A method for modifying NH3 using a supported Co3Mo3N catalyst material.

Abstract

The present invention relates to a method for reforming ammonia, the method comprising the step of contacting a feed gas stream containing NH3 with a catalyst material containing Co3Mo3N and one or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, wherein one or more first promoting metals M1 are supported on the Co3Mo3N, and the contact is carried out at a pressure exceeding 5 bar and a temperature in the range of 200 to 700°C.

Description

[Technical Field]

[0001] The present invention relates in particular to a method for reforming NH3 under relatively high pressure, wherein a catalyst comprising a supported Co3Mo3N catalyst material is used. [Background technology]

[0002] NH3 is considered a future energy vector capable of chemically storing a significant amount of H2. Therefore, it is possible to produce sustainable NH3 on a large scale from renewable energy sources. Reforming NH3 at sites where H2 is needed (see Equation 1 below) could be the final step in closing a renewable electricity-based H2 value chain. 2 NH3 ⇔ N2+ 3 H2

[0003] I. Lucentini et al., Ind.Eng.Chem.Res.2021,60,18560-18611 and T. Le et al., KoreanJ.Chem.Eng.,2021,38(6),1087-1103, respectively, provide overviews of catalysts used for ammonia decomposition. X.-K.Li et al., Journal of Catalysis,2005,236,181-189, specifically discusses ammonia decomposition using Ni and Ru catalysts. Bell et al., Top Catal.,2016,59,1438-1457, discusses ammonia decomposition using non-precious metal catalysts, mainly focusing on catalysts containing Co and Ni. S. Sayas et al., Catal.Sci.Technol.2020,10,5027-5035, studied high-pressure ammonia decomposition using Ru-K / CaO catalysts at pressures below 40 bar. A. Srifa et al. published a study on hydrogen production by ammonia decomposition using a Cs-modified Co3Mo3N catalyst under standard pressure in Applied Catalysis B:Environmental 218 (2017), pp. 1-8. [Prior art documents] [Non-patent literature]

[0004] [Non-Patent Document 1] I. Lucentini et al., Ind. Eng. Chem. Res. 2021, 60, 18560-18611 [Non-Patent Document 2] T.Le et al., KoreanJ.Chem.Eng.,2021,38(6),1087-1103 [Non-Patent Document 3] X.-K.Li et al., Journal of Catalysis, 2005, 236, 181-189. [Non-Patent Document 4] Bell et al., Top Catal., 2016, 59, 1438-1457 [Non-Patent Document 5] S.Sayas et al., Catal.Sci.Technol.2020,10,5027-5035 [Non-Patent Document 6] A. Srifa et al., Applied Catalysis B:Environmental 218(2017), pp. 1-8 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, there is still a need for improved, cost-effective NH3 reforming methods that can produce exhaust gas flows containing hydrogen at relatively high pressures, especially under relatively high reaction pressures. [Means for solving the problem]

[0006] Therefore, surprisingly, it was found that an NH3 reforming method with improved ammonia conversion rates compared to commonly used industrial catalyst materials could be provided, especially under relatively high reaction pressures.

[0007] Therefore, the present invention relates to a method for reforming ammonia, and this method is (i) A step of providing a reactor containing a catalyst material, wherein the catalyst material comprises Co3Mo3N and one or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, and the one or more first promoting metals M1 are supported on the Co3Mo3N; (ii) A process for preparing a feed gas stream containing NH3; (iii) A step of supplying the feed gas stream prepared in step (ii) to the reactor provided in step (i), and bringing the feed gas stream into contact with the catalyst material, wherein the contact is carried out at a pressure exceeding 5 bar and a temperature in the range of 200 to 700°C; (iv) A step of removing the exhaust gas flow from the reactor, wherein the exhaust gas flow includes H2 and N2. Includes.

[0008] The contact in step (iii) is preferably carried out at a pressure in the range of more than 5 bar to 100 bar, more preferably in the range of 10 to 100 bar, more preferably in the range of 12 to 100 bar, more preferably in the range of 14 to 75 bar, more preferably in the range of 15 to 50 bar, more preferably in the range of 16 to 45 bar, more preferably in the range of 17 to 40 bar, more preferably in the range of 18 to 35 bar, more preferably in the range of 19 to 28 bar, and more preferably in the range of 20 to 25 bar.

[0009] The contact in step (iii) is preferably carried out at a temperature in the range of 200 to 900°C, more preferably 250 to 750°C, more preferably 250 to 650°C, more preferably 300 to 600°C, more preferably 350 to 550°C, and more preferably 400 to 500°C.

[0010] The supply gas flow supplied to the reactor is preferably 500 to 20,000 h -1 range, more preferably 700 to 16,000 h -1 range, more preferably 800 to 12,000 h -1 The range, more preferably 900 to 10,000 hours -1The range, more preferably 1,000 to 8,000 h -1 range, more preferably 3,000 to 5,000 h -1 This is performed using gas spacetime velocities within the range of [specified range].

[0011] The feed gas stream prepared in step (ii) preferably contains 1 to 100 volume%, more preferably 3 to 99.99 volume%, more preferably 5 to 99.95 volume%, more preferably 10 to 99.9 volume%, more preferably 15 to 99.9 volume%, more preferably 20 to 99.8 volume%, more preferably 30 to 99.7 volume%, more preferably 40 to 99.6 volume%, more preferably 50 to 99.5 volume%, more preferably 60 to 99.5 volume%, more preferably 70 to 99.5 volume%, more preferably 80 to 99.5 volume%, and more preferably 90 to 99.5 volume% of NH3.

