Catalyst material containing supported Co3Mo3N for the synthesis of NH3

Abstract

The present invention relates to a catalyst material for the synthesis of NH3, wherein the catalyst material comprises Co3Mo3N, one or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, and one or more second promoting metals M2 selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La, and mixtures of two or more thereof, wherein the one or more first promoting metals M1 and the one or more second promoting metals M2 are supported on the Co3Mo3N. Furthermore, the present invention relates to a method for preparing the catalyst material and a catalyst material that can be obtained or obtained by the method. Moreover, the present invention relates to a method for using the catalyst material according to the present invention and a method for synthesizing NH3.

Description

[Technical Field]

[0001] The present invention relates to a catalyst material for the synthesis of NH3, a method for producing the catalyst material, a catalyst material obtained or that can be obtained by the production method, a method for synthesizing NH3, and a method for using the catalyst material according to the present invention for the synthesis of NH3. [Background technology]

[0002] Ternary metal nitrides are attracting attention because they possess catalytic activity that makes them suitable as catalyst materials for ammonia synthesis. In particular, ternary nitrides of Co and Mn are known to exhibit activity in the synthesis of NH3 from hydrogen and nitrogen.

[0003] D. Moszyneski et al. published their research on "Catalizatory kobaltowo-molibdenowe domieszkowane cezem do syntezy amoniaku" in Przemysle hemiczny, 2015, 94, 1399-1403. In this paper, they disclose a cobalt-molybdenum nitride catalyst containing 0.25-3.0 mass% Cs, 20-40 mass% Co2Mo3N, and the remainder being Co3Mo3N.

[0004] D. Moszyneski et al. published a study on "Surface and catalytic properties of potassium-modified cobalt-molybdenum catalysts for ammonia synthesis" in Appl.Surf.Sci., 2010, 256, 5581-5584. The paper discloses a catalyst containing 0-3.5 mass% K, 20-50 mass% Co2Mo3N, and the remainder being Co3Mo3N.

[0005] D. Moszyneski et al. published a study in Chem. Pap., 2018, 72, 425-430, titled "Cobalt-molybdenum nitride catalysts co-promoted with chromium and potassium as catalysts for ammonia synthesis." In particular, the paper reports and discloses a Co3Mo3N catalyst co-promoted with K and Cr, which contains a mixture of Co2Mo3N (26-30% by mass) and Co3Mo3N (70-74% by mass), along with 0.34-0.37% by mass of K and 0.47-1.42% by mass of Cr.

[0006] D. Moszyneski et al. published a study in Catalysts, 2022, 12, 100, entitled "Thermal Stability of Potassium-Promoting Cobalt-Molybdenum Nitride Catalysts for Ammonia Synthesis." In particular, the paper discloses cobalt-molybdenum nitride catalysts containing 0.2–3.5 mass% of K, Co2Mo3N, and Co3Mo3N.

[0007] CJH Jacobsen et al. published their research on a "novel class of ammonia synthesis catalysts" in Chem.Commun., 2000, 1057-1058. In particular, NH4Mo7O 24 A Cs-promoted phase-pure Co3Mo3N catalyst is disclosed by precipitating with Co(NO3)2.

[0008] US 6235676 B1 discloses a method for producing ammonia and a method for producing an ammonia synthesis catalyst. According to claim 1, the catalyst is in the form of a ternary nitride and has the general formula M'xM''yN (wherein M' represents a group VIB metal, M'' represents a group VIII metal, and x and y are mixed numbers from 1 to 10), and comprises an accelerator selected from group IA and group IIA metals.

[0009] R. Kojima et al. have published a study entitled "Cobalt-molybdenum dimetal nitride catalysts for ammonia synthesis: Part 1. Preparation and characterization" in Appl. Catal., A, 2001, 215, 149-160. In particular, various Co3Mo3N catalysts promoted with 0.5-15.5 mass% K or 0.4-21.7 mass% Cs are disclosed.

[0010] P. Adamski et al. have published a study on the thermal stability of potassium-promoted cobalt-molybdenum nitride catalysts for ammonia synthesis in Catalysts 2022, 12, 100. [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] US 6235676 B1 [Non-patent literature]

[0012] [Non-Patent Document 1] D. Moszyneski et al., “Katalizatory kobaltowo-molibdenowe domieszkowane cezem do syntezy amoniaku”, Przemysle hemiczny, 2015, 94, 1399-1403 [Non-Patent Document 2] D. Moszyneski et al., "Surface and catalytic properties of potassium-modified cobalt-molybdenum catalysts for ammonia synthesis," Appl. Surf. Sci., 2010, 256, 5581-5584. [Non-Patent Document 3] D. Moszyneski et al., "Cobalt-molybdenum nitride catalyst co-promoted with chromium and potassium as a catalyst for ammonia synthesis," Chem. Pap., 2018, 72, 425-430. [Non-Patent Document 4] D. Moszyneski et al., "Thermal stability of potassium-promoting cobalt-molybdenum nitride catalysts for ammonia synthesis," Catalysts, 2022, 12, 100. [Non-Patent Document 5] CJH Jacobsen et al., "A Novel Class of Ammonia Synthesis Catalysts," Chem.Commun., 2000, 1057-1058. [Non-Patent Document 6] R. Kojima et al., "Cobalt-molybdenum dimetal nitride catalysts for ammonia synthesis: Part 1. Manufacturing and characterization," Appl. Catal., A, 2001, 215, 149-160. [Non-Patent Document 7] P. Adamski et al., "Thermal stability of potassium-promoting cobalt-molybdenum nitride catalysts for ammonia synthesis," Catalysts 2022, 12, 100. [Overview of the Initiative] [Problems that the invention aims to solve]

[0013] Therefore, an object of the present invention is to provide a catalyst material for the synthesis of NH3 that enables conversion, particularly under relatively low temperatures and / or pressures. This reduces overall resource and energy costs, as well as CO2 emissions, enabling a sustainable synthesis concept. [Means for solving the problem]

[0014] Surprisingly, it was discovered that a catalyst material containing a dimetallic nitride Co3Mo3N promoted with two promoting metals can be provided. The catalyst material according to the present invention can be produced by precipitation of a suitable amorphous oxide precursor, followed by the synthesis of a dimetallic nitride catalyst by promotion of the promoted precursor and ammonia decomposition. It was unexpectedly discovered that the catalyst material thus prepared exhibits superior performance in the synthesis of NH3 compared to conventionally known systems. Furthermore, the catalyst material of the present invention 、Reducing CO2 emissions per ton of NH3 produced can impact ammonia production. Therefore, the method of the present invention can be adopted as a drop-in solution to reduce energy consumption in existing Haber-Bosch plants. This is because the Haber-Bosch process according to the present invention can be operated at relatively low temperatures. Furthermore, the catalyst material of the present invention exhibits higher tolerance to various H2 / N2 ratios, including H2-rich feedstocks, than known low-temperature NH3 catalysts.

[0015] Accordingly, the present invention relates to a catalyst material for the synthesis of NH3, which comprises one or more first promoting metals M1 selected from the group consisting of Co3Mo3N, alkali metals and mixtures of two or more thereof, and one or more second promoting metals M2 selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La and mixtures of two or more thereof, wherein one or more first promoting metals M1 and one or more second promoting metals M2 are supported on Co3Mo3N.

[0016] The Co3Mo3N preferably contains one or more Co3Mo3N crystalline phases, where it is preferable that the one or more crystalline phases are determined according to Reference Example 1.a.

[0017] When Co3Mo3N contains one or more Co3Mo3N crystalline phases, preferably 90-100% by mass, more preferably 95-100% by mass, more preferably 99-100% by mass, and more preferably 99.9-100% by mass of the Co3Mo3N is contained in one or more Co3Mo3N crystalline phases, where the amount of one or more Co3Mo3N crystalline phases in the Co3Mo3N contained in the catalyst material is preferably determined according to Reference Example 1.a.

[0018] Furthermore, if the Co3Mo3N contains one or more crystalline Co3Mo3N phases, it is preferable that the Co3Mo3N contains one or more primary particles.

