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WO2025084128A1 - Procédé de fabrication d'hydrogène - Google Patents

Procédé de fabrication d'hydrogène Download PDF

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Publication number
WO2025084128A1
WO2025084128A1 PCT/JP2024/035113 JP2024035113W WO2025084128A1 WO 2025084128 A1 WO2025084128 A1 WO 2025084128A1 JP 2024035113 W JP2024035113 W JP 2024035113W WO 2025084128 A1 WO2025084128 A1 WO 2025084128A1
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Prior art keywords
catalyst
ammonia
gas
bed reactor
decomposition
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Japanese (ja)
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大地 関根
宜也 一宮
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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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
    • 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
    • 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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/043—Sulfides with iron group metals or platinum group metals
    • B01J27/045—Platinum group metals
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This disclosure relates to a method for producing hydrogen.
  • Hydrogen energy obtained by burning hydrogen is gaining attention as a way to reduce greenhouse gas emissions.
  • hydrogen is extremely difficult to handle, including transporting and storing.
  • methods have been proposed for producing hydrogen by using ammonia as a hydrogen energy carrier, such as importing ammonia produced overseas, and decomposing the ammonia by contacting it with a catalyst.
  • Patent Document 1 shows that by using a catalyst in which a transition metal such as ruthenium with a small particle size is supported on a carrier, ammonia can be decomposed with high efficiency and hydrogen can be produced suitably.
  • the ammonia decomposition reaction is a large endothermic reaction, and a large amount of heat must be supplied to increase the reaction efficiency. For this reason, the ammonia decomposition reaction is usually carried out at high temperatures, which entails huge energy costs and a large environmental impact.
  • This disclosure was made in consideration of these problems, and aims to provide a hydrogen production method that can efficiently decompose ammonia to produce hydrogen at relatively low temperatures.
  • a method for producing hydrogen according to the present disclosure includes contacting a catalyst with a gas containing ammonia to decompose the ammonia,
  • the catalyst comprises ruthenium, at least one element selected from the group consisting of barium and cesium, and a carbon support;
  • the catalyst has pores with an average pore diameter of 3.5 nm or more and 15 nm or less,
  • the linear velocity of the gas on an empty cylinder basis when the catalyst is brought into contact with the gas is 1.0 cm/s or more at 0° C. and normal pressure.
  • the method for producing hydrogen according to this embodiment includes contacting a catalyst with a gas containing ammonia to decompose the ammonia. Decomposing the ammonia causes the reaction shown in formula (I) below to produce hydrogen.
  • the gas linear velocity based on the empty cylinder when the catalyst and gas are brought into contact is 1.0 cm/s or more, preferably 2.0 cm/s or more, and more preferably 4.0 cm/s or more, based on 0°C and normal pressure, from the viewpoint of efficiently decomposing ammonia at a relatively low temperature.
  • the gas linear velocity is preferably 100,000 cm/s or less, and more preferably 10,000 cm/s or less, based on 0°C and normal pressure, from the viewpoint of keeping the pressure loss of the catalyst layer low.
  • "normal pressure" means 0.1013 MPa (absolute).
  • the reaction temperature for decomposing the ammonia is preferably 300°C or higher and 500°C or lower, and more preferably 350°C or higher and 500°C or lower, from the viewpoint of efficiently decomposing the ammonia.
  • the reaction pressure for decomposing the ammonia is preferably 0 MPa-G or more and 0.9 MPa-G or less, and more preferably 0.2 MPa-G or more and 0.9 MPa-G or less, from the viewpoint of efficiently decomposing ammonia at a relatively low temperature.
  • the decomposition of ammonia is carried out using a reactor.
  • the reactor is preferably at least one selected from the group consisting of an external heat exchange type fixed bed reactor, an adiabatic fixed bed reactor, a fluidized bed reactor, a simulated moving bed reactor, a riser type fluidized bed reactor, and a radial flow type fixed bed reactor, and is more preferably an external heat exchange type fixed bed reactor or an adiabatic fixed bed reactor.
  • the reactor may be one type or a combination of two or more types.
  • the ammonia-containing gas may further contain, for example, oxygen, nitrogen, carbon monoxide, carbon dioxide, saturated hydrocarbons such as methane, hydrogen, helium, water vapor, etc.
