3 , Ru / CaTiO 3.
- a titanium-containing perovskite oxide such as Ru / BaTiO 3 , Ru / SrTiO 3 , Ru / CaTiO 3.
- Substituted titanium-containing oxides also called “titanium-containing perovskite-type oxides” have extremely high relative dielectric constants, so they are used as devices such as capacitor materials and dielectric films, and other perovskite-type oxides. From the viewpoint of using transition metal oxides as substrate materials and nonlinear resistors, research has been actively conducted since ancient times.
- titanate oxyhydrides of titanium based on the formula ATi (O, H) 3 (A is Ca 2+ , Sr 2+ , or Ba 2+ ) ( Non-patent documents 6 to 8, Patent document 10).
- This acid hydride is a compound in which hydrogen is mixed with oxide ions (O 2 ⁇ ) as hydride (H ⁇ ), and the precursor ATiO 3 is a metal hydride such as CaH 2 , LiH, or NaH.
- This oxyhydride is characterized by having hydride ion / electron mixed conductivity and hydrogen storage / release performance.
- a reaction of synthesizing ammonia using a gas containing hydrogen and nitrogen as a raw material is represented by N 2 + 3H 2 ⁇ 2NH 3 , but there are three points that are bottlenecks in moving the equilibrium to the right.
- the first is the difficulty of bond-breaking of nitrogen bonds between N 2 molecules
- the second is a phenomenon in which the surface of catalytic metal particles is covered with hydrogen atoms dissociated and adsorbed under high pressure. This is a decrease in catalytic activity due to hydrogen poisoning.
- the present inventor uses a titanium-containing perovskite type oxyhydride containing hydride (H ⁇ ), which has been successfully synthesized by the present inventors, as a support, and a metal having catalytic activity such as Ru or Fe. If by supporting to form the catalyst, hydride (H -) by specific action of the ammonia synthesis activity is dramatically improved, it is used for the promoter compound unstable alkali metals or alkaline earth metals and their compounds It is found that the ammonia synthesis catalyst is stable even in a long-time reaction, is significantly more active than the conventionally known catalyst having the highest activity, and can realize highly efficient ammonia synthesis at a low pressure of less than 20 MPa. It was.
- nitride ions were introduced through the H / N exchange process of “N” and BaTi (O, H, N) 3 was formed.
- the present invention is based on the above findings, and a perovskite type oxyhydride powder containing hydride (H ⁇ ) is used as a carrier, and the carrier is supported with a metal or a metal compound exhibiting catalytic activity for ammonia synthesis.
- An ammonia synthesis catalyst An ammonia synthesis catalyst,
- the perovskite-type acid hydrides, ATiO 3-x H x ( A is, Ca, Sr, or Ba, 0.1 ⁇ x ⁇ 0.6) is represented by.
- the perovskite oxyhydride may further contain nitrogen.
- Composition in containing nitrogen the formula ATi (O 3-z H x N y) (A, Ca, Sr, or Ba, 0.1 ⁇ x ⁇ 0.6,0 ⁇ y ⁇ 0.3, z ⁇ x + y, zxy Represents the amount of oxygen defects).
- the metal exhibiting catalytic activity is supported as nano metal particles on the powder surface.
- the metal compound exhibiting catalytic activity is supported by being mixed with the powder.
- the preferable metal of the metal or metal compound exhibiting the catalytic activity is Ru, and the supported amount is preferably 0.1 to 5% by weight with respect to the support as Ru metal.
- the method for producing a catalyst of the present invention uses an alkali metal or alkaline earth selected from LiH, CaH 2 , SrH 2 , and BaH 2 in a vacuum or in an inert gas atmosphere using a perovskite-type titanium-containing oxide powder as a starting material. By maintaining a temperature range of 300 ° C.
- the production method of the catalyst of the present invention may be up to the third step, but after the third step, the metal compound is further reduced by heating in a reducing atmosphere or pyrolyzing in a vacuum. It is preferable to include a fourth step of preparing a catalyst having nanometal particles supported on the powder surface.
- a step of treating the perovskite type oxyhydride powder in the presence of a nitrogen source material to cause the perovskite type oxyhydride to contain nitrogen You may have.
