EP4688255A1

EP4688255A1 - A catalytic material comprising supported co3mo3n for the synthesis of nh3

Info

Publication number: EP4688255A1
Application number: EP24718059.9A
Authority: EP
Inventors: Ivana JEVTOVIKJ; Stephan A. Schunk; Elias Christopher FREI; Sven TITLBACH; Scott Hedrick; David D. DISANTIS; Michael Geske; Matthias Mueller
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-03-31
Filing date: 2024-03-28
Publication date: 2026-02-11
Also published as: CN120957811A; JP2026513034A; KR20250160522A; WO2024200681A1

Abstract

The present invention relates to a catalytic material for the synthesis of NH3, the catalytic material comprising Co3Mo3N, one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, and one or more second promoter 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 promoter metals M1 and the one or more second promoter metals M2 are supported on the Co3Mo3N. Further, the present invention relates to a process for preparing said catalytic material and a catalytic material obtained or obtainable by said process. Yet further, the present invention relates to use of the catalytic material according to the present invention and a process for synthesizing NH3.

Description

A catalytic material comprising supported C03M03N for the synthesis of NH3

TECHNICAL FIELD

The present invention relates to a catalytic material for the synthesis of NH3, a process for the preparation of a catalytic material, a catalytic material obtained or obtainable by said process, a process for the synthesis of NH3, and use of the catalytic material according to the present invention for the synthesis of NH3.

INTRODUCTION

Ternary metallic nitrides have received considerable attention because of their potential catalytic activity utilizing them as suitable catalytic material for ammonia synthesis. In particular, ternary nitrides of Co and Mo are known to show activity in the synthesis of NH3 from hydrogen and nitrogen.

D. Moszyhski et al. disclose a study on “Katalizatory kobaltowo-molibdenowe domieszkowane cezem do syntezy amoniaku” in Przemysl Chemiczny, 2015, 94, 1399-1403. Disclosed therein are cobalt molybdenum nitride catalysts, comprising 0.25 to 3.0 weight-% Cs, 20 to 40 weight-% C02M03N, rest is C03M03N.

D. Moszyhski et al. disclose a study on “Surface and catalytic properties of potassium-modified cobalt molybdenum catalysts for ammonia synthesis", AppL Surf. Sci., 2010, 256, 5581-5584. Disclosed are catalysts comprising 0 to 3.5 weight-% K, 20 to 50 weight-% C02M03N, rest is C03M03N.

D. Moszyhski et al. disclose a study on “Cobalt molybdenum nitrides co-promoted by chromium and potassium as catalysts for ammonia synthesis" in Chem. Pap., 2018, 72, 425-430. In particular, the co-promotion of a C03M03N catalyst with K and Cr is disclosed therein, wherein the catalysts comprise of a mixture of C02M03N (26 to 30 weight-%) and C03M03N (70 to 74 weight-%) as well as 0.34 to 0.37 weight-% K and 0.47 to 1 .42 weight-% Cr.

D. Moszyhski et al. disclose a study on “Thermal Stability of Potassium-Promoted Cobalt Molybdenum Nitride Catalysts for Ammonia Synthesis” in Catalysts, 2022, 12, 100. In particular, cobalt molybdenum nitride catalysts comprising 0.2 to 3.5 weight-% K, C02M03N and C03M03N are disclosed therein.

C. J. H. Jacobsen et al. disclose a study on “Novel class of ammonia synthesis catalysts”, Chem. Commun., 2000, 1057-1058. In particular, phase pure C03M03N catalysts are disclosed by precipitation of (NH4)6MoyO24 with Co(NO3)2, which were Cs promoted. US 6235676 B1 discloses a process for the preparation of ammonia and 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” a Group VIII metal and x and y each are a mixed number between 1 and 10 and including a promoter selected from Group IA and Group HA metals.

R. Kojima et al. disclose a study on “Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis: Part 1. Preparation and characterization” in AppL CataL, A, 2001 , 215, 149-160. In particular, various C03M03N catalysts promoted with 0.5 to 15.5 weight-% K or 0.4 to 21.7 weight-% Cs are disclosed.

P. Adamski et al. disclose in Catalysts 2022, 12, 100 a study on the thermal stability of potas- sium-promoted cobalt molybdenum nitride catalysts for ammonia synthesis.

Accordingly, it was the object of the present invention to provide a catalytic material for the synthesis of NH3, in particular allowing a conversion at comparatively lower temperatures and/or lower pressures. This is desired to reduce the overall resource and energy costs, as well as a reduction of CO2 emissions, enabling a sustainable synthesis concept.

DETAILED DESCRIPTION

Thus, it has surprisingly been found that a catalytic material can be provided which comprises bimetallic nitride C03M03N being promoted with two promoter metals. The catalytic material according to the present invention can be prepared by the synthesis of a bimetallic nitride catalyst via precipitation of a suitable amorphous oxide precursor, subsequent promotion and ammonolysis of the promoted precursor. It has surprisingly been found that the catalytic material prepared in this way offer better performance in the synthesis of NH3 than commonly known systems. Additionally, the catalytic material of the present invention can impact the ammonia production by lowering the CO2 emission per ton of NH3 produced. Thus, the process of the present invention can be included as drop-in solution for existing Haber-Bosch plants to lower their energy consumption as the Haber-Bosch process driven by the present invention can operate at comparatively lower temperatures. Further, the catalytic material of the present invention is more resilient towards varying H2/N2 ratios, including H2 rich feeds, than known low temperature NH3 catalysts.

Therefore, the present invention relates to a catalytic material for the synthesis of NH3, the catalytic material comprising C03M03N, one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, and one or more second promoter 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 promoter metals M 1 and the one or more second promoter metals M2 are supported on the C03M03N. It is preferred that the C03M03N comprises one or more crystalline C03M03N phases, wherein the one or more crystalline phases are preferably determined according to Reference Example 1.a.