  • the ammonia content in the gas is preferably 20% by volume or more and 100% by volume or less, and more preferably 50% by volume or more and 100% by volume or less, from the viewpoint of efficiently decomposing ammonia at a relatively low temperature.
  • the method for producing hydrogen according to this embodiment is carried out in the presence of a catalyst containing ruthenium, at least one element selected from the group consisting of barium and cesium, and a carbon carrier.
  • the ruthenium may be derived from at least one ruthenium compound selected from the group consisting of ruthenium nitrosyl nitrate, ruthenium chloride, potassium ruthenate, ruthenium carbonyl, and ammonium ruthenate chloride. Of these, the ruthenium is preferably derived from ruthenium nitrosyl nitrate.
  • the ruthenium content is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less, based on the entire catalyst.
  • the barium and cesium may be derived from at least one compound selected from the group consisting of nitrates, sulfates, chlorides, and carbonates.
  • the barium and cesium are preferably derived from nitrates.
  • the content of at least one element selected from the group consisting of barium and cesium is preferably 0.1% by mass or more and 20% by mass or less, and more preferably 0.5% by mass or more and 15% by mass or less, based on the entire catalyst, from the viewpoint of efficiently decomposing ammonia at a relatively low temperature. Note that when the catalyst contains both barium and cesium, the content is the total content of barium and cesium.
  • the molar ratio of at least one element selected from the group consisting of barium and cesium to ruthenium is preferably 0.2 or more and 3 or less, more preferably 0.4 or more and 2 or less, from the viewpoint of efficiently decomposing ammonia at a relatively low temperature.
  • Ruthenium and at least one element selected from the group consisting of barium and cesium may be contained in the catalyst as a simple substance or as an oxide, nitrate, or carbonate.
  • Examples of carbon carriers include silicon carbide, activated carbon, carbon black, acetylene black, graphene, graphite, mesoporous carbon, carbon nanotubes, carbon nanofibers, and carbon nanohorns.
  • the carbon carrier is preferably activated carbon, mesoporous carbon, or graphene, and more preferably activated carbon or mesoporous carbon.
  • the carbon carrier may be one type or a combination of two or more types.
  • carbon carrier a commercially available product may be used, for example, mesoC+ TM manufactured by SICAT, Granulated Shirasagi (registered trademark) WH2C manufactured by Osaka Gas Chemicals, and the like.
  • the specific surface area of the carbon support is preferably 50 m 2 /g or more and 2000 m 2 /g or less, and more preferably 100 m 2 /g or more and 1500 m 2 /g or less.
  • the content of the carbon carrier is preferably 50% by mass or more and 99% by mass or less, and more preferably 80% by mass or more and 98% by mass or less, based on the entire catalyst.
  • the shape and size of the carbon carrier are not particularly limited and can be appropriately selected depending on the type, size, operating conditions, etc. of the reactor.
  • Examples of the shape of the carbon carrier include granular, spherical, cylindrical, trilobal, tetralobal, ring, honeycomb, etc.
  • the size of the carbon carrier can be, for example, when the carbon carrier is granular or spherical, the average particle size can be 0.5 mm or more and 10 mm or less.
  • the size of the carrier can be, for example, when the carbon carrier is cylindrical, trilobal, tetralobal, or ring-shaped, the average length of one side of the cross section can be 0.5 mm or more and 10 mm or less, and the average length can be 1 mm or more and 20 mm or less.
  • the catalyst may contain sulfur as an impurity.
  • the content of sulfur contained in the catalyst is preferably 0.002% by mass or more and 0.04% by mass or less so as not to inhibit the effects of the present disclosure.
  • One method for reducing the sulfur content in the catalyst is, for example, washing the carbon support with hydrochloric acid or nitric acid, as described in Patent No. 4365809.
  • the catalyst preferably has pores with an average pore diameter of 3.5 nm or more and 15 nm or less, more preferably has pores with an average pore diameter of 3.5 nm or more and 10 nm or less, and even more preferably has pores with an average pore diameter of 4.0 nm or more and 10 nm or less.
  • the catalyst can be prepared using a general method for supporting a transition metal on a carrier.
  • an impregnation method can be used in which a carrier is impregnated with a solution containing the transition metal, and then dried and calcined.
  • the catalyst can be prepared, for example, by the following method.
  • a solution containing ruthenium which is a catalyst raw material, is impregnated into a carrier by an incipient wetness method, and then dried.