[0012] The feed gas stream prepared in step (ii) preferably contains one or more inert gases in an amount of 0 to 50 vol%, more preferably 0.01 to 30 vol%, more preferably 0.03 to 15 vol%, more preferably 0.05 to 5 vol%, more preferably 0.1 to 1 vol%, more preferably 0.12 to 0.5 vol%, and more preferably 0.14 to 0.16 vol%, where one or more inert gases are selected from N2, Ar, and mixtures thereof.

[0013] The feed gas stream prepared in step (ii) preferably contains 0 to 75 volume%, more preferably 0 to 60 volume%, more preferably 0 to 50 volume%, more preferably 0 to 40 volume%, more preferably 0 to 35 volume%, and more preferably 0 to 30 volume% of H2.

[0014] The supply gas stream prepared in step (ii) is preferably 100-50,000 ppmv, more preferably 200-30,000 ppmv, more preferably 500-25,000 ppmv, more preferably 500-20,000 ppmv, more preferably 500-15,000 ppmv, more preferably 750-15,000 ppmv, more preferably 1,000-11,000 ppmv, more preferably 1, It contains H2O with a concentration of 000-10,000 ppmv, more preferably 2,000-8,000 ppmv, more preferably 3,000-7,500 ppmv, more preferably 3,100-7,400 ppmv, more preferably 3,500-7,200 ppmv, more preferably 4,000-7,100 ppmv, more preferably 4,500-7,000 ppmv, and more preferably 5,000-6,500 ppmv.

[0015] The feed gas stream prepared in step (ii) preferably further contains one or more inert gases and H2, where the total amount of NH3, inert gases, and H2 contained in the feed gas stream prepared in step (ii) is in the range of 90 to 100% by mass, more preferably in the range of 95 to 99.95% by volume, more preferably in the range of 98 to 99.9% by volume, more preferably in the range of 99 to 99.85% by volume, and more preferably in the range of 99.7 to 99.8% by volume, where the one or more inert gases are selected from N2, Ar, and mixtures thereof.

[0016] The method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) contains one or more hydrocarbons and one or more CO2 and H2O, and the exhaust gas stream removed in step (iv) further contains CO.

[0017] If the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) further contains CO2 and one or more hydrocarbons, and the feed gas stream preferably contains 5% by volume or less, more preferably 3% by volume or less, more preferably 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, and more preferably 0.01% by volume or less of H2O.

[0018] If the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) further contains H2O and one or more hydrocarbons, and the feed gas stream preferably contains 5% by volume or less, more preferably 3% by volume or less, more preferably 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, and more preferably 0.01% by volume or less of CO2.

[0019] If the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) preferably further contains CO2, H2O, and one or more hydrocarbons.

[0020] Furthermore, if the method is intended to modify ammonia and hydrocarbons, one or more hydrocarbons are preferably selected from the group consisting of alkanes and mixtures thereof, more preferably C1-C10 alkanes and mixtures thereof, more preferably C3-C9 alkanes and mixtures thereof, more preferably C4-C8 alkanes and mixtures thereof, more preferably C5-C7 alkanes and mixtures thereof, and more preferably C6 alkanes and mixtures thereof.

[0021] Furthermore, if the method is intended to modify ammonia and hydrocarbons, the contact is carried out at a pressure preferably in the range of 10 to 50 bar, more preferably 12 to 45 bar, more preferably 15 to 40 bar, more preferably 18 to 35 bar, and more preferably 20 to 30 bar.

[0022] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) preferably contains NH3 in the range of 0.1 to 75 volume%, more preferably 0.3 to 60 volume%, more preferably 0.5 to 50 volume%, more preferably 0.8 to 40 volume%, more preferably 1 to 30 volume%, and more preferably 12 to 25 volume%.

[0023] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) preferably contains one or more hydrocarbons in an amount of 10-70% by volume, more preferably 12-60% by volume, more preferably 15-50% by volume, more preferably 20-40% by volume, and more preferably 22-29% by volume.

[0024] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) preferably contains 0 to 75 volume%, more preferably 0.5 to 70 volume%, more preferably 1 to 68 volume%, more preferably 3 to 66 volume%, more preferably 5 to 64 volume%, more preferably 8 to 62 volume%, more preferably 10 to 60 volume%, more preferably 25 to 50 volume%, and more preferably 33 to 44 volume% of H2O.

[0025] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed gas stream prepared in step (ii) preferably contains 0 to 60 volume%, more preferably 1 to 58 volume%, more preferably 3 to 56 volume%, more preferably 5 to 54 volume%, more preferably 8 to 52 volume%, more preferably 10 to 50 volume%, and more preferably 12 to 20 volume% of CO2.

[0026] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed stream preferably exhibits a H2O:C molar ratio of carbon in H2O and one or more hydrocarbons in the range of 0 to 4, more preferably 0.1 to 3, more preferably 0.2 to 3, more preferably 0.3 to 2.5, more preferably 0.4 to 2, and more preferably 0.5 to 1.6.

[0027] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed stream exhibits a CO2:C molar ratio of CO2 to carbon contained in one or more hydrocarbons, preferably in the range of 0 to 4, more preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5, and more preferably 0.4 to 0.8.

[0028] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the feed stream exhibits an NH3:C molar ratio of NH3 to carbon contained in one or more hydrocarbons, preferably in the range of 0 to 5, more preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, and more preferably 0.01 to 1.

[0029] Furthermore, if the method is intended to reform ammonia and hydrocarbons, it is preferable that the exhaust gas stream removed in step (iv) also contains CO2.