In the case where the C03M03N comprises one or more crystalline C03M03N phases, it is preferred that from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the C03M03N is comprised in the one or more crystalline C03M03N phases, wherein the amount of the one or more crystalline C03M03N phases in the C03M03N comprised in the catalytic material is preferably determined according to Reference Example 1.a.

Further in the case where the C03M03N comprises one or more crystalline C03M03N phases, it is preferred that the C03M03N comprises one or more primary particles.

In the case where the C03M03N comprises one or more primary particles, it is preferred that the primary particles have an aspect ratio of the length of the primary particle to the width of the primary particle in the range of 1 .0 to 3.0, more preferably in the range of 1 .0 to 2.0, more preferably in the range of 1 .0 to 1 .5, wherein the aspect ratio is preferably determined according to Reference Example 1 .b.

Further in the case where the C03M03N comprises one or more primary particles, it is preferred that the primary particles have an average particle size D50 in the range of 10 to 200 nm, more preferably in the range of 15 to 150 nm, more preferably in the range of 20 to 90 nm, wherein the average particle size D50 is preferably determined according to Reference Example 1 .b.

Further in the case where the C03M03N comprises one or more primary particles, it is preferred that the primary particles comprise one or more agglomerates of one or more C03M03N nanocrystallites.

In the case where the primary particles comprise one or more agglomerates of one or more C03M03N nano-crystallites, it is preferred that the C03M03N nano-crystallites have an average crystallite size in the range of 50 to 75 nm, more preferably in the range of 65 to 69 nm, wherein the average crystallite size is preferably determined according to Reference Example 1.a.

It is preferred that the catalytic material comprises from 0 to 10 weight-%, more preferably from 0 to 5 weight-%, more preferably from 0 to 4 weight-%, more preferably from 0 to 3 weight-%, of C02M03N, based on the total weight of the catalytic material.

In the case the catalytic material comprises from 0 to 10 weight-% of C02M03N, it is preferred that the C02M03N comprises one or more crystalline C02M03N phases, wherein from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the C02M03N are in the one or more crystalline C02M03N phases. It is preferred that the catalytic material comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of an oxidic phase of one or more of Co and Mo, based on the total weight of the catalytic material.

It is preferred that the catalytic material comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of (M1 )2MoO4, based on the total weight of the catalytic material.

It is preferred that the catalytic material comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of a molybdate oxoanion, based on the total weight of the catalytic material, wherein the molybdate oxoanion is selected from the group consisting of MoC>4²’, MO2C>7²’, MosOw^2-, Mo4Oi3^2-, MosOie^2-, Mo₆Oi9²’, Mo₇O₂4% MosC ", and mixtures of two or more thereof.

It is preferred that from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, of the one or more first promoter metals M 1 and of the one or more second promoter metals M2 are comprised in a layer supported on the C03M03N, wherein the layer preferably is amorphous.

In the case where from 90 to 100 weight-% of the one or more first promoter metals M1 and of the one or more second promoter metals M2 are comprised in a layer supported on the C03M03N, it is preferred that the layer has a thickness 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, more preferably in the range of 2 to 5 nm, wherein the layer thickness is preferably determined according to Reference Example 1 .b.

It is preferred that the one or more first promoter metals M 1 are in the form of one or more of hydroxides and oxides.

It is preferred that the one or more first promoter metals M 1 are 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, wherein the one or more first promoter metals M1 preferably are K or Cs, wherein the one or more first promoter metals M1 more preferably are Cs.

It is preferred that the catalytic material has a molar ratio M1 :Mo, of the one or more first promoter metals M1 , calculated as sum of molar amounts of the one or more first promoter metals M1 as elements, to Mo, preferably to Mo comprised in the C03M03N, calculated as element, in the range of 1.0-1 O’³: 1 to 8.5-10²:1 , more preferably in the range of 2.0-10³:1 to 8.0-10²:1 , more preferably in the range of 3.0-10³:1 to 7.5-10²:1 , more preferably in the range of 3.6-10³:1 to 7.0-10“²:1 , more preferably in the range of 4.0-10~³:1 to 6.5-10²:1 , more preferably in the range of 4.1 -10“³:1 to 6.2-10“²:1 , more preferably in the range of 5.0-10³:1 to 6.0-10²:1 , more preferably in the range of 6.0- 10³: 1 to 5.5-10²: 1 , more preferably in the range of 7.0-10³: 1 to 5.0- 10²:1 , more preferably in the range of 8.0-10³:1 to 4.5-10²:1 , more preferably in the range of 9.0-10~³:1 to 4.0-10“²:1 , more preferably in the range of 1 .0-10~²:1 to 3.5-10²:1 , more preferably in the range of 1.2-10²:1 to 3.3-10²:1 , more preferably in the range of 2.0-10²:1 to 3.0-10²:1.

It is preferred that the one or more second promoter metals M2 are in the form of one or more of hydroxides and oxides.

It is preferred that the one or more second promoter metals M2 are selected from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more thereof, preferably from the group consisting of Mn, Fe, and mixtures thereof, wherein the one or more second promoter metals M2 more preferably are Fe or Mn, wherein the one or more second promoter metals M2 more preferably is Fe.

It is preferred that catalytic material has a molar ratio M2:Mo, of the one or more second promoter metals M2, calculated as sum of molar amounts of the one or more second promoter metals M2 as elements, to Mo, preferably to Mo comprised in the C03M03N, calculated as element, in the range of 1 .0-10³:1 to 2.0-10 ¹:1 , more preferably in the range of 2.0-10³:1 to 1.2-10 ¹:1 , more preferably in the range of 2.2-10³:1 to 1 .0-10~²:1 , more preferably in the range of 3.0-10³:1 to 9.0-10“²:1 , more preferably in the range of 4.0-10³:1 to 8.0-10²:1 , more preferably in the range of 4.3-10³:1 to 7.0-10²:1 , more preferably in the range of 5.0-10~³:1 to 6.0-10²:1 , more preferably in the range of 6.0-10³:1 to 5.0-10²:1 , more preferably in the range of 7.0-10³:1 to 4.0-10“²:1 , more preferably in the range of 8.0-10³:1 to 3.0-10²:1 , more preferably in the range of 9.0-1 O’³: 1 to 2.9-10²: 1 , more preferably in the range of 1.0-10²:1 to 2.0-10²:1.