[0019] If the Co3Mo3N contains one or more primary particles, the primary particles have an aspect ratio of the length of the primary particle to the width of the primary particle, preferably in the range of 1.0 to 3.0, more preferably in the range of 1.0 to 2.0, and more preferably in the range of 1.0 to 1.5, where the aspect ratio is preferably determined according to Reference Example 1.b.

[0020] Furthermore, if the Co3Mo3N contains one or more primary particles, the primary particles have an average particle size D50 preferably in the range of 10 to 200 nm, more preferably in the range of 15 to 150 nm, and more preferably in the range of 20 to 90 nm, where the average particle size D50 is preferably determined according to Reference Example 1.b.

[0021] Furthermore, if the Co3Mo3N contains one or more primary particles, it is preferable that the primary particles contain one or more aggregates of one or more Co3Mo3N nanocrystals.

[0022] If the primary particles contain one or more aggregates of one or more Co3Mo3N nanocrystals, the Co3Mo3N nanocrystals preferably have an average crystal size in the range of 50 to 75 nm, more preferably in the range of 65 to 69 nm, where it is preferable that the average crystal size is measured according to Reference Example 1.a.

[0023] The catalyst material preferably contains 0 to 10% by mass, more preferably 0 to 5% by mass, more preferably 0 to 4% by mass, and more preferably 0 to 3% by mass of Co2Mo3N based on the total mass of the catalyst material.

[0024] When the catalyst material contains 0 to 10% by mass of Co2Mo3N, it is preferable that the Co2Mo3N includes one or more crystalline phases of Co2Mo3N. In this case, 90% to 100% by mass of Co2Mo3N, more preferably 95% to 100%, more preferably 99% to 100%, and more preferably 99.9% to 100% by mass of Co2Mo3N is contained in one or more crystalline phases of Co2Mo3N.

[0025] The catalyst material contains one or more oxide phases of Co and Mo, preferably in an amount of 0 to 1% by mass, more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material.

[0026] The catalyst material contains (M1)2MoO4, preferably in an amount of 0 to 1% by mass, more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material.

[0027] The catalyst material contains molybdic oxoanions, preferably in an amount of 0 to 1% by mass, more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material, where the molybdic oxoanions are selected from the group consisting of MoO4 2- 、Mo2O7 2- 、Mo3O 10 2- 、Mo4O 13 2- 、Mo5O 16 2- 、Mo6O 19 2- 、Mo7O 24 6- 、Mo8O 26 4- 、and mixtures of two or more thereof.

[0028] Preferably 90 to 100% by mass, more preferably 95 to 100% by mass, and even more preferably 99 to 100% by mass of one or more first promoting metals M1 and one or more second promoting metals M2 are contained in a layer supported on Co3Mo3N, where this layer is preferably amorphous.

[0029] When 90 to 100% by mass of one or more first promoting metals M1 and one or more second promoting metals M2 are contained in a layer supported on Co3Mo3N, this layer preferably has a thickness in the range of 1 to 7 nm, more preferably 1 to 6 nm, even more preferably 2 to 6 nm, and even more preferably 2 to 5 nm, and the thickness of the layer is preferably determined according to Example 1.b.

[0030] The one or more first promoting metals M1 are preferably in the form of one or more hydroxides and oxides.

[0031] One or more first promoting metals M1 are preferably selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more of these, more preferably from the group consisting of K, Cs, and mixtures thereof, where preferably one or more first promoting metals M1 are K or Cs, and more preferably one or more first promoting metals M1 are Cs.

[0032] The catalyst material is preferably 1.0 × 10 -3 : 1~8.5×10 -2 : in the range of 1, more preferably 2.0 × 10 -3 :1~8.0×10 -2 : In the range of 1, more preferably 3.0 × 10 -3 : 1~7.5×10 -2 : in the range of 1, more preferably 3.6 × 10 -3 :1~7.0×10 -2 : In the range of 1, more preferably 4.0 × 10 -3 : 1~6.5×10 -2 : in the range of 1, more preferably 4.1 × 10 -3 :1~6.2×10 -2 : Range of 1, more preferably 5.0 × 10 -3 : 1~6.0×10 -2 : in the range of 1, more preferably 6.0 × 10 -3 : 1~5.5×10 -2 : In the range of 1, more preferably 7.0 × 10 -3 : 1~5.0×10 -2 : in the range of 1, more preferably 8.0 × 10 -3 : 1~4.5×10 -2 : In the range of 1, more preferably 9.0 × 10 -3 : 1~4.0×10 -2 : In the range of 1, more preferably 1.0 × 10 -2 : 1~3.5×10 -2 : In the range of 1, more preferably 1.2 × 10 -2 :1~3.3×10 -2 : in the range of 1, more preferably 2.0 × 10-2 : 1~3.0×10 -2 The formula has a molar ratio M1:Mo of one or more first promoting metals M1 calculated as the total molar amount of one or more first promoting metals M1 as elements in the range of :1, and Mo, preferably Mo contained in Co3Mo3N calculated as an element.

[0033] The one or more second promoting metals M2 are preferably in the form of one or more hydroxides and oxides.

[0034] One or more second promoting metals M2 are preferably selected from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more of these, and preferably from the group consisting of Mn, Fe, and mixtures thereof, where one or more second promoting metals M2 are more preferably Fe or Mn, and one or more second promoting metals M2 are more preferably Fe.

[0035] The catalyst material is preferably 1.0 × 10 -3 :1~2.0×10 -1 : in the range of 1, more preferably 2.0 × 10 -3 :1~1.2×10 -1 : Range of 1, more preferably 2.2 × 10 -3 :1~1.0×10 -2 : In the range of 1, more preferably 3.0 × 10 -3 :1~9.0×10 -2 : In the range of 1, more preferably 4.0 × 10 -3 :1~8.0×10 -2 : In the range of 1, more preferably 4.3 × 10 -3 :1~7.0×10 -2 : Range of 1, more preferably 5.0 × 10 -3 : 1~6.0×10 -2 : in the range of 1, more preferably 6.0 × 10 -3 : 1~5.0×10 -2 : In the range of 1, more preferably 7.0 × 10 -3 : 1~4.0×10 -2 : in the range of 1, more preferably 8.0 × 10 -3 : 1~3.0×10 -2: In the range of 1, more preferably 9.0 × 10 -3 :1~2.9×10 -2 The compound has a molar ratio M2:Mo of one or more secondary promoting metals M2, calculated as the total molar amount of one or more secondary promoting metals M2 as elements in the range of :1, and Mo, preferably Mo contained in Co3Mo3N as an element.

[0036] The catalyst material preferably further contains one or more co-promoting metals M3, where preferably M3 is different from M1, and M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof, more preferably from the group consisting of Li, Na, Ca, and mixtures of two or more of these.

[0037] The catalyst material preferably contains 0 to 1% by mass, more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.01% by mass, of Cr calculated as an element based on the total mass of the catalyst material.

[0038] Preferably, 90% to 100% by mass, more preferably 95% to 100% by mass, more preferably 99% to 100% by mass, and more preferably 99.9% to 100% by mass of the catalyst material consists of Co, Mo, N, one or more first promoting metals M1, one or more second promoting metals M2, one or more co-promoting metals M3, H, and O.

[0039] The catalyst material is preferably 1 to 25 m 2 Range of / g, more preferably 5-22m 2 Range of / g, more preferably 7-20m 2 It has a BET specific surface area in the range of / g, where the BET specific surface area is preferably measured according to ISO 9277:2022.

[0040] The catalyst material is preferably in the form of particles, where the particles have a particle size in the range of 200 to 365 μm, more preferably in the range of 225 to 340 μm, and more preferably in the range of 250 to 315 μm.

[0041] The catalyst material preferably has a tap density in the range of 0.5 to 1.6 g / cm³, more preferably in the range of 0.7 to 1.4 g / cm³, and even more preferably in the range of 0.9 to 1.2 g / cm³, where the tap density is preferably determined according to Reference Example 1.c.