- the third step or the fourth step there may be a step of treating the catalyst in the presence of a nitrogen source material to cause the perovskite type oxyhydride to contain nitrogen.
- the ammonia synthesis method of the present invention is a method of synthesizing ammonia by reacting hydrogen and nitrogen using a gas containing hydrogen and nitrogen as raw materials, and filling the catalyst packed bed in the synthesis reactor with the catalyst described above.
- the raw material nitrogen and hydrogen are reacted on the catalyst at a reaction temperature of 300 ° C. to 450 ° C. under a reaction pressure of 10 kPa or more and less than 20 MPa.
- the catalyst of the present invention is a conventional catalyst such as Fe / Fe 3 O 4 , Fe / C, Ru / C for synthesizing ammonia by reacting hydrogen and nitrogen using a gas containing hydrogen and nitrogen as raw materials.
- the reaction can be performed at a low pressure, with a small amount of catalyst, even at a low temperature, and the reaction can be easily controlled.
- an accelerating compound such as an alkali metal, an alkali metal compound, or an alkaline earth metal compound as in a conventional carrier such as alumina, the production is simple.
- FIG. 1 shows a comparison of the catalytic activities of the Ru / BaTiO 2.5 H 0.5 catalyst of Example 1, the Ru / BaTiO 2.4 D 0.6 catalyst of Example 2, and the conventional catalyst.
- the upper horizontal bar of each catalyst indicates the NH 3 synthesis concentration (% by volume), and the lower horizontal bar indicates the NH 3 synthesis rate (mmolg ⁇ 1 h ⁇ 1 ).
- FIG. 2 shows a comparison of the catalytic activities of the Co / BaTiO 2.5 H 0.5 catalyst of Example 3, the Fe / BaTiO 2.5 H 0.5 catalyst of Example 4, and the conventional catalyst.
- FIG. 1 shows a comparison of the catalytic activities of the Ru / BaTiO 2.5 H 0.5 catalyst of Example 1, the Ru / BaTiO 2.4 D 0.6 catalyst of Example 2, and the conventional catalyst.
- the upper horizontal bar of each catalyst indicates the NH 3 synthesis concentration (% by volume), and the lower horizontal bar indicates the NH 3 synthesis rate (mmolg ⁇ 1 h ⁇
- FIG. 3 shows a comparison (literature value) of the catalytic activity of an electride catalyst composed of Ru / CaO—Al 2 O 3 and a typical catalyst that has been conventionally reported.
- FIG. 4 is a schematic diagram of the crystal structure of a Ti-containing perovskite oxyhydride.
- FIG. 5 is a drawing-substituting photograph showing a TEM image of the Ru-supported catalyst obtained in Example 1 and Comparative Example 1.
- FIG. 6 is a schematic diagram of an apparatus used for ammonia synthesis evaluation in Example 1.
- FIG. 7 is a graph showing an ammonia production evaluation result in Example 1.
- the ammonia synthesis catalyst of the present invention is composed of a support made of a perovskite type oxyhydride powder containing hydride (H ⁇ ), and a metal or a metal compound exhibiting catalytic activity for ammonia synthesis supported on the support.
- the titanium-containing perovskite type oxyhydride is obtained by replacing a part of oxide ions contained in the titanium-containing perovskite type oxide with hydride ions (H ⁇ ).
- the Ti-containing perovskite oxide can take in hydride ions (H ⁇ ) from a low concentration to a high concentration under specific heat treatment conditions, and has the formula ATiO 3-x H x (A is Ca, Sr, Or, Ba, 0.1 ⁇ x ⁇ 0.6).
- the value of x is less than 0.1, the effect of improving the catalytic activity by hydride ions is not sufficient, and when it exceeds 0.6, the crystallinity is deteriorated and impurities are generated, which is not desirable.
- the higher the hydrogen content indicated by x the higher the catalytic activity for ammonia synthesis.
- a more preferable range of the value of x is 0.3 to 0.6.
- the Ti-containing perovskite oxyhydride maintains a perovskite structure composed of an octahedron with a shared apex. Ti atoms are present at the center of the octahedron, and oxide anions and hydride anions are present at the apexes of the octahedron.