  • the obtained solid is heated under nitrogen flow using an electric tubular furnace to obtain a catalyst precursor carrying ruthenium.
  • the catalyst precursor is impregnated with a solution containing at least one element selected from the group consisting of barium and cesium, and then dried.
  • the obtained solid is heated under nitrogen flow using an electric tubular furnace to obtain a catalyst precursor containing at least one element selected from the group consisting of barium and cesium in addition to ruthenium.
  • the catalyst can be obtained by heating the obtained catalyst precursor in an electric tubular furnace under a flow of hydrogen and nitrogen.
  • the catalyst obtained in this manner can be molded into a spherical, cylindrical, or other shape with an average particle size of 0.5 mm to 20 mm.
  • the average particle size means the average diameter if the molded body is spherical, and means the average diameter and average length if the molded body is cylindrical.
  • the specific surface area (S) of the catalyst can be determined by vacuum degassing the catalyst at 120°C for 8 hours, then measuring the nitrogen adsorption/desorption isotherm at 77K using a Microtrac-Bell BELSORP-Max, using the BET multipoint method.
  • the average pore volume (V P ) of the catalyst can be calculated from the following formula (1).
  • V P (1- ⁇ )/BD-(1/ ⁇ )...(1)
  • ⁇ represents the void ratio between catalyst particles, and the empirical value of 0.36 when spheres are closely packed can be used as the value.
  • BD represents the bulk density of the catalyst, and the mass (g/ml) of the catalyst when 1 ml of the catalyst is packed into a 5 ml measuring cylinder can be used.
  • ⁇ represents the density of the catalyst, and for example, when the catalyst composition is 2.8 mass% BaO/5.0 mass% Ru/C (the amounts of BaO and Ru supported are each outside the number when carrier C is set to 100), the value of 2.8 (g/ml) calculated from the following formula (2) can be used.
  • the average pore diameter (D) of the catalyst can be calculated using the following formula (3):
  • the hydrogen production method includes the above-mentioned decomposition of ammonia, and therefore can produce hydrogen by decomposing ammonia more efficiently at a relatively low temperature than in the past.
  • the hydrogen production method according to this embodiment is not limited to the above-described embodiment, and various modifications are possible without departing from the gist of the disclosure in this application.
  • separation into hydrogen and other components may be included.
  • hydrogen with higher purity can be produced.
  • air may be added to the gas containing ammonia to decompose the ammonia. This causes the reaction shown in formula (II) above to occur in addition to the reaction shown in formula (I) above, accelerating the decomposition of ammonia.
  • carbon dioxide gas may be added to the gas containing ammonia in order to decompose the ammonia. This causes the reaction shown in formula (III) above to occur in addition to the reaction shown in formula (I) above, accelerating the decomposition of ammonia.
  • a method for decomposing ammonia by contacting a catalyst with a gas containing ammonia comprises ruthenium, at least one element selected from the group consisting of barium and cesium, and a carbon support;
  • the catalyst has pores with an average pore diameter of 3.5 nm or more and 15 nm or less,
  • a method for producing hydrogen wherein the empty cylinder standard gas linear velocity when the catalyst and the gas are brought into contact with each other is 1.0 cm/s or more at 0° C. and normal pressure.
  • the method for producing hydrogen according to [1] wherein the catalyst further contains sulfur, and the sulfur content is 0.002 mass% or more and 0.04 mass% or less.
  • [3] The method for producing hydrogen according to [1] or [2], wherein the ruthenium is derived from ruthenium nitrosyl nitrate.
  • [4] The method for producing hydrogen according to any one of [1] to [3], wherein the reaction temperature in decomposing the ammonia is 300° C. or higher and 500° C. or lower.
  • [5] The method for producing hydrogen according to any one of [1] to [4], wherein the reaction pressure in decomposing the ammonia is 0 MPa-G or more and 0.9 MPa-G or less.
  • the method for producing hydrogen according to the present disclosure is not limited to the above-described embodiment, and various modifications are possible without departing from the gist of the present disclosure. Furthermore, the method for producing hydrogen according to the present disclosure is not limited by the effects of the above-described embodiment. In other words, the embodiments disclosed herein should be considered to be illustrative in all respects and not restrictive. The scope of the present disclosure is indicated by the claims, not by the above description. Furthermore, the scope of the present disclosure is intended to include all modifications that are equivalent in meaning and scope to the claims.