It is preferred that the catalytic material further comprises one or more co-promoter metals M3, wherein M3 is preferably different to M1 , and wherein M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof, more preferably selected from the group consisting of Li, Na, Ca, and mixtures of two or more thereof.

It is preferred that the catalytic material comprises from 0 to 1 weight-%, more preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cr, calculated as element, based on the total weight of the catalytic material.

It is preferred that from 90 to 100 weight-%, more preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the catalytic material consist of Co, Mo, N, the one or more first promoter metals M 1 , the one or more second promoter metals M2, the one or more co-promoter metals M3, H, and O.

It is preferred that the catalytic material has a BET specific surface area in the range of 1 to 25 m²/g, more preferably in the range of 5 to 22 m²/g, more preferably in the range of 7 to 20 m²/g, wherein the BET specific surface area is preferably determined according to ISO 9277:2022. It is preferred that the catalytic material is in the form of particles, wherein the particles have a particle size in the range of 200 to 365 pm, more preferably in the range of 225 to 340 pm, more preferably in the range of 250 to 315 pm.

It is preferred that the catalytic material 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, 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.

It is preferred that the catalytic material has a bulk density in the range of 0.4 to 2.5 g/cm ³, more preferably in the range of 0.6 to 2.3 g/cm ³, more preferably in the range of 0.8 to 2.1 g/cm ³, wherein the bulk density is preferably determined according to Reference Example 1.d.

It is preferred that the catalytic material has a loose bed density in the range of 0.4 to 2.3 g/cm ³, more preferably in the range of 0.8 to 2.1 g/cm ³, more preferably in the range of 1 .2 to 1 .9 g/cm ³.

Further, the present invention relates to a process for preparing a catalytic material, preferably for preparing the catalytic material according to any one of the embodiments disclosed herein, the process comprising

(i) preparing an aqueous mixture comprising one or more sources of Mo, one or more sources of Co, and 1 ,3,5,7-tetraazaadamantane (urotropine);

(ii) heating the mixture obtained in (i) to a temperature in the range of 60 to 110 °C, for obtaining a support material;

(iii) mixing the support material obtained in (ii) with an aqueous mixture comprising one or more sources of one or more first promoter metals M1 , wherein M1 is selected from the group consisting of alkali metals, and mixtures of two or more thereof, preferably 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, wherein the one or more first promoter metals M1 more preferably are K or Cs, wherein the one or more first promoter metals M1 more preferably are Cs, and one or more sources of one or more second promoter metals M2, wherein 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 mixtures of two or more thereof, preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more thereof, more preferably from the group consisting of Mn, Fe, and mixtures thereof, wherein the one or more second promoter metals M2 more preferably are Fe or Mn, wherein the one or more second promoter metals M2 more preferably are Fe, for obtaining a supported material;

(iv) reacting the supported material with NH3, for obtaining the catalytic material.

It is preferred that the one or more sources of Mo are selected from the group consisting of (N H₄)₆MO7O₂4, (N H₄)₆MO7O₂4 ■ 4 H₂O, and mixtures of two or more thereof, wherein the one or more Mo sources more preferably are (NH4)eMo7O₂4 or (NH4)eMo7O₂4 ■ 4 H₂O. It is preferred that the one or more sources of Co are selected from the group consisting of CO(NO₃)₂ ■ 6H₂O, CO(OH)₂, COCI₂, COCI₂ ■ 2 H₂O, CoCI₂ ■ 6 H₂O, CoSO₄ ■ 6 H₂O, CoSO₄ ■ 7 H₂O, and mixtures of two or more thereof, wherein the one or more Co sources preferably are CO(NO₃)₂ ■ 6H₂O.

It is preferred that the one or more sources of M1 are selected from the group consisting of salts of M1 , hydrated salts of M1 , oxidic compounds of M1 , hydrated oxidic compounds of M1 , and mixtures thereof, more preferably from the group consisting of salts of M 1 , hydrated salts of M 1 , and mixtures thereof, wherein the one or more sources of M1 more preferably are salts of M1 , wherein the salts are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, hydroxides, and mixtures thereof, wherein the salts preferably are nitrates, wherein the hydrated salts are preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated hydroxides, and mixtures thereof, wherein the hydrated salts preferably are hydrated nitrates.

It is preferred that the one or more sources for M2 are selected from the group consisting of salts of M2, hydrated salts of M2, oxidic compounds of M2, hydrated oxidic compounds of M2, and mixtures thereof, more preferably from the group consisting of hydrated salts, oxidic compounds, and mixtures thereof, wherein the salts are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, ethanolates, citrates, and mixtures of two or more thereof, wherein 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.

It is preferred that the aqueous solution prepared in (i) has a molar ratio of 1 ,3,5,7-tetraazaada- mantane (urotropine), calculated as molar amount of 1 ,3,5,7-tetraazaadamantane (urotropine), to Mo, calculated as element, in the range of 1.0:1 to 3.0:1 , more preferably in the range of 1.5:1 to 2.5:1 , more preferably in the range of 1.9:1 to 2.1 :1.

It is preferred that the mixture obtained in (i) is heated in (ii) to a temperature in the range of 70 to 100 °C, more preferably in the range of 75 to 95 °C, more preferably in the range of 80 to 90 °C.