[0030] Furthermore, if the method is intended for the reforming of ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) exhibits a stoichiometric number R in the range of 0.1 to 3, where R is defined according to equation (I):

number

[0031] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) preferably exhibits a stoichiometric number R in the range of 1 to 2.5, more preferably 1.3 to 2.2.

[0032] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) exhibits a stoichiometric number R greater than 2.

[0033] If the method is intended to reform ammonia and hydrocarbons, it is preferable that the exhaust gas stream removed in step (iv) exhibits an H2:CO molar ratio greater than 2.

[0034] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) preferably exhibits a stoichiometric number R in the range of 0.5 to 3, more preferably 1 to 2.2, and more preferably 1.3 to 1.7.

[0035] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) preferably contains 10-90% by volume, more preferably 20-80% by volume, more preferably 30-70% by volume, more preferably 40-65% by volume, and more preferably 45-60% by volume of H2.

[0036] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) preferably contains 1 to 70 volume%, more preferably 3 to 50 volume%, more preferably 5 to 40 volume%, more preferably 10 to 35 volume%, and more preferably 15 to 30 volume% of CO.

[0037] Furthermore, if the method is intended to reform ammonia and hydrocarbons, the exhaust gas stream removed in step (iv) preferably contains 1 to 50 volume%, more preferably 3 to 45 volume%, more preferably 5 to 40 volume%, more preferably 8 to 35 volume%, more preferably 10 to 30 volume%, and more preferably 12 to 25 volume% of CO2.

[0038] The Co3Mo3N used in the method of the present invention preferably contains one or more Co3Mo3N crystalline phases, and these one or more crystalline phases are preferably determined according to Reference Example 1.a.

[0039] When Co3Mo3N contains one or more Co3Mo3N crystalline phases, 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 the 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.

[0040] Furthermore, if the Co3Mo3N contains one or more Co3Mo3N crystalline phases, it is preferable that the Co3Mo3N contains one or more primary particles.

[0041] When Co3Mo3N contains one or more primary particles, the one or more primary particles have an aspect ratio of length to 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.

[0042] Furthermore, if the Co3Mo3N contains one or more primary particles, the average particle size D50 is 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.

[0043] 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 nanocrystalline materials.

[0044] When 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 the average crystal size is preferably determined according to Example 1.a.

[0045] The catalyst material used in the method of the present invention 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.

[0046] When the catalyst material contains 0 to 10% by mass of Co2Mo3N based on the total mass of the catalyst material, the Co2Mo3N preferably contains one or more Co2Mo3N crystal phases, where preferably 90 to 100% by mass, more preferably 95 to 100% by mass, more preferably 99 to 100% by mass, and most preferably 99.9 to 100% by mass of the Co2Mo3N is contained in one or more Co2Mo3N crystal phases.

[0047] The catalyst material preferably contains one or more oxide phases of Co and Mo in an amount of 0 to 1% by mass, more preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass based on the total mass of the catalyst material.

[0048] The catalyst material contains (M1)2MoO4 in an amount of preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass based on the total mass of the catalyst material.

[0049] The catalyst material contains molybdic acid oxoanions in an amount of preferably 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 acid oxoanions are MoO4 2- , Mo2O7 2- , Mo3O 10 2- , Mo4O 13 2- , Mo5O 16 2-Mo6O 19 2- Mo7O 24 6- Mo8O 26 4- Selected from the group consisting of , and mixtures of two or more of these.

[0050] In the method of the present invention, the one or more first promoting metals M1 used are preferably in the form of one or more hydroxides and oxides.

[0051] One or more first promoting metals M1 contained in the catalyst material provided in step (i) are preferably selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, 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.

[0052] The catalyst material contained in the reactor provided according to step (i) is preferably 1.0 × 10⁻⁶. -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.

[0053] The catalyst material contained in the reactor provided according to step (i) preferably further contains one or more secondary promoting metals M2 supported on Co3Mo3N, where the one or more secondary promoting metals M2 are preferably selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, La and two or more mixtures thereof; more preferably from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, La and two or more mixtures thereof; more preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re and two or more mixtures thereof; and more preferably from the group consisting of Mn, Fe and mixtures thereof, where the one or more secondary promoting metals M2 are more preferably Fe or Mn, and the one or more secondary promoting metals M2 are more preferably Fe.

[0054] Furthermore, if the catalyst material contained in the reactor provided according to step (i) further contains one or more secondary promoting metals M2 supported on Co3Mo3N, it is preferable that the one or more secondary promoting metals M2 are in the form of one or more hydroxides and oxides.

[0055] Furthermore, if the catalyst material contained in the reactor provided according to step (i) further contains one or more second promoting metals M2 supported on Co3Mo3N, 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 : 1~4.0×10 -2 : In the range of 1, more preferably 9.0 × 10 -3 :1~2.9×10 -2 : In the range of 1, more preferably 1.0 × 10 -2 :1~2.0×10 -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.

[0056] The catalyst material contained in the reactor provided according to step (1) preferably further contains one or more third promoting metals M3, where 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 thereof.

[0057] The catalyst material contained in the reactor provided according to step (1) contains, preferably 0 to 1% by mass, more preferably 0 to 0.1% by mass, and more preferably 0 to 0.01% by mass of Cr, calculated as an element, based on the total mass of Co3Mo3N, one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3.