  • the obtained solution was impregnated into 20 g of a carbon (C) carrier i (Granular Shirasagi (registered trademark) WH2C, Osaka Gas Chemicals, 1 mm to 2 mm pellets were used after sieving from 0.50 mm to 2.36 mm granular pellets) by the incipient wetness method, and then air-dried overnight at room temperature (about 25° C.) in an air atmosphere.
  • the solid thus obtained was packed into a quartz glass tube having an inner diameter of 24 mm and equipped with a sheath tube for measuring the inner temperature.
  • the tube was then heated to an inner temperature of 400°C over 1 hour in an electric tubular furnace under a nitrogen flow of 100 cm3 (0°C, normal pressure)/min, and then maintained at the same temperature for 3 hours to obtain 21 g of catalyst precursor i-1 (6.6 mass% RuO2 /C) (the amount of RuO2 supported is an external number when carrier i is taken as 100).
  • a solution obtained by adding and dissolving 0.48 g of barium nitrate in 10 g of ion-exchanged water was further impregnated into the solid thus obtained by the incipient wetness method, and then air-dried overnight in an air atmosphere at room temperature (about 25° C.), and further dried under reduced pressure at 80° C. and 9 to 20 mmHg for 1 hour.
  • the solid obtained by two impregnation operations was packed into a quartz glass tube with an inner diameter of 24 mm equipped with a sheath tube for measuring the inner temperature, and then the tube was heated to an inner temperature of 500°C in 1 hour under a nitrogen flow of 100 cm3 (0°C, normal pressure)/min using an electric tubular furnace, and then maintained at the same temperature for 1 hour to obtain catalyst precursor i-2 (2.8 mass% BaO/6.6 mass% RuO2 /C) (the amounts of BaO and RuO2 supported are each outside the number when support i is taken as 100).
  • the molar ratio of barium to ruthenium was 0.37.
  • Catalyst precursor ii-2 was obtained in the same manner as catalyst precursor i-2, except that carbon (C) support ii (mesoC+ TM manufactured by SICAT, trilobal pellets with a cross section of 1.6 mm and a length of 2 mm) was used instead of carbon (C) support i.
  • carbon (C) support ii mesoC+ TM manufactured by SICAT, trilobal pellets with a cross section of 1.6 mm and a length of 2 mm
  • Catalyst precursor iii- 2 (2.8 mass% Cs2O/6.6 mass% RuO2/C) (the amounts of Cs2O and RuO2 supported are outside the amount of carrier i taken as 100) was obtained in the same manner as in the preparation of catalyst precursor i-2, except that 0.36 g of cesium nitrate ( CsNO3 , Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of barium nitrate and the impregnation operation was performed only once. The molar ratio of cesium to ruthenium was 0.37.
  • a catalyst precursor iv-2 was obtained in the same manner as in the preparation of the catalyst precursor i-2, except that a carbon (C) support iii (1.0 mm to 2.0 mm plate-shaped pellets obtained by crushing and sieving KNOBEL (registered trademark) MJ(4)030 manufactured by Toyo Tanso Co., Ltd.) was used instead of the carbon (C) support i.
  • a carbon (C) support iii 1.0 mm to 2.0 mm plate-shaped pellets obtained by crushing and sieving KNOBEL (registered trademark) MJ(4)030 manufactured by Toyo Tanso Co., Ltd.
  • a catalyst precursor v-2 was obtained in the same manner as in the preparation of the catalyst precursor i-2, except that a carbon (C) carrier iv (Granular Shirasagi (registered trademark) LH2C manufactured by Osaka Gas Chemicals Co., Ltd., 0.43 mm to 0.50 mm pieces were used after sieving from granular pellets of 0.25 mm to 0.50 mm) was used instead of the carbon (C) carrier i.
  • C carbon
  • Catalyst i used for decomposition of ammonia was prepared according to the following procedure.
  • the reduction rate of the ammonia concentration was calculated from the following formula (3) using the remaining ammonia amount CA (cm 3 ) obtained by multiplying the amount of ammonia gas supplied CB (cm 3 ) when ammonia gas was supplied for 5 minutes and the amount of liquid (ml) obtained by dividing the amount of sulfuric acid by the amount of 1 N sodium hydroxide solution required for neutralization titration with 1 N sodium hydroxide solution from the amount of ammonia gas supplied CB (cm 3 ) when ammonia gas was supplied for 5 minutes and the amount of liquid (ml) obtained by absorbing the gas after the reaction for 5 minutes, by 22.4 (l/mol) which is the volume of gas at 0°C and normal pressure.