It is preferred that the heating according to (ii) is performed for a duration in the range of 1 to 50 h, more preferably in the range of 5 to 25 h, more preferably in the range of 10 to 20 h, more preferably in the range of 15 to 18 h.

It is preferred that the aqueous solution obtained in (ii) has a pH in the range of from 4 to 7, more preferably in the range of from 5 to 6. It is preferred that heating in (ii) is performed under autogenous pressure, more preferably in an autoclave, more preferably a PTFE-lined steel autoclave, or wherein heating is performed at ambient pressure, preferably in a flask mounted with a reflux condenser.

It is preferred that the process further comprises after (ii) and prior to (iii) (s) isolating the support material obtained in (ii), preferably by filtration.

In the case where the process comprises (s), it is preferred that the process further comprises after (s) and prior to (iii)

(w) washing the support material obtained from (s) with water, more preferably with an amount of water in the range of 1 to 100 mL/g(support material), more preferably in the range of 10 to 30 mL/g(support material).

It is preferred that the process further comprises after (ii) and prior to (iii), more preferably after (s) as defined hereinabove and prior to (iii), more preferably after (w) as defined hereinabove and prior to (iii),

(d1) drying the support material obtained in (ii), (s), or (w) 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 more preferably comprises, more preferably consists of, one or more of oxygen and nitrogen, preferably air, more preferably synthetic air.

In the case where the process further comprises (d1), it is preferred that drying according to (d1) is performed for a duration in the range of 1 to 30 h, more preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

It is preferred that the process further comprises after (ii) and prior to (iii), preferably after (s) as defined hereinabove and prior to (iii), more preferably after (w) as defined in claim 41 and prior to (iii),

(d2) freeze drying the solids obtained in (ii), (s), or (w) in a gas atmosphere having a pressure in the range of 1 to 8 mbar(abs), more preferably in the range of 2 to 4 mbar(abs), at a condenser temperature in the range of -100 to -50 °C, more preferably in the range of - 80 to -60 °C, and wherein the solids have a temperature in the range of -30 to 0 °C, more preferably in the range of -20 to -10 °C, wherein the gas atmosphere more preferably comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air.

In the case where the process comprises (d2), it is preferred that freeze drying according to (d2) is performed for a duration in the range of 1 to 30 h, more preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

It is preferred that the process further comprises after (ii) and prior to (iii), preferably after (d1) as defined hereinabove and prior to (iii), or after (d2) as defined hereinabove and prior to (iii), (c) calcining the solids obtained in (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 more preferably comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air.

It is preferred that mixing according to (iii) comprises impregnation, more preferably incipient wetness impregnation.

In the case where mixing according to (iii) comprises impregnation, it is preferred that the volume ratio of the aqueous mixture to the pore volume of the support material obtained in (ii), (s), (w), (d1), or (d2) is in the range of 0.9:1 to 1.1 :1 , more preferably in the range of 0.95:1 to 1.05:1 , more preferably in the range of 0.99:1 to 1.01 :1.

It is preferred that (iv) is performed in a stream of NH3 having a flow rate in the range of 250 to 400 ml min ¹, more preferably in the range of 275 to 375 ml min ¹, more preferably in the range of 300 to 350 ml min ¹.

It is preferred that (iv) comprises heating the supported material to a temperature in the range of 600 to 900 °C, more preferably in the range of 700 to 800 °C, more preferably in the range of 725 to 775 °C.

It is preferred that (iv) is performed for a duration in the range of 1 .0 to 15.0 h, more preferably in the range of 5.0 to 11 .0 h, more preferably in the range of 7.0 to 9.0 h, more preferably in the range of 7.5 to 8.5 h.

It is preferred that the process further comprises

(d3) drying the supported material obtained in (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 more preferably comprises, preferably consists of, one or more of oxygen and nitrogen, more preferably air, more preferably synthetic air.

In the case where the process further comprises (d3), it is preferred that drying according to (d3) is performed for a duration in the range of 1 to 30 h, more preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

Yet further, the present invention relates to a catalytic material, preferably a catalytic material according to any one of the embodiments disclosed herein, wherein the catalytic material is obtained or obtainable by the process of any one of the embodiments disclosed herein.

Yet further, the present invention relates to a process for the synthesis of NH3, the process comprising (A) providing a reactor comprising a reaction zone, wherein the reaction zone comprises the catalytic material of any one of the embodiments disclosed herein, wherein the catalytic material has a temperature in the range of 200 to 600 °C;

(B) feeding a gas stream comprising hydrogen and nitrogen into the reactor, wherein the gas stream is brought into contact with the catalytic material for obtaining a product gas stream comprising NH3.

It is preferred that the catalytic material has a temperature in the range of 250 to 550 °C, more preferably in the range of 275 to 525 °C.

It is preferred that the gas stream according to (B) comprises from 45 to 95 volume-%, more preferably from 50 to 90 volume-%, more preferably from 60 to 80 volume-%, of hydrogen.

It is preferred that the hydrogen comprised in the gas stream according to (B) is prepared from one or more renewable sources.

It is preferred that the gas stream according to (B) comprises from 5 to 55 volume-%, more preferably from 10 to 50 volume-%, more preferably from 20 to 40 volume-%, of nitrogen.

It is preferred that the gas stream is fed into the reactor at a pressure in the range of 40 to 150 bar(abs), more preferably in the range of 50 to 120 bar(abs), more preferably in the range of 55 to 100 bar(abs).

Yet further, the present invention relates to a use of the catalytic material according to any one of the embodiments disclosed herein for the synthesis of NH3.

The unit bar(abs) refers to an absolute pressure wherein 1 bar equals 10⁵ Pa.

The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The catalytic material of any one of embodiments 1 to 4", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The catalytic material of any one of embodiments 1 , 2, 3, and 4". Further, it is explicitly noted that the following set of embodiments is not the set of claims determining the extent of protection, but represents a suitably structured part of the description directed to general and preferred aspects of the present invention.