[0058] Preferably, 90 to 100% by mass, more preferably 95 to 100% by mass, and more preferably 99 to 100% by mass of one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3 contained in the catalyst material contained in the reactor provided according to step (1) are contained in a layer supported on Co3Mo3N, where the layer is preferably amorphous.

[0059] Furthermore, if one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3 contained in the catalyst material provided in the reactor according to step (1) are included in a layer supported on Co3Mo3N, the layer thickness is preferably in the range of 1 to 7 nm, more 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 layer thickness is preferably determined according to Reference Example 1.b.

[0060] 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 catalyst material consists of Co, Mo, N, one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3, H, and O.

[0061] The catalyst material used in the method of the present invention is preferably 1 to 25 m 2 Range of / g, more preferably 5-22m 2 Range of / g, more preferably 7-20m 2 The BET specific surface area is in the range of / g, where the BET specific surface area is preferably determined according to ISO 9277:2022.

[0062] The catalyst material used in the method of the present invention 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.

[0063] The catalyst material used in the method of the present invention preferably has a tap density in the range of 0.5 to 1.6 g / cm, more preferably in the range of 0.7 to 1.4 g / cm, and more preferably in the range of 0.9 to 1.2 g / cm, where the tap density is preferably determined according to Reference Example 1.c.

[0064] The catalyst material used in the method of the present invention is preferably 0.4 to 2.5 g / cm³. -3 The range, 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 of, where the bulk density is preferably determined according to Reference Example 1.d.

[0065] The catalyst material used in the method of the present invention 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].

[0066] The exhaust gas stream removed in step (iv) is preferably used in a methanol production process, a dimethyl ether production process, or a methanol and dimethyl ether production process.

[0067] The exhaust gas stream removed in step (iv) is preferably used in a hydrocarbon production process, preferably according to the Fischer-Tropsch process.

[0068] The exhaust gas stream removed in step (iv) is preferably used in the production process of alcohol, more preferably alkanol, more preferably C1-C10 alkanol, more preferably C2-C8 alkanol, more preferably C2-C6 alkanol, more preferably C2-C4 alkanol, more preferably C2 alkanol, and more preferably ethanol.

[0069] The feed gas stream prepared in step (ii) and supplied to the reactor in step (iii) preferably contains H2 for reducing the catalyst material.

[0070] Furthermore, if the feed gas stream prepared in step (ii) and supplied to the reactor in step (iii) contains H2 for reducing the catalyst material, the feed gas stream prepared in step (ii) and supplied to the reactor in step (iii) preferably contains 0.5 to 80 volume%, more preferably 1 to 70 volume%, more preferably 2 to 60 volume%, more preferably 5 to 50 volume%, and more preferably 15 to 40 volume% of H2.

[0071] The unit refers to absolute pressure, where 1 bar is equal to 10 5 This corresponds to Pa. [Brief explanation of the drawing]

[0072] [Figure 1] Figure 1 shows the catalyst test results for a Ni catalyst as a reference, a Co3Mo3N catalyst supported with Cs as a reference, and a Co3Mo3N catalyst supported with both Cs and Re. The horizontal axis shows temperature (°C), and the vertical axis shows the NH3 conversion rate (%). [Modes for carrying out the invention]

[0073] 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 method 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 method 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.

[0074] 1. A method for reforming ammonia, comprising the following steps: (i) A step of providing a reactor containing a catalyst material, wherein the catalyst material comprises Co3Mo3N and one or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, and the one or more first promoting metals M1 are supported on the Co3Mo3N; (ii) A step of preparing a feed gas flow containing NH3; (iii) A step of supplying the feed gas stream prepared in step (ii) to the reactor provided in step (i), and bringing the feed gas stream into contact with the catalyst material, wherein the contact is carried out at a pressure exceeding 5 bar and a temperature in the range of 200 to 700°C; (iv) A step of removing the exhaust gas flow from the reactor, wherein the exhaust gas flow includes H2 and N2, and Methods that include...

[0075] 2. The method according to Embodiment 1, wherein the contact in step (iii) is performed at a pressure in the range of more than 5 bar to 100 bar, preferably in the range of 10 to 100 bar, more preferably in the range of 12 to 100 bar, more preferably in the range of 14 to 75 bar, more preferably in the range of 15 to 50 bar, more preferably in the range of 16 to 45 bar, more preferably in the range of 17 to 40 bar, more preferably in the range of 18 to 35 bar, more preferably in the range of 19 to 28 bar, and more preferably in the range of 20 to 25 bar.

[0076] 3. The method according to Embodiment 1 or 2, wherein the contact in step (iii) is performed at a temperature in the range of 200 to 900°C, preferably in the range of 250 to 750°C, more preferably in the range of 250 to 650°C, more preferably in the range of 300 to 600°C, more preferably in the range of 350 to 550°C, and more preferably in the range of 400 to 500°C.

[0077] 4. The supply gas flow is 500 to 20,000 h -1 Preferably 700 to 16,000 hours -1 More preferably 800 to 12,000 hours -1 Comfortable 900-10,000h -1 More preferably 1,000 to 8,000 hours -1 , more preferably 3,000 to 5,000 hours -1 The method according to any one of embodiments 1 to 3, wherein the gas is supplied to the reactor at a gas time-space velocity within the range of .

[0078] 5. The method according to any one of Embodiments 1 to 4, wherein the supply gas stream prepared in step (ii) contains 1 to 100 volume%, preferably 3 to 99.99 volume%, more preferably 5 to 99.95 volume%, more preferably 10 to 99.9 volume%, more preferably 15 to 99.9 volume%, more preferably 20 to 99.8 volume%, more preferably 30 to 99.7 volume%, more preferably 40 to 99.6 volume%, more preferably 50 to 99.5 volume%, more preferably 60 to 99.5 volume%, more preferably 70 to 99.5 volume%, more preferably 80 to 99.5 volume%, and more preferably 90 to 99.5 volume% of NH3.