  • Ammonia concentration reduction rate (%) [(CB-CA)/CB] ⁇ 100 ... (3)
  • ammonia decomposition rate ammonia gas flow rate (cm 3 /min) ⁇ Decrease rate of ammonia concentration/100 / catalyst precursor charge amount (g) ... (4)
  • the reduction rate of the ammonia concentration was 25%, and the ammonia decomposition rate was 61 cm 3 /g cat ⁇ min.
  • Catalyst i used for calculating the average pore diameter and measuring the total sulfur content was prepared by changing the amount of catalyst precursor i-2. Specifically, it is as follows. Catalyst precursor i-2: 0.50 g was filled into a quartz glass tube with an inner diameter of 12 mm equipped with a sheath tube with an outer diameter of 4 mm for measuring the inner temperature, and then the temperature was raised to 400° C.
  • V P The pore volume (V P ) of the catalyst i was calculated from the following formula (1).
  • V P (1- ⁇ )/BD-(1/ ⁇ )...(1)
  • ⁇ represents the void ratio between particles of catalyst i, and the empirical value of 0.36 when spheres are closely packed was used.
  • BD represents the bulk density of catalyst i, and the weight (g/ml) of catalyst i when 1 ml of catalyst i is packed into a 5 ml measuring cylinder was used.
  • ⁇ represents the density of catalyst i, and the value 2.8 (g/ml) calculated from the following formula (2) was used.
  • the average pore diameter (D) of catalyst i was calculated using the following formula (3).
  • Catalyst i had a specific surface area (S) of 1172 m 2 /g, a bulk density (BD) of 0.44 g/ml, a pore volume (V P ) of 1.1 ml/g, and an average pore diameter (D) of 3.7 nm.
  • Catalyst ii(1) was prepared in the same manner as in Example 1, except that 0.10 g of catalyst precursor ii-2 was used, and an ammonia decomposition reaction was carried out to calculate the reduction rate of the ammonia concentration and the decomposition rate of ammonia.
  • the reduction rate of the ammonia concentration was 55%, and the decomposition rate of ammonia was 134 cm 3 /g cat min.
  • Catalyst ii(1) was prepared in the same manner as in Example 1, except that 0.50 g of catalyst precursor ii-2 was used, and the average pore diameter was calculated and the total sulfur content was measured.
  • the specific surface area (S) of catalyst ii(1) was 315 m 2 /g
  • the bulk density (BD) was 0.49 g/ml
  • the pore volume (V P ) was 0.93 ml/g
  • the average pore diameter (D) was 12 nm.
  • Catalyst precursor iii-2 Catalyst iii (2.6 mass % Cs 2 O/5.0 mass % Ru/C) (the amounts of Cs 2 O and Ru supported are each an outside number when carrier i is taken as 100) was prepared in the same manner as in Example 1, except that 0.10 g was used, and an ammonia decomposition reaction was carried out to calculate the reduction rate of ammonia concentration and the decomposition rate of ammonia. The reduction rate of ammonia concentration was 26%, and the decomposition rate of ammonia was 64 cm 3 /g cat min.
  • Catalyst precursor iii-2 Catalyst iii (2.6 mass% Cs 2 O/5.0 mass% Ru/C) (the amounts of Cs 2 O and Ru supported are each an extra number relative to the amount of carrier i taken as 100) was prepared in the same manner as in Example 1, except that 0.50 g of catalyst precursor iii-2 was used.
  • the average pore diameter was calculated in the same manner as in Example 1, except that catalyst iii was used, the density of Cs 2 O (4.7 (g/ml)) was used instead of the density of BaO, and the amount of Cs 2 O supported was 2.6 (mass%) instead of the amount of BaO supported.
  • the specific surface area (S) of catalyst iii was 315 m 2 /g, the bulk density (BD) was 0.49 g/ml, the pore volume (V P ) was 0.93 ml/g, and the average pore diameter (D) was 12 nm.
  • Catalyst ii(2) was prepared in the same manner as in Example 1, except that 0.10 g of catalyst precursor ii-2 was packed into a quartz glass tube having an inner diameter of 8 mm and equipped with a sheath tube having an outer diameter of 4 mm for measuring the inner temperature.