1 . A catalytic material for the synthesis of NH3, the catalytic material comprising C03M03N, one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, and one or more second promoter 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 promoter metals M1 and the one or more second promoter metals M2 are supported on the C03M03N. The catalytic material of embodiment 1 , wherein the C03M03N comprises one or more crystalline C03M03N phases, wherein the one or more crystalline phases are preferably determined according to Reference Example 1.a. The catalytic material of embodiment 2, wherein from 90 to 100 weight-%, preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the C03M03N is comprised in the one or more crystalline C03M03N phases, wherein the amount of the one or more crystalline C03M03N phases in the C03M03N comprised in the catalytic material is preferably determined according to Reference Example 1.a. The catalytic material of embodiment 2 or 3, wherein the C03M03N comprises one or more primary particles. The catalytic material of embodiment 4, wherein the primary particles have an aspect ratio of the length of the primary particle to the width of the primary particle in the range of 1 .0 to 3.0, preferably in the range of 1 .0 to 2.0, more preferably in the range of 1.0 to 1.5, wherein the aspect ratio is preferably determined according to Reference Example 1.b. The catalytic material of 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, wherein the average particle size D50 is preferably determined according to Reference Example 1.b. The catalytic material of any one of embodiments 4 to 6, wherein the primary particles comprise one or more agglomerates of one or more C03M03N nano-crystallites. The catalytic material of embodiment 7, wherein the C03M03N nano-crystallites have an average crystallite size in the range of 50 to 75 nm, preferably in the range of 65 to 69 nm, wherein the average crystallite size is preferably determined according to Reference Example 1.a. The catalytic material of any one of embodiments 1 to 8, comprising from 0 to 10 weight- %, preferably from 0 to 5 weight-%, more preferably from 0 to 4 weight-%, more preferably from 0 to 3 weight-%, of C02M03N, based on the total weight of the catalytic material. 10. The catalytic material of embodiment 9, wherein the C02M03N comprises one or more crystalline C02M03N phases, wherein from 90 to 100 weight-%, preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the C02M03N are in the one or more crystalline C02M03N phases.

11 . The catalytic material of any one of embodiments 1 to 10, comprising from 0 to 1 weight- %, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of an oxidic phase of one or more of Co and Mo, based on the total weight of the catalytic material.

12. The catalytic material of any one of embodiments 1 to 11 , comprising from 0 to 1 weight- %, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of (M 1 )2MOC>4, based on the total weight of the catalytic material.

13. The catalytic material of any one of embodiments 1 to 12, comprising from 0 to 1 weight- %, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of a molybdate oxoanion, based on the total weight of the catalytic material, wherein the molybdate oxoanion is selected from the group consisting of MoC>4²’, Mo2C>7²’, MosOw^2-, MO4O13²", Mo₅Oi6²-, Mo₆Oi9% MoyC -, MOSC ", and mixtures of two or more thereof.

14. The catalytic material of any one of embodiments 1 to 13, wherein from 90 to 100 weight- %, preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, of the one or more first promoter metals M 1 and of the one or more second promoter metals M2 are comprised in a layer supported on the C03M03N, wherein the layer preferably is amorphous.

15. The catalytic material of 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, more preferably in the range of 2 to 5 nm, wherein the layer thickness is preferably determined according to Reference Example 1.b.

16. The catalytic material of any one of embodiments 1 to 15, wherein the one or more first promoter metals M1 are in the form of one or more of hydroxides and oxides.

17. The catalytic material of any one of embodiments 1 to 16, wherein the one or more first promoter 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, wherein the one or more first promoter metals M1 preferably are K or Cs, wherein the one or more first promoter metals M1 more preferably are Cs.

18. The catalytic material of any one of embodiments 1 to 17, having a molar ratio M1 :Mo, of the one or more first promoter metals M1 , calculated as sum of molar amounts of the one or more first promoter metals M 1 as elements, to Mo, preferably to Mo comprised in the C03M03N, calculated as element, in the range of 1 .0-10³:1 to 8.5-10²:1 , preferably in the range of 2.0-10³:1 to 8.0-10²:1 , more preferably in the range of 3.0-10³:1 to 7.5-10²:1 , more preferably in the range of 3.6-10~³:1 to 7.0-10~²:1 , more preferably in the range of 4.0- 10“³:1 to 6.5-10’²:1 , more preferably in the range of 4.1 -10³:1 to 6.2-10²:1 , more preferably in the range of 5.0-1 O’³: 1 to 6.0-10²:1 , more preferably in the range of 6.0-10³:1 to 5.5- 10“²:1 , more preferably in the range of 7.0- 10³: 1 to 5.0- 10²:1 , more preferably in the range of 8.0-10³:1 to 4.5-10“²:1 , more preferably in the range of 9.0-10~³:1 to 4.0-10²:1 , more preferably in the range of 1 .0-10²:1 to 3.5-10²:1 , more preferably in the range of 1 .2-10²:1 to 3.3-10“²:1 , more preferably in the range of 2.0-10²:1 to 3.0-10²:1.

19. The catalytic material of any one of embodiments 1 to 18, wherein the one or more second promoter metals M2 are in the form of one or more of hydroxides and oxides.

20. The catalytic material of any one of embodiments 1 to 19, wherein the one or more second promoter metals M2 are selected from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more thereof, preferably from the group consisting of Mn, Fe, and mixtures thereof, wherein the one or more second promoter metals M2 more preferably are Fe or Mn, wherein the one or more second promoter metals M2 more preferably is Fe.