[0042] The catalyst material is preferably 0.4 to 2.5 g / cm³. -3 The range is, more preferably, 0.6 to 2.3 g / cm³. -3 The range is, more preferably, 0.8 to 2.1 g / cm³. -3 It has a bulk density in the range, where the bulk density is preferably measured according to Reference Example 1.d.

[0043] The catalyst material is preferably 0.4 to 2.3 g / cm³. -3 The range is, more preferably, 0.8 to 2.1 g / cm³. -3 The range is, more preferably 1.2 to 1.9 g / cm³. -3 It has a loose bed density in the range of [this].

[0044] Furthermore, the present invention relates to the following steps: (i) the step of preparing an aqueous mixture comprising one or more Mo sources, one or more Co sources, and 1,3,5,7-tetraazaadamantane (urotropin); (ii) A step of heating the mixture obtained in step (i) at a temperature in the range of 60 to 110°C to obtain a carrier material; (iii) A step to obtain a supported material by mixing the carrier material obtained in step (ii) with an aqueous mixture containing one or more sources of one or more first promoting metals M1 and one or more sources of one or more second promoting metals M2, wherein M1 is selected from the group consisting of alkali metals and two or more mixtures thereof, preferably from the group consisting of Li, Na, K, Rb, Cs and two or more mixtures thereof, more preferably from the group consisting of K, Cs and mixtures thereof, more preferably one or more first promoting metals M1 is K or Cs, and more preferably one or more The first promoting metal M1 is Cs, and M2 is selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La and two or more mixtures thereof, preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re and two or more mixtures thereof, more preferably from the group consisting of Mn, Fe and mixtures thereof, more preferably one or more second promoting metals M2 are Fe or Mn, and more preferably one or more second promoting metals M2 are Fe; (iv) A step of reacting the supported material with NH3 to obtain a catalyst material. The present invention relates to a method for preparing a catalyst material, preferably one of the embodiments described herein, which includes the following:

[0045] One or more Mo sources are (NH4)6Mo7O 24 (NH4)6Mo7O 24 It is preferable that the Mo source be selected from the group consisting of 4H2O and mixtures of two or more thereof, and preferably one or more Mo sources are (NH4)6Mo7O 24 Or (NH4)6Mo7O 24 It is 4H2O.

[0046] One or more Co sources are preferably selected from the group consisting of Co(NO3)2·6H2O, Co(OH)2, CoCl2, CoCl2·2H2O, CoCl2·6H2O, CoSO4·6H2O, CoSO4·7H2O, and mixtures of two or more of these, and preferably one or more Co sources are Co(NO3)2·6H2O.

[0047] One or more Mo sources are preferably selected from the group consisting of salts of M1, hydrated salts of M1, oxide compounds of M1, hydrated oxide compounds of M1, and mixtures thereof, more preferably from the group consisting of salts of M1, hydrated salts of M1, and mixtures thereof, where more preferably one or more Mo sources are salts of M1, which are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, hydroxides, and mixtures thereof, which are preferably nitrates, which are preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated hydroxides, and mixtures thereof, which are preferably hydrated nitrates.

[0048] One or more sources of M2 are preferably selected from the group consisting of salts of M2, hydrated salts of M2, oxide compounds of M2, hydrated oxide compounds of M2, and mixtures thereof, more preferably from the group consisting of hydrated salts, oxide compounds, and mixtures thereof, where the salts are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, ethanolates, citrates, and mixtures of two or more thereof, and the hydrated salts are preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated ethanolates, hydrated citrates, and mixtures of two or more thereof.

[0049] The aqueous solution prepared in step (i) preferably has a molar ratio of 1,3,5,7-tetraazaadamantane (urotropin), calculated as the molar amount of 1,3,5,7-tetraazaadamantane (urotropin), to Mo, calculated as the elemental amount, in the range of 1.0:1 to 3.0:1, more preferably in the range of 1.5:1 to 2.5:1, and more preferably in the range of 1.9:1 to 2.1:1.

[0050] The mixture obtained in step (i) is heated in step (ii) at a temperature preferably in the range of 70°C to 100°C, more preferably in the range of 75°C to 95°C, and more preferably in the range of 80°C to 90°C.

[0051] The heating in step (ii) is preferably carried out for a duration ranging from 1 to 50 hours, more preferably from 5 to 25 hours, more preferably from 10 to 20 hours, and more preferably from 15 to 18 hours.

[0052] The aqueous solution obtained in step (ii) preferably has a pH in the range of 4 to 7, more preferably in the range of 5 to 6.

[0053] The heating in step (ii) is preferably carried out under self-sharpening pressure in an autoclave, more preferably in a PTFE-lined steel autoclave, or the heating is carried out under atmospheric pressure, preferably in a flask fitted with a recirculating condenser.

[0054] The method is to perform step (ii) after step (iii) and before step (iii). (s) A step of separating the carrier material obtained in step (ii) by filtration, preferably. It is preferable to further include the following.

[0055] If the method includes step (s), the method proceeds after step (s) and before step (iii). (w) A step of washing the carrier material obtained from step (s) with water, in an amount of water ranging from 1 to 100 mL / g (carrier material), more preferably in an amount of water ranging from 10 to 30 mL / g (carrier material). It is preferable to further include the following.

[0056] The method is to perform the procedure after step (ii) and before step (iii), more preferably after step (s) as defined above and before step (iii), more preferably after step (w) as defined above and before step (iii), (d1) A step of drying the carrier material obtained in step (ii), (s), or (w) in a gas atmosphere at a temperature in the range of 50 to 130°C, more preferably in the range of 60 to 110°C, more preferably in the range of 70 to 90°C, wherein the gas atmosphere comprises one or more of oxygen and nitrogen, preferably air, more preferably synthetic air, and more preferably one or more of oxygen and nitrogen, preferably air, more preferably synthetic air. It is preferable to further include the following.

[0057] If the method further includes step (d1), the drying by step (d1) is preferably carried out for a duration of 1 to 30 hours, more preferably 8 to 24 hours, and more preferably 12 to 18 hours.

[0058] The method is to perform the procedure after step (ii) and before step (iii), preferably after step (s) as defined above and before step (iii), more preferably after step (w) as defined in claim 41 and before step (iii), (d2) A step of freeze-drying the solid obtained in step (ii), (s), or (w) in a gas atmosphere having a pressure in the range of 1 to 8 millibars (abs), more preferably in the range of 2 to 4 millibars (abs), at a condenser temperature in the range of -100 to -50°C, more preferably in the range of -80 to -60°C, wherein the solid has a temperature in the range of -30 to 0°C, more preferably in the range of -20 to -10°C, and the gas atmosphere comprises one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air, and preferably one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air. It is preferable to further include the following.

[0059] If the method includes step (d2), the freeze-drying by step (d2) is preferably carried out for a duration in the range of 1 to 30 hours, more preferably in the range of 8 to 24 hours, and more preferably in the range of 12 to 18 hours.

[0060] The method is to perform the process after step (ii) and before step (iii), preferably after step (d1) as defined above and before step (iii), or after step (d2) as defined above and before step (iii), (c) A step of calcining the solid obtained in step (ii), (s), (w), (d1) or (d2) in a gas atmosphere having a temperature in the range of 350 to 650°C, more preferably in the range of 400 to 600°C, wherein the gas atmosphere preferably comprises one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air, and preferably consists of one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air. It is preferable to further include the following.

[0061] The mixing in step (iii) preferably includes impregnation, more preferably initial wetting impregnation.

[0062] If the mixing in step (iii) includes impregnation, the ratio of the volume of the aqueous mixture to the pore volume of the carrier material obtained in steps (ii), (s), (w), (d1), or (d2) is preferably in the range of 0.9:1 to 1.1:1, more preferably in the range of 0.95:1 to 1.05:1, and more preferably in the range of 0.99:1 to 1.01:1.

[0063] Step (iv) is preferably 250-400 ml min -1 The range, more preferably 275-375 ml min -1 range, more preferably 300-350 ml min -1 This is carried out in an NH3 airflow having a flow velocity in the range of [specify range].