  • ammonia decomposition reaction was carried out in the same manner as in Example 1, except that catalyst ii(2) was used, ammonia gas was circulated at 50 cm3 (0°C, normal pressure)/min, and the empty gas linear velocity was 2.2 cm/s at 0°C and normal pressure, and the ammonia concentration reduction rate and ammonia decomposition rate were calculated.
  • the ammonia concentration reduction rate was 61%, and the ammonia decomposition rate was 152 cm3 /g cat min.
  • Catalyst precursor iv-2 Catalyst iv was prepared in the same manner as in Example 1, except that 0.10 g of catalyst precursor iv-2 was used. In addition, an ammonia decomposition reaction was carried out in the same manner as in Example 1, except that catalyst iv was used, and the reduction rate of the ammonia concentration and the decomposition rate of ammonia were calculated. The reduction rate of the ammonia concentration was 10%, and the decomposition rate of ammonia was 26 cm 3 /g cat min.
  • Catalyst precursor iv-2 Catalyst iv was prepared, its average pore diameter was calculated, and its total sulfur content was measured in the same manner as in Example 1, except that 0.50 g of catalyst precursor iv-2 was used.
  • the specific surface area (S) of catalyst iv was 479 m 2 /g
  • the bulk density (BD) was 0.22 g/ml
  • the pore volume (V P ) was 2.6 ml/g
  • the average pore diameter (D) was 22 nm.
  • Catalyst V-2 Catalyst V was prepared in the same manner as in Example 1, except that 0.10 g of catalyst V was used. In addition, an ammonia decomposition reaction was carried out in the same manner as in Example 1, except that catalyst V was used, and the reduction rate of the ammonia concentration and the decomposition rate of ammonia were calculated. The reduction rate of the ammonia concentration was 14%, and the decomposition rate of ammonia was 35 cm 3 /g cat min.
  • Catalyst v was prepared in the same manner as in Example 1, except that 0.50 g of catalyst precursor v-2 was used, and the average pore diameter was calculated to measure the total sulfur content.
  • Catalyst iv had a specific surface area (S) of 1865 m 2 /g, a bulk density (BD) of 0.37 g/ml, a pore volume (V P ) of 1.4 ml/g, and an average pore diameter (D) of 3.0 nm.
  • S specific surface area
  • BD bulk density
  • V P pore volume
  • D average pore diameter
  • Catalyst ii-2 0.30 g was used, and catalyst precursor ii-2 was packed in a quartz glass tube having an inner diameter of 12 mm and equipped with a sheath tube having an outer diameter of 4 mm for measuring the inner temperature.
  • a catalyst ii(3) was prepared in the same manner as in Example 1.
  • ⁇ Ammonia decomposition reaction> The reduction rate of ammonia concentration and the decomposition rate of ammonia were determined in the same manner as in Example 1, except that catalyst ii(3) was used and the empty gas linear velocity was 0.41 cm/s at 0° C. and normal pressure. The reduction rate of ammonia concentration was 53%, and the decomposition rate of ammonia was 44 cm 3 /g cat ⁇ min.
  • Catalyst ii-2 0.06 g was used, and catalyst precursor ii-2 was packed in a quartz glass tube having an inner diameter of 12 mm and equipped with a sheath tube having an outer diameter of 4 mm for measuring the inner temperature.
  • a catalyst ii(4) was prepared in the same manner as in Example 1.
  • ammonia decomposition reaction was carried out in the same manner as in Example 1, except that catalyst ii(4) was used and ammonia gas was passed through at 5 cm3 (0°C, normal pressure)/min, resulting in a linear gas velocity of 0.08 cm/s based on the empty cylinder at 0°C and normal pressure.
  • the ammonia concentration reduction rate and ammonia decomposition rate were calculated.
  • the ammonia concentration reduction rate was 53%, and the ammonia decomposition rate was 44 cm3 /g cat min.
  • Table 2 also shows the reaction gas linear velocity, ammonia decomposition rate, catalyst pore diameter, and total sulfur content for Examples 1 to 5 and Comparative Examples 1 to 4.
  • Table 2 shows that when all of the constituent elements of the present disclosure are met, ammonia can be efficiently decomposed to produce hydrogen at relatively low temperatures.