- oxyhydrides of Ti-containing perovskite oxides include ATi (O, H) 3 (A is Ca, Sr, or Ba), SrTi (O, H) 3 , and Sr 3 Ti 2 (O , H) 7 , Sr 2 Ti (O, H) 4 and the like.
- the catalyst of the present invention can be produced by the following steps. ⁇ First step: Preparation of Ti-containing perovskite oxyhydride>
- the titanium-containing perovskite type oxyhydride is obtained by using a perovskite type titanium-containing oxide powder as a starting material, and in a vacuum or in an inert gas atmosphere, lithium hydride (LiH), calcium hydride (CaH 2 ), strontium hydride ( SrH 2 ), alkali metal or alkaline earth metal hydride powder selected from barium hydride (BaH 2 ), maintained at a temperature range of 300 ° C. or higher and lower than the melting point of the hydride, preferably 300 ° C. or higher and 600 ° C. or lower.
- the starting Ti-containing perovskite oxide can be represented by the general formula ATiO 3 (A is Ca, Sr, or Ba).
- the Ti-containing perovskite oxide used as a starting material is not particularly limited in its production method and form.
- the perovskite oxide is manufactured by various methods such as a solid phase method, an oxalic acid method, a citric acid method, a hydrothermal method, and a sol-gel method.
- As the catalyst a larger specific surface area is desirable, and a specific surface area is 30 m 2 / g or more and a particle size distribution of about 5 to 500 nm are desirable.
- the resulting Ti-containing perovskite oxide containing hydride ions has both hydride ion conductivity and electron conductivity, and further has reactivity with an external hydrogen gas at a low temperature of about 450 ° C. or less.
- the obtained Ti-containing perovskite oxyhydride is treated in the presence of a nitrogen source material such as ammonia gas, nitrogen gas, or nitrogen compound to contain nitrogen in the perovskite oxyhydride.
- a nitrogen source material such as ammonia gas, nitrogen gas, or nitrogen compound to contain nitrogen in the perovskite oxyhydride.
- Ti-containing perovskite oxyhydrides into which nitride ions are introduced have the formula BTi (O 3 ⁇ z H x N y ) (0.1 ⁇ x ⁇ 0.6, 0 ⁇ y ⁇ 0.3, z ⁇ x + y, zxy is an oxygen defect Represents the amount).
- the metal is supported on the perovskite oxyhydride support by an impregnation method.
- a compound such as chloride is used as the metal compound used as a raw material.
- examples of the ruthenium compound include ruthenium chloride, ruthenium carbonyl, ruthenium acetylacetonate, potassium ruthenium cyanate, potassium ruthenate, ruthenium oxide, and ruthenium nitrate. These metal compounds are dissolved in a polar organic solvent such as acetone or tetrahydrofuran, or water to form a solvent solution. A perovskite type oxyhydride powder is dispersed in this solvent solution, and then the solvent is evaporated to prepare a catalyst precursor.
- a polar organic solvent such as acetone or tetrahydrofuran
- the catalyst precursor obtained in the second step is dried to prepare a catalyst in which the powder is loaded with a metal compound exhibiting catalytic activity.
- a hydrogen reduction treatment is usually performed, and therefore the subsequent reduction step of the metal compound may be omitted.
- the metal compound is further reduced by heating in a reducing atmosphere or thermally decomposed in a vacuum, and nanometal particles are supported on the powder surface.
- the hydrogen reduction temperature is preferably 100 ° C. to 700 ° C., preferably 300 ° C. to 600 ° C., and the hydrogen reduction time is usually preferably 1 to 5 hours.
- the supported amount of metal or metal compound exhibiting catalytic activity is 0.1 to 20 wt% with respect to the support as metal.
- the most preferable metal exhibiting catalytic activity is ruthenium. However, since it is an expensive metal, ruthenium is preferably 0.1 to 5 wt%.
- the catalyst may be treated in the presence of a nitrogen source material to cause the perovskite oxyhydride to contain nitrogen.
- a nitrogen source material to cause the perovskite oxyhydride to contain nitrogen.