[0079] 6. The method according to any one of Embodiments 1 to 5, wherein the supply gas stream prepared in step (ii) contains 0 to 50 volume%, preferably 0.01 to 30 volume%, more preferably 0.03 to 15 volume%, more preferably 0.05 to 5 volume%, more preferably 0.1 to 1 volume%, more preferably 0.12 to 0.5 volume%, and more preferably 0.14 to 0.16 volume%, of one or more inert gases, the one or more inert gases being selected from N2, Ar, and mixtures thereof.

[0080] 7. The method according to any one of Embodiments 1 to 6, wherein the supply gas flow prepared in step (ii) contains 0 to 75 volume%, preferably 0 to 60 volume%, more preferably 0 to 50 volume%, more preferably 0 to 40 volume%, more preferably 0 to 35 volume%, and more preferably 0 to 30 volume% of H2.

[0081] 8. The supply gas flow prepared in step (ii) is 100 to 50,000 ppmv, preferably 200 to 30,000 ppmv, more preferably 500 to 25,000 ppmv, more preferably 500 to 20,000 ppmv, more preferably 500 to 15,000 ppmv, more preferably 750 to 15,000 ppmv, more preferably 1,000 to 11,000 ppmv, more preferably 1,000 to 10,000 ppmv. The method according to any one of Embodiments 1 to 7, comprising H2O in a more preferably 2,000 to 8,000 ppmv, more preferably 3,000 to 7,500 ppmv, more preferably 3,100 to 7,400 ppmv, more preferably 3,500 to 7,200 ppmv, more preferably 4,000 to 7,100 ppmv, more preferably 4,500 to 7,000 ppmv, and more preferably 5,000 to 6,500 ppmv.

[0082] 9. The method according to any one of Embodiments 1 to 8, wherein the feed gas stream prepared in step (ii) further comprises one or more inert gases and H2, and the total amount of NH3, inert gases, and H2 contained in the feed gas stream prepared in step (ii) is in the range of 90 to 100% by mass, preferably 95 to 99.95% by volume, more preferably 98 to 99.9% by volume, more preferably 99 to 99.85% by volume, and the one or more inert gases are preferably selected from N2, Ar, and mixtures thereof.

[0083] 10. The method according to any one of Embodiments 1 to 9, wherein the method is for the purpose of reforming ammonia and hydrocarbons, the feed gas stream prepared in step (ii) contains one or more hydrocarbons and one or more CO2 and H2O, and the exhaust gas stream removed in step (iv) further contains CO.

[0084] 11. The method according to Embodiment 10, wherein the feed gas stream prepared in step (ii) further contains CO2 and one or more hydrocarbons, and the feed gas stream contains H2O, preferably 5% by volume or less, more preferably 3% by volume or less, more preferably 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, and more preferably 0.01% by volume or less.

[0085] 12. The method according to Embodiment 10, wherein the feed gas stream prepared in step (ii) further comprises H2O and one or more hydrocarbons, and the feed gas stream contains CO2, preferably 5% by volume or less, more preferably 3% by volume or less, more preferably 1% by volume or less, more preferably 0.5% by volume or less, more preferably 0.1% by volume or less, more preferably 0.05% by volume or less, and more preferably 0.01% by volume or less.

[0086] 13. The method according to Embodiment 10, wherein the feed gas stream prepared in step (ii) further comprises CO2, H2O, and one or more hydrocarbons.

[0087] 14. The method according to any one of embodiments 10 to 13, wherein the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, preferably C1 to C10 alkanes and mixtures thereof, more preferably C3 to C9 alkanes and mixtures thereof, more preferably C4 to C8 alkanes and mixtures thereof, more preferably C5 to C7 alkanes and mixtures thereof, and more preferably C6 alkanes and mixtures thereof.

[0088] 15. The method according to any one of embodiments 10 to 14, wherein the contact is made at a pressure in the range of 10 to 50 bar, preferably 12 to 45 bar, more preferably 15 to 40 bar, more preferably 18 to 35 bar, and more preferably 20 to 30 bar.

[0089] 16. The method according to any one of Embodiments 10 to 15, wherein the supply gas stream prepared in step (ii) contains 0.1 to 75 volume%, preferably 0.3 to 60 volume%, more preferably 0.5 to 50 volume%, more preferably 0.8 to 40 volume%, more preferably 1 to 30 volume%, and more preferably 12 to 25 volume% of NH3.

[0090] 17. The method according to any one of embodiments 10 to 16, wherein the supply gas stream prepared in step (ii) contains 10 to 70 volume%, preferably 12 to 60 volume%, more preferably 15 to 50 volume%, more preferably 20 to 40 volume%, and more preferably 22 to 29 volume%, of the one or more hydrocarbons.

[0091] 18. The method according to any one of embodiments 10 to 17, wherein the supply gas stream prepared in step (ii) contains 0 to 75 volume%, preferably 0.5 to 70 volume%, more preferably 1 to 68 volume%, more preferably 3 to 66 volume%, more preferably 5 to 64 volume%, more preferably 8 to 62 volume%, more preferably 10 to 60 volume%, more preferably 25 to 50 volume%, and more preferably 33 to 44 volume% of H2O.