21 . The catalytic material of any one of embodiments 1 to 20, having a molar ratio M2:Mo, of the one or more second promoter metals M2, calculated as sum of molar amounts of the one or more second promoter metals M2 as elements, to Mo, preferably to Mo comprised in the C03M03N, calculated as element, in the range of 1 .0-10³:1 to 2.0-10 ¹:1 , preferably in the range of 2.0-10³:1 to 1.2-10 ¹:1 , more preferably in the range of 2.2-10³:1 to 1.0-

10“²:1 , more preferably in the range of 3.0- 10³:1 to 9.0- 10²:1 , more preferably in the range of 4.0-10“³:1 to 8.0-10“²:1 , more preferably in the range of 4.3-10³:1 to 7.0-10²:1 , more preferably in the range of 5.0-10³:1 to 6.0-10²:1 , more preferably in the range of 6.0-10³:1 to 5.0-10’²:1 , more preferably in the range of 7.0-10~³:1 to 4.0-10²:1 , more preferably in the range of 8.0-10’³:1 to 3.0-10²:1 , more preferably in the range of 9.0-10³:1 to 2.9-10²:1 , more preferably in the range of 1 .0-10²:1 to 2.0-10~²:1 .

22. The catalytic material of any one of embodiments 1 to 21 , further comprising one or more co-promoter metals M3, wherein M3 is preferably different to M1 , and wherein M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof, preferably selected from the group consisting of Li, Na, Ca, and mixtures of two or more thereof.

23. The catalytic material of any one of embodiments 1 to 22, comprising from 0 to 1 weight- %, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of Cr, calculated as element, based on the total weight of the catalytic material.

24. The catalytic material of any one of embodiments 1 to 23, wherein from 90 to 100 weight- %, preferably from 95 to 100 weight-%, more preferably from 99 to 100 weight-%, more preferably from 99.9 to 100 weight-%, of the catalytic material consist of Co, Mo, N, the one or more first promoter metals M 1 , the one or more second promoter metals M2, optionally the one or more co-promoter metals M3, H, and O.

25. The catalytic material of any one of embodiments 1 to 24, having a BET specific surface area in the range of 1 to 25 m²/g, preferably in the range of 5 to 22 m²/g, more preferably in the range of 7 to 20 m²/g, wherein the BET specific surface area is preferably determined according to ISO 9277:2022.

26. The catalytic material of any one of embodiments 1 to 25, being in the form of particles, wherein the particles have a particle size in the range of 200 to 365 pm, preferably in the range of 225 to 340 pm, more preferably in the range of 250 to 315 pm.

27. The catalytic material of 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.

28. The catalytic material of any one of embodiments 1 to 27, having a bulk density in the range of 0.4 to 2.5 g/cm ³, preferably in the range of 0.6 to 2.3 g/cm ³, more preferably in the range of 0.8 to 2.1 g/cm ³, wherein the bulk density is preferably determined according to Reference Example 1.d.

29. The catalytic material of any one of embodiments 1 to 28, having a loose bed density in the range of 0.4 to 2.3 g/cm ³, preferably in the range of 0.8 to 2.1 g/cm ³, more preferably in the range of 1 .2 to 1 .9 g/cm ³.

30. A process for the preparation of a catalytic material, preferably for the preparation of the catalytic material according to any one of embodiments 1 to 29, the process comprising

(iii) mixing the support material obtained in (ii) with an aqueous mixture comprising one or more sources of one or more first promoter metals M 1 , wherein M 1 is selected from the group consisting of alkali metals, and mixtures of two or more thereof, preferably 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, wherein the one or more first promoter metals M1 more preferably are K or Cs, wherein the one or more first promoter metals M1 more preferably are Cs, and one or more sources of one or more second promoter metals M2, wherein 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 mixtures of two or more thereof, preferably from the group consisting of Mn, Fe, Co, Ga, La, Ta, W, Re, and mixtures of two or more thereof, more preferably from the group consisting of Mn, Fe, and mixtures thereof, wherein the one or more second promoter metals M2 more preferably are Fe or Mn, wherein the one or more second promoter metals M2 more preferably are Fe, for obtaining a supported material;

(iv) reacting the supported material with NH3, for obtaining the catalytic material. The process of embodiment 30, wherein the one or more sources of Mo are selected from the group consisting of (NH^eMoyC^, (NH^eMoyC^ ■ 4 H2O, and mixtures of two or more thereof, wherein the one or more Mo sources preferably are (NH4)eMoyO24 or (NH₄)₆MoyO24 ■ 4 H₂O. The process of embodiment 30 or 31 , wherein the one or more sources of Co are selected from the group consisting of Co(NO3)2 ■ 6H2O, Co(OH)2, C0CI2, C0CI2 ■ 2 H2O, C0CI2 ■ 6 H2O, COSO4 ■ 6 H2O, COSO4 ■ 7 H2O, and mixtures of two or more thereof, wherein the one or more Co sources preferably are Co(NO3)2 ■ 6H2O. The process of any one of embodiments 30 to 32, wherein the one or more sources of M1 are selected from the group consisting of salts of M1 , hydrated salts of M1 , oxidic compounds of M1 , hydrated oxidic compounds of M1 , and mixtures thereof, preferably from the group consisting of salts of M1 , hydrated salts of M1 , and mixtures thereof, wherein the one or more sources of M 1 more preferably are salts of M 1 , wherein the salts are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, hydroxides, and mixtures thereof, wherein the salts preferably are nitrates, wherein the hydrated salts are preferably selected from the group consisting of hydrated nitrates, hydrated chlorides, hydrated sulfates, hydrated oxalates, hydrated hydroxides, and mixtures thereof, wherein the hydrated salts preferably are hydrated nitrates. The process of any one of embodiments 30 to 33, wherein the one or more sources for M2 are selected from the group consisting of salts of M2, hydrated salts of M2, oxidic compounds of M2, hydrated oxidic compounds of M2, and mixtures thereof, preferably from the group consisting of hydrated salts, oxidic compounds, and mixtures thereof, wherein the salts are preferably selected from the group consisting of nitrates, chlorides, sulfates, oxalates, ethanolates, citrates, and mixtures of two or more thereof, wherein 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. The process of any one of embodiments 30 to 34, wherein the aqueous solution prepared in (i) has a molar ratio of 1 ,3,5,7-tetraazaadamantane (urotropine), calculated as molar amount of 1 ,3,5,7-tetraazaadamantane (urotropine), to Mo, calculated as element, in the range of 1.0:1 to 3.0:1 , preferably in the range of 1.5:1 to 2.5:1 , more preferably in the range of 1.9:1 to 2.1 :1. 36. The process of any one of embodiments 30 to 35, wherein the mixture obtained in (i) is heated in (ii) to a temperature in the range of 70 to 100 °C, preferably in the range of 75 to 95 °C, more preferably in the range of 80 to 90 °C.