- Ti-containing perovskite oxyhydride is converted into ammonia gas or N 2 / H 2 in the same manner as in the case where nitride ions are previously introduced into the perovskite oxyhydride after the first step and before the second step. What is necessary is just to heat to the low temperature of 400-600 degreeC in mixed airflow.
- the catalyst powder in order to react hydrogen and nitrogen using a gas containing hydrogen and nitrogen as raw materials, the catalyst powder is filled in a catalyst packed bed in a synthesis reactor, and the raw material gas is used as a catalyst.
- ammonia is synthesized by reacting on the powder layer.
- a typical form of the reaction is the same as in the conventional Harbor Bosch method, in which a mixed gas of nitrogen and hydrogen is directly reacted under heat and pressure, and the ammonia produced by the reaction of N 2 + 3H 2 ⁇ 2NH 3 is cooled or with water. It is a method of absorbing and separating. Nitrogen and hydrogen gas are supplied in contact with the catalyst powder layer installed in the reactor. Before supplying nitrogen and hydrogen gas, it is preferable to reduce the surface of the catalyst with hydrogen gas or a mixed gas of hydrogen and nitrogen to remove oxides and the like adhering to the supported catalyst surface.
- the ammonia synthesis reaction is preferably carried out in an atmosphere containing as little water as possible, that is, in dry nitrogen and hydrogen, which is an atmosphere having a water vapor partial pressure of about 0.1 kPa or less.
- ammonia is synthesized by heating the catalyst in a mixed gas atmosphere of raw material nitrogen and hydrogen. It is preferable to carry out under the condition that the molar ratio of nitrogen to hydrogen is about 1/10 to 1/1.
- the reaction temperature is from room temperature to less than 500 ° C.
- the reaction temperature is more preferably about 300 to 350 ° C. The lower the reaction temperature, the more favorable the equilibrium is for ammonia production, and the above range is preferred in order to obtain a sufficient ammonia production rate and at the same time favor the equilibrium for ammonia production.
- the reaction pressure of the mixed gas of nitrogen and hydrogen during the synthesis reaction is not particularly limited, but is preferably 10 kPa to 20 MPa, more preferably 10 kPa to 5 MPa. In consideration of practical use, it is preferable that use under atmospheric pressure to pressurized conditions is possible. Therefore, practically, about 100 kPa to 1.5 MPa is more preferable.
- the reaction apparatus may be a batch-type reaction vessel, a closed circulation system reaction apparatus, or a distribution system reaction apparatus, but the distribution system reaction apparatus is most preferable from a practical viewpoint.
- the function of the catalyst of the present invention will be described below, but this is an estimate and does not limit the scope of the present invention.
- the reason why the catalyst of the present invention exhibits excellent performance is considered to be due to a unique function that hydride ions in the carrier exert on the raw material nitrogen molecules and hydrogen molecules. That is, the heterogeneous catalyst is usually constituted by supporting metal catalyst particles on a carbon or metal oxide support. In the oxidation reaction by the catalyst, the metal oxide may directly participate in the reaction, but in various hydrogenation reactions, the metal oxide itself is inactive as a carrier, and has a relatively indirect role such as simply supporting metal particles. I played.
- Ti-containing perovskite oxyhydrides dissociate gas molecules such as hydrogen molecules directly at around 300 to 450 ° C. and preferentially adsorb on the support, and directly by the conversion reaction between hydride ions and nitrogen molecules. It is presumed to participate in a reaction that dissociates nitrogen molecules. This is considered to prevent poisoning due to hydrogen accumulation in metal particles. This is considered to be due to an unknown attribute of the perovskite type oxyhydride containing hydride (H ⁇ ) under ammonia synthesis conditions, which is completely different from the conventional catalyst support.
- Synthesis of oxyhydride 0.3 g of commercially available BaTiO 3 powder having a particle size ranging from 100 nm to 200 nm was mixed with 3 equivalents of CaH 2 powder in a glove box, shaped into tablets with a hand press, and then the internal volume BaTiO 2.5 H 0.5 powder in which some of the oxide ions are replaced with hydride ions by vacuum-sealing into a glass tube of about 15 cm 3 , holding at 500 to 600 ° C. for 168 hours (one week), and performing a hydrogenation reaction. Synthesized.