[0092] 19. The method according to any one of embodiments 10 to 18, wherein the supply gas stream prepared in step (ii) contains 0 to 60 volume%, preferably 1 to 58 volume%, more preferably 3 to 56 volume%, more preferably 5 to 54 volume%, more preferably 8 to 52 volume%, more preferably 10 to 50 volume%, and more preferably 12 to 20 volume% CO2.

[0093] 20. The method according to any one of embodiments 10 to 19, wherein the supply flow exhibits an H2O:C molar ratio of H2O to carbon contained in the one or more hydrocarbons in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.2 to 3, more preferably 0.3 to 2.5, more preferably 0.4 to 2, and more preferably 0.5 to 1.6.

[0094] 21. The method according to any one of Embodiments 10 to 20, wherein the supply flow exhibits a CO2:C molar ratio of CO2 to carbon contained in the one or more hydrocarbons in the range of 0 to 4, preferably 0.1 to 3, more preferably 0.2 to 2, more preferably 0.3 to 1.5, and more preferably 0.4 to 0.8.

[0095] 22. The method according to any one of Embodiments 10 to 21, wherein the supply flow exhibits an NH3:C molar ratio of NH3 to carbon contained in the one or more hydrocarbons in the range of 0 to 5, preferably 0 to 4, more preferably 0.001 to 3, more preferably 0.005 to 2, and more preferably 0.01 to 1.

[0096] 23. The method according to any one of embodiments 10 to 22, wherein the exhaust gas flow removed in step (iv) further contains CO2.

[0097] 24. The exhaust gas flow removed in step (iv) exhibits a stoichiometric number R in the range of 0.1 to 3, where R is defined according to equation (I):

number

[0098] 25. The method according to Embodiment 24, wherein the stoichiometric number R is in the range of 1 to 2.5, preferably 1.3 to 2.2.

[0099] 26. The method according to Embodiment 24, wherein R is greater than 2.

[0100] 27. The method according to any one of embodiments 10 to 23 and 26, wherein the exhaust gas flow removed in step (iv) exhibits an H2:CO molar ratio greater than 2.

[0101] 28. The method according to Embodiment 24, wherein the stoichiometric number R is in the range of 0.5 to 3, preferably 1 to 2.2, and more preferably 1.3 to 1.7.

[0102] 29. The method according to any one of embodiments 10 to 28, wherein the exhaust gas flow removed in step (iv) contains 10 to 90 volume%, preferably 20 to 80 volume%, more preferably 30 to 70 volume%, more preferably 40 to 65 volume%, and more preferably 45 to 60 volume% of H2.

[0103] 30. The method according to any one of embodiments 10 to 29, wherein the exhaust gas flow removed in step (iv) contains 1 to 70 volume%, preferably 3 to 50 volume%, more preferably 5 to 40 volume%, more preferably 10 to 35 volume%, and more preferably 15 to 30 volume% of CO.

[0104] 31. The method according to any one of Embodiments 10 to 30, wherein the exhaust gas flow removed in step (iv) contains 1 to 50 volume%, preferably 3 to 45 volume%, more preferably 5 to 40 volume%, more preferably 8 to 35 volume%, more preferably 10 to 30 volume%, and more preferably 12 to 25 volume% of CO2.

[0105] 32. The method according to any one of Embodiments 1 to 31, wherein the Co3Mo3N comprises one or more Co3Mo3N crystalline phases, and the one or more crystalline phases are preferably determined according to Reference Example 1.a.

[0106] 33. The method according to Embodiment 32, 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.

[0107] 34. The method according to Embodiment 32 or 33, wherein the Co3Mo3N comprises one or more primary particles.

[0108] 35. The method according to Embodiment 34, 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.

[0109] 36. The method according to Embodiment 34 or 35, 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.

[0110] 37. The method according to any one of embodiments 34 to 36, wherein the primary particles comprise one or more aggregates of one or more Co3Mo3N nanocrystalline materials.

[0111] 38. The method according to Embodiment 37, wherein the Co3Mo3N nanocrystal has 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 Example 1.a.

[0112] 39. The method according to any one of Embodiments 1 to 38, wherein the catalyst material contains 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.

[0113] 40. The method according to Embodiment 39, wherein the Co2Mo3N comprises one or more Co2Mo3N crystalline phases, and 90 to 100% by mass, preferably 95 to 100% by mass, more preferably 99 to 100% by mass, and most preferably 99.9 to 100% by mass of the Co2Mo3N is contained in the one or more Co2Mo3N crystalline phases.

[0114] 41. The method according to any one of Embodiments 1 to 40, wherein the catalyst material 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, more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material.

[0115] 42. The method according to any one of Embodiments 1 to 41, wherein the catalyst material contains (M1)2MoO4 in an amount of 0 to 1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material.

[0116] 43. The catalyst material contains molybdic acid oxoanion in an amount of 0 to 1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, based on the total mass of the catalyst material, and the molybdic acid oxoanion is 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 thereof. The method according to any one of Embodiments 1 to 42.

[0117] 44. The method according to any one of Embodiments 1 to 43, wherein the one or more first promoter metals M1 are in the form of one or more hydroxides and oxides.

[0118] 45. The method according to any one of Embodiments 1 to 44, wherein the one or more first promoting metals M1 contained in the catalyst material provided in the reactor according to step (i) 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.

[0119] 46. ​​The catalyst material contained in the reactor provided according to step (i) is 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 The method according to any one of Embodiments 1 to 45, wherein the molar ratio M1:Mo of the one or more first promoting metals M1 calculated as the total molar amount of the 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.