[0064] Step (iv) includes heating the supported material to a temperature preferably in the range of 600 to 900°C, more preferably in the range of 700 to 800°C, and more preferably in the range of 725 to 775°C.

[0065] Step (iv) is carried out for a duration of preferably 1.0 to 15.0 hours, more preferably 5.0 to 11.0 hours, more preferably 7.0 to 9.0 hours, and more preferably 7.5 to 8.5 hours.

[0066] Preferably, the method is (d3) A step of drying the supported material obtained in step (iii) in a gas atmosphere having a temperature in the range of 50 to 130°C, more preferably in the range of 60 to 110°C, more preferably in the range of 70 to 90°C, wherein the gas atmosphere preferably comprises one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air, and preferably consists of one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air. It also includes.

[0067] If the method includes step (d3), the drying by step (d3) is preferably carried out for a duration of 1 to 30 hours, more preferably 8 to 24 hours, and more preferably 12 to 18 hours.

[0068] Furthermore, the present invention relates to a catalyst material, preferably a catalyst material described in any one of the embodiments disclosed herein, wherein the catalyst material is obtained or can be obtained by the method described in any one of the embodiments disclosed herein.

[0069] Furthermore, the present invention provides (A) A step of providing a reactor having a reaction zone, wherein the reaction zone comprises a catalyst material described in any one of the embodiments disclosed herein, and the catalyst material has a temperature in the range of 200 to 600°C; and (B) A step of supplying a gas stream containing hydrogen and nitrogen to a reactor, wherein this gas stream is brought into contact with a catalyst material to obtain a product gas stream containing NH3. This relates to a method for synthesizing NH3 containing [specifically, a specific group of NH3 groups].

[0070] The catalyst material preferably has a temperature in the range of 250 to 550°C, more preferably in the range of 275 to 525°C.

[0071] The gas flow in step (B) preferably contains 45-95% by volume, more preferably 50-90% by volume, and more preferably 60-80% by volume of hydrogen.

[0072] The hydrogen contained in the gas stream in process (B) is preferably produced from one or more renewable resources.

[0073] The gas flow in step (B) preferably contains 5 to 55 volume%, more preferably 10 to 50 volume%, and more preferably 20 to 40 volume%, of nitrogen.

[0074] The gas flow is supplied to the reactor at a pressure preferably in the range of 40 to 150 bar (abs), more preferably in the range of 50 to 120 bar (abs), and more preferably in the range of 55 to 100 bar (abs).

[0075] Furthermore, the present invention relates to a method for using a catalyst material described in any one of the embodiments disclosed herein for the synthesis of NH3.

[0076] The unit "bar (abs)" refers to absolute pressure, where 1 bar is equal to 10 5 This corresponds to Pa. [Modes for carrying out the invention]

[0077] The present invention is further described by the following set of embodiments and combinations of embodiments arising from the indicated dependencies and backreferences. In particular, it should be noted that in each example where the scope of an embodiment is referred to, for example, in the context of terms such as "the catalyst material according to any one of Embodiments 1 to 4", all embodiments within this scope are expressly disclosed to those skilled in the art, that is, the expression of this term is understood to those skilled in the art to be synonymous with "the catalyst material according to any one of Embodiments 1, 2, 3, and 4". Furthermore, it should be explicitly noted that the following set of embodiments does not constitute a set of claims that would determine the scope of protection, but rather represents a suitably configured portion of the description directed toward general and preferred embodiments of the present invention.

[0078] 1. A catalyst material for the synthesis of NH3, Co3Mo3N, One or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, and One or more secondary promoting metals M2 selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La, and mixtures of two or more of these. Includes, A catalyst material in which one or more first promoting metals M1 and one or more second promoting metals M2 are supported on Co3Mo3N.

[0079] 2. The catalyst material according to Embodiment 1, wherein the Co3Mo3N comprises one or more crystalline Co3Mo3N phases, and the one or more crystalline phases are determined according to Reference Example 1.a.

[0080] 3. The catalyst material according to Embodiment 2, wherein 90 to 100% by mass, preferably 95 to 100% by mass, more preferably 99 to 100% by mass, and more preferably 99.9 to 100% by mass of the Co3Mo3N is contained in the one or more Co3Mo3N crystalline phases, and the amount of the one or more Co3Mo3N crystalline phases in the Co3Mo3N contained in the catalyst material is preferably determined according to Reference Example 1.a.

[0081] 4. The catalyst material according to Embodiment 2 or 3, wherein the Co3Mo3N comprises one or more primary particles.

[0082] 5. The catalyst material according to Embodiment 4, wherein the primary particles have an aspect ratio of the length of the primary particles to the width of the primary particles in the range of 1.0 to 3.0, preferably in the range of 1.0 to 2.0, and more preferably in the range of 1.0 to 1.5, and the aspect ratio is preferably determined according to Reference Example 1.b.

[0083] 6. The catalyst material according to Embodiment 4 or 5, wherein the primary particles have an average particle size D50 in the range of 10 to 200 nm, preferably in the range of 15 to 150 nm, more preferably in the range of 20 to 90 nm, and the average particle size D50 is preferably determined according to Reference Example 1.b.

[0084] 7. The catalyst material according to any one of Embodiments 4 to 6, wherein the primary particles include one or more aggregates of one or more Co3Mo3N nanocrystals.

[0085] 8. The catalyst material according to Embodiment 7, wherein the Co3Mo3N nanocrystals have an average crystal size in the range of 50 to 75 nm, preferably in the range of 65 to 69 nm, and the average crystal size is preferably determined according to Reference Example 1.a.

[0086] 9. The catalyst material according to any one of Embodiments 1 to 8, comprising 0 to 10% by mass, preferably 0 to 5% by mass, more preferably 0 to 4% by mass, and more preferably 0 to 3% by mass of Co2Mo3N based on the total mass of the catalyst material.

[0087] 10. The Co2Mo3N contains one or more crystal phases of Co2Mo3N, and 90% to 100% by mass, preferably 95% to 100% by mass, more preferably 99% to 100% by mass, and still more preferably 99.9% to 100% by mass of the Co2Mo3N is contained in the one or more crystal phases of Co2Mo3N. The catalyst material according to Embodiment 9.

[0088] 11. Based on the total mass of the catalyst material, it contains one or more oxide phases of Co and Mo in an amount of 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass. The catalyst material according to any one of Embodiments 1 to 10.

[0089] 12. Based on the total mass of the catalyst material, it contains (M1)2MoO4 in an amount of 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass. The catalyst material according to any one of Embodiments 1 to 11.

[0090] 13. Based on the total mass of the catalyst material, it contains oxoanions of molybdic acid in an amount of 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass. The oxoanions of molybdic acid are MoO4 2- 、Mo2O7 2- 、Mo3O 10 2- 、Mo4O 13 2- 、Mo5O 16 2- 、Mo6O 19 2- 、Mo7O 24 6- 、Mo8O 26 4- 、and is selected from the group consisting of mixtures of two or more of these. The catalyst material according to any one of Embodiments 1 to 12.

[0091] 14. The catalyst material according to any one of Embodiments 1 to 13, wherein 90 to 100% by mass, preferably 95 to 100% by mass, and more preferably 99 to 100% by mass, of the one or more first promoting metals M1 and the one or more second promoting metals M2 is contained in a layer supported on Co3Mo3N, and the layer is preferably amorphous.

[0092] 15. The catalyst material according to Embodiment 14, wherein the layer has a thickness in the range of 1 to 7 nm, preferably in the range of 1 to 6 nm, more preferably in the range of 2 to 6 nm, and more preferably in the range of 2 to 5 nm, and the thickness of the layer is preferably determined according to Example 1.b.

[0093] 16. The catalyst material according to any one of Embodiments 1 to 15, wherein the one or more first promoting metals M1 are in the form of one or more hydroxides and oxides.

[0094] 17. The catalyst material according to any one of Embodiments 1 to 16, wherein the one or more first promoting metals M1 are selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, preferably from the group consisting of K, Cs, and mixtures thereof, preferably the one or more first promoting metals M1 are K or Cs, and more preferably the one or more first promoting metals M1 are Cs.