- Ru support The synthesized BaTiO 2.5 H 0.5 powder was mixed with Ru 3 (CO) 12 in THF and stirred for 3 hours, and then the solvent was evaporated at 40 ° C. under reduced pressure to prepare a catalyst precursor. Next, this precursor was dried and vacuum-sealed again in a glass tube, and then heated to 390 ° C. for 3 hours to thermally decompose the carbonyl compound to obtain Ru / BaTiO 2.5 H 0.5 powder carrying Ru metal particles. The amount of ruthenium supported in the obtained Ru / BaTiO 2.5 H 0.5 powder was 1.0 wt% as Ru.
- FIG. 5 shows TEM images of the catalysts obtained in Example 1 (FIG. 5A) and Comparative Example 1 (FIG. 5B). From the TEM image, it can be seen that the particle diameter of the carrier of Example 1 is about 100 to 200 nm and the Ru particle diameter is around 5 nm.
- Ammonia synthesis was performed in a fixed bed flow type apparatus as shown in FIG.
- a vertical reaction tube 1 was used as a synthesis reactor, and 0.1 g of Ru / BaTiO 2.5 H 0.5 catalyst (Ru 1 wt%) 3 of Example 1 was packed in the catalyst packed layer on the glass wool 2 at the center.
- the valve 4 was opened, the valves 5, 6, and 7 were closed, the temperature in the reaction tube 1 was set to 400 ° C., and the catalyst was reduced in a hydrogen stream for 2 hours.
- FIG. 7 the result of ammonia production
- the horizontal axis represents relative time
- the vertical left axis represents ion current
- the vertical right axis represents reaction temperature.
- Temperature transition between 200 ° C. and 400 ° C. Is indicated by a dotted line.
- the amount of NH 3 produced increased as the temperature increased, and the NH 3 production rate did not decline while the temperature was kept constant at 400 ° C.
- Example 1 and Example 2 exhibited significantly higher catalytic activity than the Ru / BaTiO 3 catalyst of Comparative Example 1 in which Ru was supported on BaTiO 3 powder that was not subjected to hydrogenation reaction.
- the Ru—Cs / MgO catalyst of Comparative Example 3 has been reported as a highly active catalyst for a long time, and the catalyst of the present invention has been confirmed to have an activity exceeding this.
- the catalysts supporting Co and Fe of Examples 3 and 4 are not as active as Ru / BaTiO 2.5 H 0.5 catalysts, but the activity was remarkably improved by using an oxyhydride support. .
- Literature values are the evaluation conditions of Examples 1, 2, 3, 4 and Comparative Examples 1 and 3 in that the pressurizing condition is 0.1 MPa and the flow rate is 60 ml / min (the pressurizing condition is 5.0 MPa, flow rate; 110 ml / min) and so differs from example 1, 2, 3, 4, the catalytic catalyst activity and Ru-Cs / MgO and Ru / C12A7: e - can not be a simple comparison between the catalytic activity of the catalyst However, it can be seen that the Ru—Cs / MgO of Comparative Example 3 has a larger catalytic activity than the typical catalysts reported so far, and the second largest after Ru / C12A7: e ⁇ .
- the catalyst of the present invention utilizes a general-purpose Ti-containing perovskite oxide in place of a Ru catalyst using various carriers in a method for industrially synthesizing ammonia using a gas containing hydrogen and nitrogen as raw materials.
- a catalyst with significantly improved catalytic activity can be obtained even when used at low pressure instead of conventional high-pressure reaction conditions, so that ammonia can be synthesized with low energy and high efficiency.