[0120] 47. The method according to any one of Embodiments 1 to 46, wherein the catalyst material contained in the reactor provided according to step (i) further comprises one or more second promoting metals M2 supported on the Co3Mo3N, the one or more second promoting metals M2 being selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, La and two or more mixtures thereof, more preferably from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, La and two or more mixtures thereof, more preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re and two or more mixtures thereof, and more preferably from the group consisting of Mn, Fe and mixtures thereof, the one or more second promoting metals M2 being more preferably Fe or Mn, and the one or more second promoting metals M2 being more preferably Fe.

[0121] 48. The method according to Embodiment 47, wherein the one or more second promoting metals M2 are in the form of one or more hydroxides and oxides.

[0122] 49. The catalyst material is 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 : 1~4.0×10 -2 : In the range of 1, more preferably 9.0 × 10 -3 :1~2.9×10 -2 : In the range of 1, more preferably 1.0 × 10 -2 :1~2.0×10 -2 The method according to Embodiment 47 or 48, wherein the molar ratio M2:Mo of the one or more second promoting metals M2, calculated as the total molar amount of the one or more second promoting metals M2 as elements in the range of :1, and Mo, preferably Mo contained in the Co3Mo3N, calculated as elements.

[0123] 50. The method according to any one of Embodiments 1 to 49, wherein the catalyst material contained in the reactor provided in step (i) further comprises one or more third 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 Li, Na, Ca, and mixtures of two or more thereof.

[0124] 51. The method according to any one of Embodiments 1 to 50, wherein the catalyst material contained in the reactor provided in step (1) comprises 0 to 1% by mass, preferably 0 to 0.1% by mass, more preferably 0 to 0.01% by mass, of elemental Cr, based on the total mass of Co3Mo3N, one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3.

[0125] 52. The method according to any one of Embodiments 1 to 51, wherein 90 to 100% by mass, preferably 95 to 100% by mass, more preferably 99 to 100% by mass, of the one or more first promoting metals M1, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3 contained in the catalyst material contained in the reactor provided in step (1) is contained in a layer supported on Co3Mo3N, and the layer is preferably amorphous.

[0126] 53. The method according to Embodiment 52, 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 layer thickness is preferably determined according to Reference Example 1.b.

[0127] 54. The method according to any one of Embodiments 1 to 53, 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, optionally one or more second promoting metals M2, and optionally one or more third promoting metals M3, H, and O.

[0128] 55. The catalyst material is 1 to 25 m 2 Range of / g, preferably 5-22m 2 Range of / g, more preferably 7-20m 2 The method according to any one of Embodiments 1 to 54, 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.

[0129] 56. The method according to any one of Embodiments 1 to 55, wherein the catalyst material is 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.

[0130] 57. The method according to any one of Embodiments 1 to 56, wherein the catalyst material has 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, and the tap density is preferably determined according to Reference Example 1.c.

[0131] 58. The catalyst material is 0.4 to 2.5 g / cm³ -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 The method according to any one of Embodiments 1 to 57, wherein the bulk density is in the range of , and the bulk density is preferably determined according to Reference Example 1.d.

[0132] 59. The catalyst material is 0.4 to 2.3 g / cm³ -3 The range is preferably 0.8 to 2.1 g / cm³. -3 The range is, more preferably 1.2 to 1.9 g / cm³. -3 The method according to any one of embodiments 1 to 58, having a loose bed density in the range of .

[0133] 60. The method according to any one of Embodiments 1 to 59, wherein the exhaust gas stream removed in step (iv) is used in a methanol production process, a dimethyl ether production process, or a methanol and dimethyl ether production process.

[0134] 61. The method according to any one of Embodiments 1 to 60, wherein the exhaust gas stream removed in step (iv) is used in a hydrocarbon production process, preferably according to the Fischer-Tropsch process.

[0135] 62. The method according to any one of embodiments 1 to 61, wherein the exhaust gas stream removed in step (iv) is used in a process for producing alcohol, preferably alkanol, more preferably C1-C10 alkanol, more preferably C2-C8 alkanol, more preferably C2-C6 alkanol, more preferably C2-C4 alkanol, more preferably C2 alkanol, and more preferably ethanol.

[0136] 63. The method according to any one of Embodiments 1 to 62, wherein the feed gas stream prepared in step (ii) and supplied to the reactor in step (iii) contains H2 for reducing the catalyst material.

[0137] 64. The method according to Embodiment 63, wherein the feed gas stream prepared in step (ii) and supplied to the reactor in step (iii) contains 0.5 to 80 volume%, preferably 1 to 70 volume%, more preferably 2 to 60 volume%, more preferably 5 to 50 volume%, and more preferably 15 to 40 volume% of H2.

[0138] The present invention is further illustrated by the following reference examples, examples, and comparative examples. [Examples]

[0139] 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).

[0140] 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).

[0141] 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

[0142] 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.

[0143] 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.

[0144] The aspect ratio of the primary particles was manually determined by TEM based on the TEM images.

[0145] Particle size was estimated based on the evaluation of several TEM images.

[0146] The layer thickness was determined visually based on TEM images.

[0147] 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.

[0148] Reference Example 1.d: Measurement of bulk density The bulk density was determined by helium picrometry.

[0149] 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. 244H2O (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.

[0150] Reference Example 3: Preparation of Catalyst Materials A 13 g sample of CoMoO4·nH2O obtained from Reference Example 2 was subjected to impregnation with a water-soluble accelerator and a co-accelerator solution. Impregnation with the accelerator Cs was performed by the initial wet impregnation method. For this purpose, the solvent absorption of the sample obtained from Reference Example 2 was measured to be 0.6 mL / g, and the accelerator solution was prepared with a total volume of 7.8 mL and mixed with CoMoO4·nH2O. The resulting wet material was dried in synthetic air at 80°C for 16 hours.