[0095] 18.1.0×10 -3 : 1~8.5×10 -2 : A range of 1, preferably 2.0 × 10 -3 :1~8.0×10 -2 : In the range of 1, more preferably 3.0 × 10 -3 : 1~7.5×10 -2 : in the range of 1, more preferably 3.6 × 10 -3 :1~7.0×10 -2 : In the range of 1, more preferably 4.0 × 10 -3 : 1~6.5×10 -2 : in the range of 1, more preferably 4.1 × 10 -3 :1~6.2×10 -2 : Range of 1, more preferably 5.0 × 10 -3: 1~6.0×10 -2 : in the range of 1, more preferably 6.0 × 10 -3 : 1~5.5×10 -2 : In the range of 1, more preferably 7.0 × 10 -3 : 1~5.0×10 -2 : in the range of 1, more preferably 8.0 × 10 -3 : 1~4.5×10 -2 : In the range of 1, more preferably 9.0 × 10 -3 : 1~4.0×10 -2 : In the range of 1, more preferably 1.0 × 10 -2 : 1~3.5×10 -2 : In the range of 1, more preferably 1.2 × 10 -2 :1~3.3×10 -2 : in the range of 1, more preferably 2.0 × 10 -2 : 1~3.0×10 -2 A catalyst material according to any one of Embodiments 1 to 17, having a molar ratio M1:Mo of one or more first promoting metals M1 calculated as the total molar amount of one or more first promoting metals M1 as elements in the range of :1, and Mo, preferably Mo contained in the Co3Mo3N calculated as elements.

[0096] 19. The catalyst material according to any one of Embodiments 1 to 18, wherein the one or more second promoting metals M2 are in the form of one or more hydroxides and oxides.

[0097] 20. The catalyst material according to any one of Embodiments 1 to 19, wherein the one or more second promoting metals M2 are selected from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more of these, preferably from the group consisting of Mn, Fe, and mixtures thereof, and the one or more second promoting metals M2 are more preferably Fe or Mn, and the one or more second promoting metals M2 are more preferably Fe.

[0098] 21.1.0×10 -3 :1~2.0×10 -1 : A range of 1, preferably 2.0 × 10 -3 :1~1.2×10 -1: Range of 1, more preferably 2.2 × 10 -3 :1~1.0×10 -2 : In the range of 1, more preferably 3.0 × 10 -3 :1~9.0×10 -2 : In the range of 1, more preferably 4.0 × 10 -3 :1~8.0×10 -2 : In the range of 1, more preferably 4.3 × 10 -3 :1~7.0×10 -2 : Range of 1, more preferably 5.0 × 10 -3 : 1~6.0×10 -2 : in the range of 1, more preferably 6.0 × 10 -3 : 1~5.0×10 -2 : In the range of 1, more preferably 7.0 × 10 -3 : 1~4.0×10 -2 : in the range of 1, more preferably 8.0 × 10 -3 : 1~3.0×10 -2 : In the range of 1, more preferably 9.0 × 10 -3 :1~2.9×10 -2 A catalyst material according to any one of Embodiments 1 to 20, having a molar ratio M2:Mo of one or more second promoting metals M2 calculated as the total molar amount of one or more second promoting metals M2 as elements in the range of :1, and Mo, preferably Mo contained in zeCo3Mo3N calculated as elements.

[0099] 22. The catalyst material according to any one of Embodiments 1 to 21, further comprising one or more co-promoting metals M3, preferably M3 being different from M1, and M3 being selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof, preferably being selected from the group consisting of Li, Na, Ca, and mixtures of two or more thereof.

[0100] 23. The catalyst material according to any one of Embodiments 1 to 22, comprising 0 to 1% by mass, preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass, calculated as elemental Cr based on the total mass of the catalyst material.

[0101] 24. The catalyst material according to any one of Embodiments 1 to 23, wherein 90% to 100% by mass, preferably 95% to 100% by mass, more preferably 99% to 100% by mass, and more preferably 99.9% to 100% by mass of the catalyst material consists of Co, Mo, N, one or more first promoting metals M1, one or more second promoting metals M2, optionally one or more co-promoting metals M3, H, and O.

[0102] 25.1~25m 2 Range of / g, preferably 5-22m 2 Range of / g, more preferably 7-20m 2 A catalyst material according to any one of Embodiments 1 to 24, having a BET specific surface area in the range of / g, wherein the BET specific surface area is preferably determined in accordance with ISO 9277:2022.

[0103] 26. The catalyst material according to any one of Embodiments 1 to 25, wherein the particles are in the form of particles, and the particles have a particle size in the range of 200 to 365 μm, preferably in the range of 225 to 340 μm, and more preferably in the range of 250 to 315 μm.

[0104] 27. A catalyst material according to any one of Embodiments 1 to 26, having a tap density in the range of 0.5 to 1.6 g / cm, preferably in the range of 0.7 to 1.4 g / cm, more preferably in the range of 0.9 to 1.2 g / cm, wherein the tap density is preferably determined according to Reference Example 1.c.

[0105] 28.0.4~2.5g / cm -3 The range is preferably 0.6 to 2.3 g / cm³. -3 The range is, more preferably 0.8 to 2.1 g / cm³. -3 A catalyst material according to any one of Embodiments 1 to 27, having a bulk density in the range, wherein the bulk density is preferably determined according to Reference Example 1.d.

[0106] 29.0.4~2.3g / cm -3 The range is preferably 0.8 to 2.1 g / cm³. -3The range is, more preferably 1.2 to 1.9 g / cm³. -3 A catalyst material according to any one of embodiments 1 to 28, having a loose bed density in the range of .

[0107] 30. A method for preparing a catalyst material, preferably one of the catalyst materials described in any one of Embodiments 1 to 29, comprising the following steps: (i) the step of preparing an aqueous mixture comprising one or more Mo sources, one or more Co sources, and 1,3,5,7-tetraazaadamantane (urotropin); (ii) A step of heating the mixture obtained in step (i) at a temperature in the range of 60 to 110°C to obtain a carrier material; (iii) A step of obtaining a supported material by mixing the carrier material obtained in step (ii) with an aqueous mixture containing one or more sources of one or more first promoting metals M1 and one or more sources of one or more second promoting metals M2, wherein M1 is selected from the group consisting of alkali metals and two or more mixtures thereof, preferably from the group consisting of Li, Na, K, Rb, Cs and two or more mixtures thereof, more preferably from the group consisting of K, Cs and mixtures thereof, more preferably the one or more first promoting metals M1 is K or Cs, and more preferably the one The first promoting metal M1 is Cs, and M2 is selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La, and two or more mixtures thereof, preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and two or more mixtures thereof, more preferably from the group consisting of Mn, Fe, and mixtures thereof, more preferably the one or more second promoting metals M2 being Fe or Mn, and more preferably the one or more second promoting metals M2 being Fe; (iv) A step of reacting the supported material with NH3 to obtain a catalyst material. Methods that include...

[0108] 31. The one or more Mo sources are (NH4)6Mo7O 24(NH4)6Mo7O 24 A selection from the group consisting of 4H2O and two or more mixtures thereof, preferably, the one or more Mo sources being (NH4)6Mo7O 24 Or (NH4)6Mo7O 24 The method according to Embodiment 30, wherein the solution is 4H2O.

[0109] 32. The method according to Embodiment 30 or 31, wherein the one or more Co sources are selected from the group consisting of Co(NO3)2·6H2O, Co(OH)2, CoCl2, CoCl2·2H2O, CoCl2·6H2O, CoSO4·6H2O, CoSO4·7H2O, and mixtures of two or more thereof, preferably the one or more Co sources are Co(NO3)2·6H2O.

[0110] 33. The method according to any one of Embodiments 30 to 32, wherein the one or more Mo sources are selected from the group consisting of salts of M1, hydrated salts of M1, oxide compounds of M1, hydrated oxide compounds of M1, and mixtures thereof, preferably from the group consisting of salts of M1, hydrated salts of M1, and mixtures thereof, more preferably the one or more Mo sources are salts of M1, the salt is preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, hydroxides, and mixtures thereof, the salt is preferably a nitrate, the hydrated salt is preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated hydroxides, and mixtures thereof, and the hydrated salt is preferably a hydrated nitrate.