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Abstract
Description
チタン含有ペロブスカイト型酸水素化物は、チタン含有ペロブスカイト型酸化物に含まれる酸化物イオンの一部を水素化物イオン(H-)で置換したものである。Ti含有ペロブスカイト型酸化物は、水素化物イオン(H-)を特定の熱処理条件で低濃度からから高濃度まで取り込むことが可能であり、式ATiO3-xHx(Aは、Ca,Sr,又はBa、0.1≦x≦0.6)で表すことができる。xの値が、0.1未満では、水素化物イオンによる触媒活性向上の効果が十分ではなく、また0.6を超えると、結晶性が悪くなり、不純物が出てくるので望ましくない。この範囲内でxで示される水素含有量が大きいほどアンモニア合成に対する触媒活性は高くなる。xの値のより好ましい範囲は、0.3~0.6である。
<第1工程;Ti含有ペロブスカイト型酸水素化物の調製>
チタン含有ペロブスカイト型酸水素化物は、ペロブスカイト型チタン含有酸化物の粉末を出発原料とし、真空中又は不活性ガス雰囲気中で水素化リチウム(LiH)、水素化カルシウム(CaH2)、水素化ストロンチウム(SrH2)、水素化バリウム(BaH2)から選ばれるアルカリ金属又はアルカリ土類金属の水素化物粉末とともに300℃以上、該水素化物の融点未満の温度範囲、望ましくは300℃以上600℃以下に保持した後、室温に冷却して、該酸化物中の酸化物イオンの一部を水素化物イオンで置換することによってペロブスカイト型酸水素化物の粉末として調製できる。保持温度までの昇温速度、室温までの降温速度には制限はない。保持に要する時間は温度にもよるが1時間程度以上1週間程度まででよい。
ペロブスカイト型酸水素化物担体への金属の担持は、含浸法により行う。原料として使用される金属化合物は塩化物をはじめとする化合物を使用する。特にペロブスカイト型酸水素化物の特異な性質を維持でき、分解が容易なカルボニル化合物又は錯体の使用が好ましい。例えば、触媒活性を示す金属としてRuを用いる場合は、ルテニウム化合物として、塩化ルテニウム、ルテニウムカルボニル、ルテニウムアセチルアセトナート、ルテニウムシアン酸カリウム、ルテニウム酸カリウム、酸化ルテニウム、硝酸ルテニウム等が挙げられる。これらの金属化合物はアセトン、テトラヒドロフラン等の極性有機溶媒、又は水に溶解させて溶媒溶液とする。ペロブスカイト型酸水素化物粉末をこの溶媒溶液に分散し、次いで、溶媒を蒸発させて、触媒前駆体を調製する。
さらに、第2工程で得られた触媒前駆体を乾燥して、該粉末に触媒活性を示す金属化合物を担持した触媒を調製する。アンモニア合成反応に触媒を使用する前には、通常、水素還元処理を行うので次工程の金属化合物の還元工程を省略してもよい。
第3工程の後に、さらに前記金属化合物を還元雰囲気中で加熱して還元するか真空中で熱分解して、該粉末表面にナノ金属粒子を担持させる。金属化合物を水素還元して該粉末表面にナノ金属粒子を形成する場合、水素還元温度は100℃~700℃、好ましくは300℃~600℃、水素還元時間は通常1~5時間が好ましい。
本発明のアンモニア合成方法は、水素と窒素を含有するガスを原料として水素と窒素とを反応させるために、前記の触媒粉末を合成反応器内の触媒充填層に充填して、原料ガスを触媒粉末層上で反応させてアンモニアを合成する方法である。反応の代表的一形態は、従来のハーバー・ボッシュ法と同じく、窒素と水素の混合気体を加熱加圧下で直接反応させ、N2+3H2→2NH3の反応よって生成したアンモニアを冷却又は水で吸収して分離する方法である。窒素及び水素ガスは、反応器内に設置した触媒粉末層に接触するように供給する。窒素及び水素ガスを供給する前に触媒の表面を水素ガス又は水素と窒素の混合ガスで還元処理を行い、担持された触媒表面に付着している酸化物等を除去することが好ましい。