37. The process of any one of embodiments 30 to 36, wherein heating according to (ii) is performed for a duration in the range of 1 to 50 h, preferably in the range of 5 to 25 h, more preferably in the range of 10 to 20 h, more preferably in the range of 15 to 18 h.

38. The process of any one of embodiments 30 to 37, wherein the aqueous solution obtained in (ii) has a pH in the range of from 4 to 7, preferably in the range of from 5 to 6.

39. The process of any one of embodiments 30 to 38, wherein heating in (ii) is performed under autogenous pressure, preferably in an autoclave, more preferably a PTFE-lined steel autoclave, or wherein heating is performed at ambient pressure, preferably in a flask mounted with a reflux condenser.

40. The process of any one of embodiments 30 to 39, further comprising after (ii) and prior to (iii)

(s) isolating the support material obtained in (ii), preferably by filtration.

41 . The process of embodiment 40, further comprising after (s) and prior to (iii)

(w) washing the support material obtained from (s) with water, preferably with an amount of water in the range of 1 to 100 mL/g(support material), preferably in the range of 10 to 30 mL/g(support material).

42. The process of any one of embodiments 30 to 41 , further comprising after (ii) and prior to (iii), preferably after (s) as defined in embodiment 40 and prior to (iii), more preferably after (w) as defined in embodiment 41 and prior to (iii),

(d1) drying the support material obtained in (ii), (s), or (w) 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 comprises, more preferably consists of, one or more of oxygen and nitrogen, preferably air, more preferably synthetic air.

43. The process of embodiment 42, wherein drying according to (d1 ) is performed for a duration in the range of 1 to 30 h, preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

44. The process of any one of embodiments 30 to 43, further comprising after (ii) and prior to (iii), preferably after (s) as defined in embodiment 40 and prior to (iii), more preferably after (w) as defined in embodiment 41 and prior to (iii),

(d2) freeze drying the solids obtained in (ii), (s), or (w) in a gas atmosphere having a pressure in the range of 1 to 8 mbar(abs), preferably in the range of 2 to 4 mbar(abs), at a condenser temperature in the range of -100 to -50 °C, preferably in the range of -80 to -60 °C, and wherein the solids have a temperature in the range of -30 to 0 °C, preferably in the range of -20 to -10 °C, wherein the gas atmosphere preferably comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air, more preferably synthetic air.

45. The process of embodiment 44, wherein freeze drying according to (d2) is performed for a duration in the range of 1 to 30 h, preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

46. The process of any one of embodiments 30 to 45, further comprising after (ii) and prior to (iii), preferably after (d1) as defined in embodiment 42 or 43 and prior to (iii), or after (d2) as defined in embodiment 44 or 45 and prior to (iii),

(c) calcining the solids obtained in (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 comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air, more preferably synthetic air.

47. The process of any one of embodiments 30 to 46, wherein mixing according to (iii) comprises impregnation, preferably incipient wetness impregnation.

48. The process of embodiment 47, wherein the volume ratio of the aqueous mixture to the pore volume of the support material obtained in (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 , more preferably in the range of 0.99:1 to 1.01 :1.

49. The process of any one of embodiments 30 to 48, wherein (iv) is performed in a stream of NH3 having a flow rate in the range of 250 to 400 ml min ¹, preferably in the range of 275 to 375 ml min ¹, more preferably in the range of 300 to 350 ml min ¹.

50. The process of any one of embodiments 30 to 49, wherein (iv) comprises heating the supported material to a temperature in the range of 600 to 900 °C, preferably in the range of 700 to 800 °C, more preferably in the range of 725 to 775 °C.

51 . The process of any one of embodiments 30 to 50, wherein (iv) is performed for a duration in the range of 1.0 to 15.0 h, preferably in the range of 5.0 to 11 .0 h, more preferably in the range of 7.0 to 9.0 h, more preferably in the range of 7.5 to 8.5 h.

52. The process of any one of embodiments 30 to 51 , further comprising

(d3) drying the supported material obtained in (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 comprises, preferably consists of, one or more of oxygen and nitrogen, preferably air, more preferably synthetic air.

53. The process of embodiment 52, wherein drying according to (d3) is performed for a duration in the range of 1 to 30 h, preferably in the range of 8 to 24 h, more preferably in the range of 12 to 18 h.

54. A catalytic material, preferably a catalytic material according to any of embodiments 1 to 29, wherein the catalytic material is obtained or obtainable by the process of any one of embodiments 30 to 53.

55. A process for the synthesis of NH3, the process comprising

(A) providing a reactor comprising a reaction zone, wherein the reaction zone comprises the catalytic material of any one of embodiments 1 to 29 and 54, wherein the catalytic material has a temperature in the range of 200 to 600 °C;

56. The process of embodiment 55, wherein the catalytic material has a temperature in the range of 250 to 550 °C, preferably in the range of 275 to 525 °C.

57. The process of embodiment 55 or 56, wherein the gas stream according to (B) comprises from 45 to 95 volume-%, preferably from 50 to 90 volume-%, more preferably from 60 to 80 volume-%, of hydrogen.