[0111] 34. The method according to any one of embodiments 30 to 33, wherein the one or more sources of M2 are selected from the group consisting of salts of M2, hydrated salts of M2, oxide compounds of M2, hydrated oxide compounds of M2, and mixtures thereof, preferably from the group consisting of hydrated salts, oxide compounds, and mixtures thereof, the salt is preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, ethanolates, citrates, and mixtures of two or more thereof, and the hydrated salt is preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated ethanolates, hydrated citrates, and mixtures of two or more thereof.

[0112] 35. The method according to any one of embodiments 30 to 34, wherein the aqueous solution prepared in step (i) has a molar ratio of 1,3,5,7-tetraazaadamantane (urotropin), calculated as the molar amount of 1,3,5,7-tetraazaadamantane (urotropin), to Mo, calculated as the elemental amount, in the range of 1.0:1 to 3.0:1, preferably in the range of 1.5:1 to 2.5:1, and more preferably in the range of 1.9:1 to 2.1:1.

[0113] 36. The method according to any one of embodiments 30 to 35, wherein the mixture obtained in step (i) is heated in step (ii) at a temperature in the range of 70°C to 100°C, preferably in the range of 75°C to 95°C, more preferably in the range of 80°C to 90°C.

[0114] 37. The method according to any one of embodiments 30 to 36, wherein the heating in step (ii) is carried out for a duration ranging from 1 hour to 50 hours, preferably from 5 hours to 25 hours, more preferably from 10 hours to 20 hours, and more preferably from 15 hours to 18 hours.

[0115] 38. The method according to any one of embodiments 30 to 37, wherein the aqueous solution obtained in step (ii) has a pH in the range of 4 to 7, preferably in the range of 5 to 6.

[0116] 39. The method according to any one of embodiments 30 to 38, wherein the heating in step (ii) is carried out under self-sharpening pressure, preferably in an autoclave, more preferably in a PTFE-lined steel autoclave, or the heating is carried out under atmospheric pressure, preferably in a flask fitted with a recirculating condenser.

[0117] 40. After step (ii) and before step (iii), (s) A step of separating the carrier material obtained in step (ii) preferably by filtration. The method according to any one of embodiments 30 to 39, further including the method according to any one of embodiments 30 to 39.

[0118] 41. After process (s) and before process (iii), (w) A step of washing the carrier material obtained from step (s) with water, preferably in an amount of water in the range of 1 to 100 mL / g (carrier material), preferably in an amount of water in the range of 10 to 30 mL / g (carrier material). The method according to embodiment 40, further including the method described in embodiment 40.

[0119] 42. After step (ii) and before step (iii), preferably after step (s) as defined in embodiment 40 and before step (iii), more preferably after step (w) as defined in embodiment 41 and before step (iii), (d1) A step of drying the carrier material obtained in step (ii), (s), or (w) in a gas atmosphere at a temperature in the range of 50 to 130°C, preferably in the range of 60 to 110°C, more preferably in the range of 70 to 90°C, wherein the gas atmosphere preferably comprises one or more of oxygen and nitrogen, preferably air, more preferably synthetic air, and more preferably consists of one or more of oxygen and nitrogen, preferably air, more preferably synthetic air. The method according to any one of embodiments 30 to 41, further comprising:

[0120] 43. The method according to Embodiment 42, wherein the drying by step (d1) is carried out for a duration of 1 to 30 hours, preferably 8 to 24 hours, and more preferably 12 to 18 hours.

[0121] 44. After step (ii) and before step (iii), preferably after step (s) as defined in embodiment 40 and before step (iii), more preferably after step (w) as defined in embodiment 41 and before step (iii), (d2) A step of freeze-drying the solid obtained in step (ii), (s), or (w) in a gas atmosphere having a pressure in the range of 1 to 8 millibars (abs), preferably in the range of 2 to 4 millibars (abs), at a condenser temperature in the range of -100 to -50°C, preferably in the range of -80 to -60°C, wherein the solid has a temperature in the range of -30 to 0°C, preferably in the range of -20 to -10°C, and preferably the gas atmosphere contains one or more of oxygen and nitrogen, preferably air, more preferably synthetic air, and preferably consists of one or more of oxygen and nitrogen, preferably air, more preferably synthetic air. The method according to any one of embodiments 30 to 43, further including the method according to any one of embodiments 30 to 43.

[0122] 45. The method according to Embodiment 44, wherein the freeze-drying by step (d2) is carried out for a duration in the range of 1 to 30 hours, preferably in the range of 8 to 24 hours, and more preferably in the range of 12 to 18 hours.

[0123] 46. ​​After step (ii) and before step (iii), preferably after step (d1) as defined in embodiment 42 or 43 and before step (iii), or after step (d2) as defined in embodiment 44 or 45 and before step (iii), (c) A step of calcining the solid obtained in step (ii), (s), (w), (d1) or (d2) in a gas atmosphere having a temperature in the range of 350 to 650°C, preferably in the range of 400 to 600°C, wherein the gas atmosphere preferably contains one or more of oxygen and nitrogen, preferably air, more preferably synthetic air, and preferably consists of one or more of oxygen and nitrogen, preferably air, more preferably synthetic air. The method according to any one of embodiments 30 to 45, further including the method according to any one of embodiments 30 to 45.

[0124] 47. The method according to any one of embodiments 30 to 46, wherein the mixing by step (iii) includes impregnation, preferably initial wet impregnation.

[0125] 48. The method according to Embodiment 47, wherein the ratio of the volume of the aqueous mixture to the pore volume of the carrier material obtained in step (ii), (s), (w), (d1) or (d2) is in the range of 0.9:1 to 1.1:1, preferably in the range of 0.95:1 to 1.05:1, and more preferably in the range of 0.99:1 to 1.01:1.

[0126] 49. Step (iv) is 250-400 ml min -1 The range is preferably 275-375 ml min -1 range, more preferably 300-350 ml min -1 The method according to any one of embodiments 30 to 48, carried out in an airflow of NH3 having a flow velocity in the range of .

[0127] 50. The method according to any one of Embodiments 30 to 49, wherein step (iv) includes heating the supported material to a temperature in the range of 600 to 900°C, preferably in the range of 700 to 800°C, and more preferably in the range of 725 to 775°C.

[0128] 51. The method according to any one of embodiments 30 to 50, wherein step (iv) is carried out for a duration in the range of 1.0 to 15.0 hours, preferably in the range of 5.0 to 11.0 hours, more preferably in the range of 7.0 to 9.0 hours, and more preferably in the range of 7.5 to 8.5 hours.

[0129] 52. (d3) A step of drying the supported material obtained in step (iii) in a gas atmosphere having a temperature in the range of 50 to 130°C, preferably in the range of 60 to 110°C, more preferably in the range of 70 to 90°C, wherein the gas atmosphere preferably consists of one or more of oxygen and nitrogen, preferably air, more preferably synthetic air. The method according to any one of embodiments 30 to 51, further including the method according to any one of embodiments 30 to 51.

[0130] 53. The method according to Embodiment 52, wherein the drying by step (d3) is carried out for a duration of 1 to 30 hours, preferably 8 to 24 hours, and more preferably 12 to 18 hours.

[0131] 54. A catalyst material, preferably a catalyst material according to any one of Embodiments 1 to 29, wherein the catalyst material is obtained or can be obtained by the method described in any one of Embodiments 30 to 53.

[0132] 55. A method for synthesizing NH3, comprising the following steps (A) A step of providing a reactor having a reaction zone, wherein the reaction zone includes a catalyst material according to any one of embodiments 1 to 29 and 54, and the catalyst material has a temperature in the range of 200 to 600°C; and (B) A step of supplying a gas stream containing hydrogen and nitrogen to the reactor, wherein the gas stream is brought into contact with the catalyst material to obtain a product gas stream containing NH3. Methods that include...