[0151] To promote co-acceleration with Re, a sequential initial wet impregnation method was applied, and the accelerator was first added according to the procedure described above. Subsequently, Re was added as a co-accelerator using diluted perlenic acid. The resulting material was dried in synthetic air at 80°C for 16 hours.

[0152] The metal compounds 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 decomposition catalyst, and the molar ratios of alkali metals and 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.

[0153] [Table 1]

[0154] [Table 2]

[0155] The resulting supported CoMoO4·nH2O was subjected to ammonia decomposition treatment according to the following procedure.

[0156] 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.

[0157] [Table 3]

[0158] Example 1: The supply flow contains 94.5 vol% NH3 and 5 vol% inert gas, at a pressure of 20 bar, and for 4000 h -1 It had a gas time-space velocity (GHSV) of 5,000 volumes and contained 5,000 ppm (ppmv) of H2O.

[0159] The results of the catalyst tests are shown in Figure 1 and Table 1.

[0160] [Table 4]

[0161] As is clear from the results, the method of the present invention achieves a relatively high NH3 conversion rate compared to the reference Ni catalyst, particularly in the temperature range of 450 to 650°C. Description: - A.Srifaら,Applied Catalysis B:Environmental 218(2017),p.1-8 - I.Lucentiniら,Ind.Eng.Chem.Res.2021,60,18560-18611 - T.Leら,Korean J.Chem.Eng.,2021,38(6),1087-1103 - X.-K.Liら, Journal of Catalysis, 2005, 236, 181-189 - Bellら, Top Catal., 2016,59,1438-1457 - S. Sayasら, Catalog.Sci.Technol.,2020,10,5027-5

Claims

1. A method for reforming ammonia, comprising the following steps: (i) A step of providing a reactor including a catalyst material, wherein the catalyst material is Co ３ Mo ３ The material comprises N and one or more first promoting metals M1 selected from the group consisting of alkali metals and mixtures of two or more thereof, wherein the one or more first promoting metals M1 is Co ３ Mo ３ The process is supported on N; (ii) NH ３ A step of preparing a supply gas flow including; (iii) A step of supplying the supply gas flow prepared in step (ii) to the reactor provided in step (i), and bringing the supply gas flow into contact with the catalyst material, wherein the contact is carried out at a pressure exceeding 5 bar and a temperature in the range of 200 to 700°C; (iv) A step of removing the exhaust gas flow from the reactor, wherein the exhaust gas flow is H ２ and N ２ Processes and Methods that include...

2. The supply gas flow prepared in step (ii) is H100 to 50,000 ppmv. ２ The method according to claim 1, comprising O.

3. The supply gas stream prepared in step (ii) further comprises one or more inert gases and H ２ and the NH ３ contained in the supply gas stream prepared in step (ii), inert gas, and H ２ The method according to claim 1 or 2, wherein the total amount of is in the range of 90 to 100% by mass.

4. The method described above is for the purpose of reforming ammonia and hydrocarbons, and the feed gas stream prepared in step (ii) is composed of one or more hydrocarbons and CO ２ and H ２ The method according to claim 1 or 2, wherein the exhaust gas flow removed in step (iv) further contains one or more O, and further contains CO.

5. The aforementioned Co ３ Mo ３ Co with one or more N ３ Mo ３ The method according to claim 1 or 2, comprising an N crystalline phase.

6. The aforementioned Co ３ Mo ３ The method according to claim 5, wherein N comprises one or more primary particles.

7. The method according to claim 6, wherein the primary particles have an average particle size D50 in the range of 10 to 200 nm.

8. The method according to claim 1 or 2, wherein the one or more first promoting metals M1 contained in the catalyst material provided in the reactor according to step (i) are selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof.

9. The catalyst material contained in the reactor provided according to step (i) is 1.0 × 10 －３ : 1-8.5 x 10 －２ The method according to claim 1 or 2, wherein the molar ratio M1:Mo of the one or more first promoting metals M1 calculated as the total molar amount of the one or more first promoting metals M1 as elements, in the range of :1, and Mo calculated as elements.

10. The catalyst material contained in the reactor provided according to step (i) is the Co ３ Mo ３ The method according to claim 1 or 2, further comprising one or more second promoting metals M2 supported on N, wherein the one or more second promoting metals M2 are selected from the group consisting of V, Nb, Ta, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Ga, In, Sc, La, and mixtures of two or more thereof.

11. The catalyst material is 1.0 × 10 －３ : 1-2.0 x 10 －１ The method according to claim 10, wherein the molar ratio M2:Mo of the one or more second promoting metals M2 calculated as the total molar amount of the one or more second promoting metals M2 as elements, in the range of :1, and Mo calculated as elements.

12. The method according to claim 1 or 2, wherein the catalyst material contained in the reactor provided in step (i) further comprises one or more third promoting metals M3, wherein M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof.

13. The method according to claim 1 or 2, wherein the exhaust gas stream removed in step (iv) is used in a methanol production process, a dimethyl ether production process, or a methanol and dimethyl ether production process.

14. The method according to claim 1 or 2, wherein the exhaust gas flow removed in step (iv) is used in a hydrocarbon production process.

15. The method according to claim 1 or 2, wherein the exhaust gas stream removed in step (iv) is used in the alcohol production process.

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