本発明の触媒の機能を以下に説明するが、これは推定であって本発明の範囲を限定するものではない。本発明の触媒が優れた性能を示す理由は、担体中の水素化物イオンが原料の窒素分子、水素分子に及ぼす特異な機能によるものと考えられる。すなわち、不均一触媒は通常、炭素や金属酸化物担体の上に、金属触媒粒子を担持することにより構成される。触媒による酸化反応では金属酸化物が直接反応に加わることがあるが、様々な水素化反応では金属酸化物自身は担体として不活性であり、単に金属粒子の担持など、比較的間接的な役割を果たしていた。
粒径が100nmから200nmの範囲に分布する市販のBaTiO3粉末0.3gを3当量のCaH2粉末とグローブボックス中で混合し、ハンドプレス器により錠剤整形した後、内部容量約15cm3のガラス管へ真空封入し、500~600℃で168時間(一週間)保持し水素化反応を行なって酸化物イオンの一部が水素化物イオンで置換されたBaTiO2.5H0.5粉末を合成した。
合成したBaTiO2.5H0.5粉末をRu3(CO)12のTHF溶液に混合し3時間撹拌した後、減圧状態、40℃で溶媒を蒸発させて触媒前駆体を調製した。次いで、この前駆体を乾燥した後、ガラス管へ再び真空封入した後、390℃に3時間加熱しカルボニル化合物を熱分解してRu金属粒子を担持したRu/BaTiO2.5H0.5粉末を得た。得られたRu/BaTiO2.5H0.5粉末中のルテニウム担持量はRuとして1.0wt%であった。
図5に、実施例1(図5A)と比較例1(図5B)で得られた触媒のTEM像を示す。TEM像から、実施例1の担体の粒子径が約100~200nmであり、Ru粒子径は5nm前後であることが分かる。
実施例1のCaH2粉末に代えてCaD2(Dは、重水素)粉末を用いる以外は実施例1と同一の条件でヒドリドの濃度が高いBaTiO2.4D0.6粉末を合成した。CaD2は、塊状のCaをD2と600℃で30分反応させ、これを窒素雰囲気下で砕いた後、粉砕物を再びD2と反応させ、この作業を3回繰り返し純粋な粉末を作成した。
2.Ru担持
この粉末に実施例1と同様にRuを担持させた。
実施例1と同一の条件でBaTiO2.5H0.5粉末を合成した。
2.Co担持
合成したBaTiO2.5H0.5粉末をCo(アセチルアセトナート)3のTHF溶液に混合し3時間撹拌した後、減圧状態、40℃で溶媒を蒸発させて触媒前駆体を調製した。この触媒前駆体は、アンモニア合成評価装置の触媒充填層に充填して水素気流中で2時間還元してCo/BaTiO2.5H0.5触媒として用いた。
実施例1と同一の条件でBaTiO2.5H0.5粉末を合成した。
2.Fe担持
合成したBaTiO2.5H0.5粉末をFe(アセチルアセトナート)3のTHF溶液に混合し3時間撹拌した後、減圧状態、40℃で溶媒を蒸発させて触媒前駆体を調製した。この触媒前駆体は、アンモニア合成評価装置の触媒充填層に充填して水素気流中で2時間還元してFe/BaTiO2.5H0.5触媒として用いた。
水素化反応を行なっていないBaTiO3粉末に実施例1と同じ条件でRuを担持させてRu/BaTiO3触媒を得た。
比較例1のBaTiO3粉末の代わりにMgO粉末を用いた以外は実施例1と同じ条件でRuを担持させてRu/MgO触媒を得た。
比較例2で得たRu/MgOをCs2CO3のエタノール溶液で含浸してCs2CO3を熱分解してRu-Cs/MgO(Ru/Cs=1)触媒を得た。触媒中のRu-Cs担持量は1.0wt%であった。
図6に示すような、固定床流通式装置でアンモニア合成を行った。合成反応器として縦型反応管1を用い、その中央のガラスウール2上の触媒充填層に実施例1のRu/BaTiO2.5H0.5触媒(Ru 1 wt%)3を0.1g充填した。バルブ4を開、バルブ5,6,7を閉にして、反応管1内の温度を400℃とし、この触媒を水素気流中で2時間還元した。