[0133] 56. The method according to Embodiment 55, wherein the catalyst material has a temperature in the range of 250 to 550°C, preferably in the range of 275 to 525°C.

[0134] 57. The method according to Embodiment 55 or 56, wherein the gas flow in step (B) contains 45 to 95 volume%, preferably 50 to 90 volume%, and more preferably 60 to 80 volume%, of hydrogen.

[0135] 58. The method according to any one of embodiments 55 to 57, wherein the hydrogen contained in the gas stream by step (B) is prepared from one or more renewable resources.

[0136] 59. The method according to any one of embodiments 55 to 58, wherein the gas flow by step (B) contains 5 to 55 volume%, preferably 10 to 50 volume%, and more preferably 20 to 40 volume%, of nitrogen.

[0137] 60. The method according to any one of embodiments 55 to 59, wherein the gas flow is supplied to the reactor at a pressure in the range of 40 to 150 bar (abs), preferably in the range of 50 to 120 bar (abs), and more preferably in the range of 55 to 100 bar (abs).

[0138] 61. A method for using the catalyst material according to any one of Embodiments 1 to 29 and 54 for the synthesis of NH3.

[0139] The present invention is further illustrated by the following reference examples, examples, and comparative examples. [Examples]

[0140] Reference example 1: Measurement method Reference Example 1.a: Determination of crystalline phase by powder X-ray diffraction Powder diffraction patterns were recorded using an IP Guinier-Camera G670 (Huber, Germany) and a Bragg-Brentano diffractometer D8 Advanced (Bruker AXS), and Cu-Kα1 radiation (wavelength = 1.54059 Å). Lattice constants were determined manually or using the software package SOS (Reference: J. Soose, G. Meyer, SOS-Programme zur Auswertung von Guinier-Aufnahmen (English: "SOS - Program for Evaluating Guinier Records"); University of Giessen, Germany, 1980).

[0141] Based on the powder diffraction pattern, the average crystal size of the Co3Mo3N crystal was estimated by subjecting the reflection of Co3Mo3N to Scherrer analysis (see Scherrer's equation).

[0142] To determine the amounts of crystalline and amorphous phases in the powder sample, the standard addition method was used. In this method, a known amount of standard sample was added to the powder sample in an appropriate quantity. Common standard samples used were quartz (SiO2), yttrium oxide (Y2O3), or corundum (Al2O3). The amount of crystalline phase and the amount of added standard sample were determined by quantitative phase analysis (QPA) using a common Rietveld analysis program (TOPAS, Fullprof, etc.). Based on the QPA, the relative mass fraction (W) of crystalline phase / analyte was calculated. i ) is calculated, and the absolute mass fraction (W) is calculated using equation (I). i,abs. The amount of amorphous phase was calculated by subtracting the total amount of crystalline phase from the total amount (100%) according to equation (II).

number

number

[0143] References: Ian C. Madsen, Nicola VYScarlett, and Arnt Kern, Z. Kristallogr. 2011, 226, 944.

[0144] The obtained diffraction patterns were analyzed by comparing them with reference diffraction patterns from ICSDs of Co3Mo3N, Co2Mo3N, CoMoO4, Co3O4, CoO, MoO2, MoO3, MoN, and Mo2N.

[0145] Reference Example 1.b: Transmission Electron Microscopy (TEM) Measurement The samples were dispersed in cyclohexane and applied to a TEM carrier. The automated software suite ParticleSizer was used for data evaluation.

[0146] The aspect ratio of the primary particles was manually determined by TEM based on the TEM images.

[0147] Particle size was estimated based on the evaluation of several TEM images.

[0148] The layer thickness was determined visually based on TEM images.

[0149] Reference Example 1.c: Determining Tap Density Samples from the sieve fractions of 250-315 μm were filled into a 10 mL measuring cylinder, and their mass was measured. The cylinder was tapped 200 times, and the volume of the material was visually determined from the scale.

[0150] Reference Example 1.d: Measurement of bulk density The bulk density was determined by helium picrometry.

[0151] Reference Example 2: Preparation of CoMoO4·nH2O precursor The CoMoO4·nH2O precursor is (NH4)6Mo7O 24 40.5 g of (NH4)6Mo7O was prepared as a bulk material using 4H2O and Co(NO3)2·6H2O as starting materials. 24 4H2O (32.8 mmol; 1 equivalent of Mo) and 67.0 g of Co(NO3)2·6H2O (230 mol; 1 equivalent of Co) were dissolved in 1.0 L of water. While stirring, 64.0 g of 1,3,5,7-tetraazaadamantane (also called urotropin or hexamethylenetetramine; 460 mmol; 2 equivalents), dissolved in 300 mL of water, was added to the solution. After the addition of urotropin, no change occurred from the initial bluish-pink color. The suspension was heated at 80°C for 16 hours with stirring under a circulating solvent, thereby changing the color of the suspension to purple. The suspension was separated from the solution by vacuum filtration, the filter cake was washed with 1.5 L of water, and dried in a drying oven (Binder ED115) in synthetic air at 80°C for 16 hours. The resulting bulk material was pulverized and homogenized.

[0152] Reference Example 3: Preparation of CoMoO4·nH2O precursor The CoMoO4·nH2O precursor is (NH4)6Mo7O 24 4H2O and Co(NO3)2·6H2O were used as starting materials to prepare the bulk material. 2.6g of (NH4)6Mo7O 24 4H2O (2.1 mmol; 1 equivalent of Mo) and 4.4 g of Co(NO3)2·6H2O (15.0 mmol; 1 equivalent of Co) were dissolved in 60 mL of water in a PTFE-lined autoclave (50% of the autoclave volume). With stirring, 5.0 g of 1,3,5,7-tetraazaadamantane (also known as urotropin or hexamethylenetetramine; 35.7 mmol; 2.4 equivalents) was added to the solution. The autoclave was sealed and heated at 80°C for 12 hours under magnetic stirring. After natural cooling, the suspension was separated from the solution by vacuum filtration, the filter cake was washed with 150 mL of water and dried in synthetic air at 80°C for 16 hours. The resulting bulk material was pulverized and homogenized.

[0153] Examples 4-21 and Comparative Examples 22-23: Preparation of Catalyst Materials A 13g sample of the CoMoO4·nH2O precursor obtained from Reference Example 2 was subjected to impregnation with aqueous solutions of accelerators and co-accelerators. Except for the co-accelerators which consisted of one or more Ta and Re atoms, the initial wetting impregnation was carried out as co-impregnation of the accelerator and co-accelerators.

[0154] For this reason, the solvent absorption amount of the sample obtained from Reference Example 2 was 0.6 mL g. -1 The solution was measured and mixed with CoMoO4·nH2O to prepare a total of 7.8 mL of accelerating solution. The resulting wet material was dried in synthetic air at 80°C for 16 hours.

[0155] For co-promotion with one or more Ta and Re, a sequential wet initial impregnation method was applied. First, the accelerator was added according to the procedure described above. Then, one or more co-promoters, consisting of Ta and Re, were added in the same manner. The resulting material was dried in synthetic air at 80°C for 16 hours. For co-promotion with Re, diluted perlenic acid was used.

[0156] The metal salts used for impregnation were used without prior purification and are shown in Table 1. Table 2 contains the impregnation amounts of accelerators and co-accelerators, expressed in mass%, based on the ammonia-decomposed catalyst, and the molar ratios of alkali metals to Mo. To relate the desired total mass amount of accelerators and co-accelerators in the completed catalyst to the CoMoO4·nH2O sample obtained from Reference Example 2, the combustion loss (LOI) during ammonia decomposition of the CoMoO4·nH2O sample was measured at 50.8 mass%, and the LOI when the CoMoO4·nH2O sample was converted to CoMoO4 by calcination in synthetic air at 600°C was measured at 31.0 mass%. These LOIs were taken into consideration when calculating the required amounts.

[0157] [Table 1]

[0158] [Table 2]

[0159] The resulting supported CoMoO4·nH2O was subjected to ammonia decomposition treatment according to the following procedure.