  • Comparative Example 1 shows that when the average pore diameter of the catalyst is greater than 15 nm, or the results of Comparative Example 2 show that when the average pore diameter of the catalyst is less than 3.5 nm, the ammonia decomposition rate is low, and ammonia cannot be decomposed efficiently to produce hydrogen at relatively low temperatures. In other words, it was found that the hydrogen production methods of Comparative Examples 1 and 2 are not sufficient for industrial use.
  • Comparative Example 3 and Comparative Example 4 show that when the gas linear velocity in the ammonia decomposition reaction is less than 1.0 cm/s, the ammonia decomposition rate is low, and ammonia cannot be efficiently decomposed to produce hydrogen at relatively low temperatures. In other words, it was found that the hydrogen production methods such as those of Comparative Example 4 and Comparative Example 5 are not sufficient for industrial use.

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  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Le procédé de fabrication d'hydrogène de l'invention inclut une étape au cours de laquelle un catalyseur et un gaz contenant un ammoniac sont mis en contact, et l'ammoniac est ainsi dégradé. Ledit catalyseur contient un ruthénium, au moins un élément choisi dans un groupe constitué d'un baryum et d'un césium, et un support de carbone. En outre, ledit catalyseur présente des pores de diamètre moyen supérieur ou égal à ３,５ｎｍ et inférieur ou égal à １５ｎｍ. La vitesse linéaire de gaz sur la base d'un cylindre lorsque ledit catalyseur et ledit gaz sont mis en contact, et supérieure ou égale à １,０ｃｍ／ｓ sur la base d'une pression normale à 0°C.
PCT/JP2024/035113 2023-10-19 2024-10-01 Procédé de fabrication d'hydrogène Pending WO2025084128A1 (fr)

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JP2000176284A (ja) * 1998-12-16 2000-06-27 Hitachi Zosen Corp アンモニア合成触媒の製造方法および同方法で得られた触媒
JP2001261302A (ja) * 2000-03-15 2001-09-26 Univ Tohoku アンモニアガスの分解方法
JP2008536795A (ja) * 2005-04-18 2008-09-11 インテリジェント エナジー インコーポレイテッド アンモニアに基づく水素発生装置及びその使用方法
JP2009248009A (ja) * 2008-04-08 2009-10-29 Hitachi Zosen Corp 貴金属担持触媒の製造方法
JP2010194518A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒
JP2016023126A (ja) * 2014-07-24 2016-02-08 国立大学法人群馬大学 アンモニア態窒素含有廃棄物からのアンモニア分解水素製造方法
JP2019189467A (ja) * 2018-04-18 2019-10-31 三菱重工エンジニアリング株式会社 アンモニア分解システム及びアンモニア分解方法
JP2020082079A (ja) * 2018-11-22 2020-06-04 ナショナル エンジニアリング リサーチ センター オブ ケミカル ファーティライザー キャタリスト、フージョウ ユニバーシティ アンモニア分解による水素製造のためのルテニウム系触媒及びその調製方法、並びに応用

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000176284A (ja) * 1998-12-16 2000-06-27 Hitachi Zosen Corp アンモニア合成触媒の製造方法および同方法で得られた触媒
JP2001261302A (ja) * 2000-03-15 2001-09-26 Univ Tohoku アンモニアガスの分解方法
JP2008536795A (ja) * 2005-04-18 2008-09-11 インテリジェント エナジー インコーポレイテッド アンモニアに基づく水素発生装置及びその使用方法
JP2009248009A (ja) * 2008-04-08 2009-10-29 Hitachi Zosen Corp 貴金属担持触媒の製造方法
JP2010194518A (ja) * 2009-02-27 2010-09-09 Hitachi Zosen Corp アンモニア分解触媒
JP2016023126A (ja) * 2014-07-24 2016-02-08 国立大学法人群馬大学 アンモニア態窒素含有廃棄物からのアンモニア分解水素製造方法
JP2019189467A (ja) * 2018-04-18 2019-10-31 三菱重工エンジニアリング株式会社 アンモニア分解システム及びアンモニア分解方法
JP2020082079A (ja) * 2018-11-22 2020-06-04 ナショナル エンジニアリング リサーチ センター オブ ケミカル ファーティライザー キャタリスト、フージョウ ユニバーシティ アンモニア分解による水素製造のためのルテニウム系触媒及びその調製方法、並びに応用

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