実施例2、3、4、比較例1~3の触媒についても実施例1の触媒のアンモニア合成評価(H2/N2=3,流量;110ml/min)と同様に評価した。図1、図2に、アンモニア合成反応における様々な触媒の活性をNH3合成速度(mmolg-1h-1)により比較した。図1のグラフでは、実施例1のRu/BaTiO2.5H0.5触媒よりも実施例2のBaTiO2.4D0.6の方が活性が高く、これは担体中のヒドリド濃度が高いほど活性が高いことを示している。実施例1及び実施例2のいずれも、水素化反応を行なっていないBaTiO3粉末にRuを担持させた比較例1のRu/BaTiO3触媒に比べて著しく高い触媒活性を示した。比較例3のRu-Cs/MgO触媒は以前から活性が高い触媒として報告されており、本発明の触媒は、これを上回る活性を確認できた。図2のグラフでは、実施例3、4のCo、Feを担持した触媒は、Ru/BaTiO2.5H0.5触媒ほど活性は高くないものの、酸水素化物担体を使用したことにより、活性が著しく向上した。
Claims (12)
- ヒドリド(H-)を含有させたペロブスカイト型酸水素化物粉末を担体とし、該担体にアンモニア合成に触媒活性を示す金属又は金属化合物が担持されていることを特徴とするアンモニア合成触媒。
- 前記ペロブスカイト型酸水素化物は、ATiO3-xHx(Aは、Ca,Sr,又はBa、0.1≦x≦0.6)で表わされることを特徴とする請求項1に記載のアンモニア合成触媒。
- 前記ペロブスカイト型酸水素化物がさらに窒素を含むことを特徴とする請求項1記載のアンモニア合成触媒。
- 前記ペロブスカイト型酸水素化物は、ATi(O3-zHxNy)(Aは、Ca,Sr,又はBa、0.1≦x≦0.6、0<y≦0.3、z≧x+y、z-x-yは酸素欠陥量を表す)で表わされることを特徴とする請求項3に記載のアンモニア合成触媒。
- 前記触媒活性を示す金属は、該粉末表面にナノ金属粒子として担持されていることを特徴とする請求項1~4のいずれかに記載のアンモニア合成触媒。
- 前記触媒活性を示す金属化合物は、該粉末に混合されて担持されたものであることを特徴とする請求項1~4のいずれかに記載のアンモニア合成触媒。
- 前記触媒活性を示す金属又は金属化合物の金属はRuであり、担持されている量がRu金属として担体に対して0.1~5重量%であることを特徴とする請求項5又は6に記載のアンモニア合成触媒。
- ペロブスカイト型チタン含有酸化物の粉末を出発原料とし、真空中又は不活性ガス雰囲気中で、LiH、CaH2、SrH2、BaH2から選ばれるアルカリ金属又はアルカリ土類金属の水素化物粉末とともに300℃以上、該水素化物の融点未満の温度範囲に保持することによって、該酸化物中の酸化物イオンの一部を水素化物イオンで置換することによってヒドリド(H-)を含有させたペロブスカイト型酸水素化物の粉末を調製する第1工程、
第1工程で得られたペロブスカイト型酸水素化物粉末を、アンモニア合成活性を持つ金属の化合物の溶媒溶液に分散し、次いで、溶媒を蒸発させて触媒前駆体を調製する第2工程、
第2工程で得られた触媒前駆体を乾燥して、該粉末に触媒活性を示す金属化合物を担持した触媒を調製する第3工程、
を含むことを特徴とするアンモニア合成触媒の製造方法。 - 請求項8記載の製造方法において、第3工程の後に、さらに、前記金属化合物を還元雰囲気中で加熱して還元するか真空中で熱分解して、該粉末表面にナノ金属粒子を担持した触媒を調製する第4工程、を含むことを特徴とするアンモニア合成触媒の製造方法。
- 請求項8記載の製造方法において、第1工程の後、第2工程の前に、ペロブスカイト型酸水素化物の粉末を窒素供給源物質の存在下で処理してペロブスカイト型酸水素化物に窒素を含有させる工程を有することを特徴とするアンモニア合成触媒の製造方法。
- 請求項8又は9記載の製造方法において、第3工程又は第4工程の後、触媒を窒素供給源物質の存在下で処理してペロブスカイト型酸水素化物に窒素を含有させる工程を有することを特徴とするアンモニア合成触媒の製造方法。
- 水素と窒素を含有するガスを原料として水素と窒素とを反応させてアンモニアを合成する方法において、請求項1~7のいずれかに記載の触媒を合成反応器内の触媒充填層に充填して、300℃~450℃の反応温度、10kPa以上、20MPa未満の反応圧力条件で、原料の窒素と水素を該触媒上で反応させることを特徴とするアンモニア合成方法。
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