[0160] A sample of supported CoMoO4·nH2O was subjected to ammonia decomposition. The sample was packed into a fused silica tube with an inner diameter of approximately 15 mm. The fused silica tube was approximately 800 mm long and was divided in the middle with fused silica frit to hold the applied sample in place. The tube was placed in a tubular furnace (HTM Reetz GmbH LK 1100-60-350-1-V) connected to a gas supply, and after leak testing, it was washed with anhydrous ammonia gas. After setting an ammonia flow of approximately 300-350 mL / min, the sample was heated to 750°C at a heating rate of 5 K / min. After a residence time of 8 hours, the furnace was stopped, the ammonia flow was replaced with a nitrogen flow of approximately 350 mL / min, and the sample was allowed to cool naturally. After cooling, the sample was transferred to an argon-filled glove box, pulverized into a fine powder, and the powder was passivated with 10 vol% air in argon before handling in the atmosphere to prevent sudden ignition. The resulting powder is processed at a rate of 1.5 t / cm² using a hydraulic press equipped with a 40 mm tablet die. 2 The material was molded under pressure, crushed, and sieved in air into fractions of 250-315 μm.

[0161] [Table 3]

[0162] Example 24: Catalyst Test Catalyst testing was conducted at hte GmbH in Germany using a 16x solid-gas reactor system. The reactor system used conforms to the reactor system described in (DOI: 10.1002 / 14356007.s13_s01; Chemie Ingenieur Technik, 2002, 74, 557; DE10036633A1). The reactor (stainless steel 1.4841, inner diameter 4 mm, length 450 mm) was packed with 0.5 mL of catalyst material from Examples 4-21 and Comparative Examples 22-23 (250-315 μm) along with silicon carbide (SiC) layers before and after the reaction. Before the reaction started, each catalyst was heated at 60 bar, GHSV = 35,000 h -1 , 69.8% by volume of H 2、 23.2% by volume of N 2、The catalyst was heated at 500°C for 10 hours with 7.0 volume% Ar. The activated catalyst was then tested according to the test program shown in Table 5.

[0163] [Table 4]

[0164] Table 6 below shows the results of the catalyst test. The activity of the catalyst material of the present invention is expressed as mass-based time yield (WTY), and the volume fraction of ammonia in the product gas stream is expressed as NH3 by volume.

[0165] [Table 5]

[0166] As is evident from the catalyst test results, all catalyst materials showed superior performance compared to the catalyst material of Comparative Example 22, which was not metal-enhanced. Furthermore, the catalyst material of Example 4 achieved a higher mass-based time yield and a higher volume % of NH3 than the catalyst material of Comparative Example 24, which did not contain the second accelerator. Similarly, the catalyst material of Example 5, which had a lower Fe content than Example 4, showed a higher mass-based time yield than the catalyst material of Comparative Example 24. In addition, while the catalyst material of Comparative Example 25 showed a significant decrease in performance under the conditions of Experiment No. 6, the catalyst material of Example 9, which was further enhanced with iron, showed good performance in subsequent Experiments No. 14, 21, and 26.

[0167] References: - D.Moszyneski et al., "Katalizatory kobaltowo-molibdenowe domieszkowane cezem do syntezy amoniaku", Przemysle hemiczny,2015,94,1399-1403;doi:10.15199 / 62.2015.8.31 - D. Moszyneski et al., "Surface and catalytic properties of potassium-modified cobalt-molybdenum catalysts for ammonia synthesis," Appl. Surf. Sci., 2010, 256, 5581-5584. - D. Moszyneski et al., "Cobalt-molybdenum nitride catalyst co-promoted with chromium and potassium as a catalyst for ammonia synthesis," Chem. Pap., 2018, 72, 425-430. - D. Moszyneski et al., "Thermal stability of potassium-promoting cobalt-molybdenum nitride catalysts for ammonia synthesis," Catalysts, 2022, 12, 100. - CJH Jacobsen et al., "A Novel Class of Ammonia Synthesis Catalysts," Chem.Commun., 2000, 1057-1058. - US 6235676 B1 - R. Kojima et al., "Cobalt-molybdenum dimetal nitride catalysts for ammonia synthesis: Part 1. Manufacturing and characterization," Appl. Catal., A, 2001, 215, 149-160. - P. Adamski et al., "Study on the thermal stability of potassium-promoting cobalt-molybdenum nitride catalysts for ammonia synthesis," Catalysts 2022, 12, 100.

Claims

1. NH ３ A catalyst material for the synthesis of, Co ３ Mo ３ It comprises one or more first promoting metals M1 selected from the group consisting of N, alkali metals and mixtures of two or more of these, and one or more second promoting metals M2 selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La, and mixtures of two or more of these. The one or more first promoting metals M1 and the one or more second promoting metals M2 are the Co ３ Mo ３ A catalytic material supported on nitrogen.

2. The above Co ３ Mo ３ where N is one or more Co ３ Mo ３ The catalyst material according to claim 1, comprising an N crystal phase.

3. The catalyst material according to claim 1 or 2, wherein the one or more first promoting metals M1 are in the form of one or more hydroxides and oxides.

4. The catalyst material according to any one of claims 1 to 3, wherein the one or more first promoting metals M1 are selected from the group consisting of K, Cs, and mixtures thereof.

5. 1.0 × 10 －３ : 1-8.5 x 10 －２ A catalyst material according to any one of claims 1 to 4, having a molar ratio M1:Mo of one or more first promoting metals M1 calculated as the total molar amount of one or more first promoting metals M1 as elements, in the range of :1, and Mo calculated as elements.

6. The catalyst material according to any one of claims 1 to 5, wherein the one or more second promoting metals M2 are in the form of one or more hydroxides and oxides.

7. The catalyst material according to any one of claims 1 to 6, wherein the one or more second promoting metals M2 are selected from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more of these.

8. 1.0 × 10 －３ : 1-2.0 x 10 －１ A catalyst material according to any one of claims 1 to 7, having a molar ratio M2:Mo of one or more second promoting metals M2 calculated as the total molar amount of one or more second promoting metals M2 as elements, in the range of 1, and Mo calculated as elements.

9. The catalyst material according to any one of claims 1 to 8, further comprising one or more co-promoting metals M3, wherein M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof.

10. The catalyst material according to any one of claims 1 to 9, comprising 0 to 1 mass% of Cr calculated as an element based on the total mass of the catalyst material.

11. The catalyst material according to any one of claims 1 to 10, wherein 90% to 100% by mass of the catalyst material consists of Co, Mo, N, one or more first promoting metals M1, one or more second promoting metals M2, and optionally one or more co-promoting metals M3, H, and O.

12. A method for preparing a catalyst material, comprising the following steps: (i) the step of preparing an aqueous mixture containing one or more Mo sources, one or more Co sources, and 1,3,5,7-tetraazaadamantane (urotropin); (ii) A step of heating the mixture obtained in step (i) at a temperature in the range of 60 to 110°C to obtain a carrier material; (iii) A step of obtaining a supported material by mixing the carrier material obtained in step (iii) with an aqueous mixture containing one or more sources of one or more first promoting metals M1 and one or more sources of one or more second promoting metals M2, wherein M1 is selected from the group consisting of alkali metals and two or more mixtures thereof, and M2 is selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, Y, La, and two or more mixtures thereof; (iv) The supported material is NH ３ The process involves reacting with to obtain a catalyst material. Methods that include...

13. A catalyst material obtained or obtainable by the method of claim 12.

14. NH ３ A method for synthesizing the following steps (A) A step of providing a reactor having a reaction zone, wherein the reaction zone includes a catalyst material according to any one of claims 1 to 11 and 13, and the catalyst material has a temperature in the range of 200 to 600°C; and (B) A step of supplying a gas stream containing hydrogen and nitrogen to the reactor, wherein the gas stream is brought into contact with the catalyst material and NH ３ A process to obtain a product gas stream containing the product. Methods that include...

15. NH ３ A method for using the catalyst material according to any one of claims 1 to 11 and 13 for the synthesis of [the specified material].

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