58. The process of any one of embodiments 55 to 57, wherein the hydrogen comprised in the gas stream according to (B) is prepared from one or more renewable sources.

59. The process of any one of embodiments 55 to 58, wherein the gas stream according to (B) comprises from 5 to 55 volume-%, preferably from 10 to 50 volume-%, more preferably from 20 to 40 volume-%, of nitrogen.

60. The process of any one of embodiments 55 to 59, wherein the gas stream is fed into the reactor at a pressure in the range of 40 to 150 bar(abs), preferably in the range of 50 to 120 bar(abs), more preferably in the range of 55 to 100 bar(abs).

61 . Use of the catalytic material according to any one of embodiments 1 to 29 and 54 for the synthesis of NH3.

The present invention is further illustrated by the following reference examples, examples, and comparative examples. EXPERIMENTAL SECTION

Reference Example 1 : Determination methods

Reference Example 1.a: Determination of crystalline phases via powder X-ray diffraction

Powder diffraction patterns were recorded with an IP Guinier-Camera G670 (Huber company, Germany) and a Bragg-Brentano Diffractometer D8 Advanced (Bruker AXS) and Cu-Kalpha1 radiation (lambda = 1 .54059 Angstrom). Lattice parameters were determined manually or with the software package S.O.S. (Literature: J. Soose, G. Meyer, SOS - Programme zur Auswer- tung von Guinier-Aufnahmen (engl. “SOS - programs for evaluating Guinier recordings”); University of GieR>en, Germany 1980).

Based on the powder diffraction patterns, the reflexes of C03M03N were taken for a Scherrer analysis (see Scherrer equation) to estimate the average crystallite size of the C03M03N crystallites.

To determine the amount of crystalline and amorphous phases in a powder sample a standard addition method is used, where a known amount of a standard is added to a decent amount of the powder sample. Typical standards used are quartz (SiC>2), yttrium oxide (Y2O3) or corundum (AI2O3). The amounts of crystalline phases and the respective added standard are determined within a quantitative phase analysis (QPA) with common Rietveld refinement programs (TOPAS, Fullprof, etc.). Based on the QPA the relative mass fractions of crystalline phases/ analyte (Wj) are calculated and converted to absolute mass fractions (Wj,_abs.) with equation (I). The amount of amorphous phase is derived from the overall amount (100 %) minus the sum of crystalline phases according to equation (II).

Sabs. = Rietveld scale factor of the analyte

Sj = Rietveld scale factor of the standard

Literature: Ian C. Madsen, Nicola V. Y. Scarlett and Arnt Kern, Z. Kristallogr. 2011 , 226, 944.

The obtained diffraction patterns were analyzed against reference diffraction patterns from the ICSD for CosMosN, C02M03N, CoMoO4, CO3O4, CoO, MOO2, MoOs, MoN, M02N.

Reference Example 1.b: Transition electron microscopy (TEM) measurements

Samples were dispersed in cyclohexane and applied to the TEM carrier. The automated software suite ParticleSizer was used for data evaluation. The aspect ratio of primary particles was determined via TEM manually based on TEM images.

The particle size was estimated based on the evaluation of a few TEM images.

The layer thickness was determined visually on the basis of TEM images.

Reference Example 1.c: Determination of tap density

Samples in the sieves fraction 250-315 pm were filled into a 10 mL measuring cylinder and weight. The cylinder was tapped 200 times and the volume of the material was taken visually from the graduation.

Reference Example 1.d: Determination of bulk density

The bulk density was determined via He-pyknometry.

Reference Example 2: Preparation of a CoMoO^nFW precursor

A CoMoC>4-nH2O precursor was prepared as bulk material using (NH4)6MoyO24-4H2O and CO(NC>3)2-6H2O as starting materials. 40.5 g (NH4)6MoyO24-4H2O (32.8 mmol; 1 eq. Mo) and 67.0 g CO(NC>3)2-6H2O (230 mmol; 1 eq. Co) were dissolved in 1.0 L of water. While stirring, 64.0 g 1 ,3,5,7-tetraazaadamantane (also designated as urotropine or hexamethylenetetramine; 460 mmol; 2 eq.), dissolved in 300 mL of water, were added to the solution. After the addition of urotropine no initial change of the initial blue pinkish color occurred. The suspension was heated to 80 °C for 16 h under solvent reflux while stirring, whereby the color of the suspension changed into purple. The suspension was separated from the solution via vacuum filtration, the filter cake was washed with 1.5 L water, dried at 80 °C in synthetic air for 16 h inside a drying oven (Binder ED115). The obtained bulk material was crushed and homogenized.

Reference Example 3: Preparation of a CoMoC^ nFW precursor

A CoMoC>4-nH2O precursor was prepared as bulk material using (NH4)eMoyO24-4H2O and CO(NC>3)2-6H2O as starting materials. 2.6 g (NH4)eMoyO24-4H2O (2.1 mmol; 1 eq. Mo) and 4.4 g CO(NC>3)2-6H2O (15.0 mmol; 1 eq. Co) were dissolved in 60 mL of water in a PTFE-lined autoclave (50% of the autoclave volume). While stirring, 5.0 g 1 ,3,5,7-tetraazaadamantane (also designated as urotropine or hexamethylenetetramine; 35.7 mmol; 2.4 eq.) were added to the solution. The autoclave was sealed, and the suspension was heated to 80 °C for 12 h while magnetically stirred. After cooling down naturally, the suspension was separated from the solution via vacuum filtration, the filter cake was washed with 150 mL water, dried at 80 °C in synthetic air for 16 h. The obtained bulk material was crushed and homogenized.

Examples 4-21 and Comparative Examples 22-23: Preparation of catalytic materials A 13 g sample of the CoMoO^nFW precursor as obtained from Reference Example 2 was subject to impregnation with aqueous promotor and co-promotor solutions. Except for co-promoting with one or more of Ta and Re, the incipient wetness impregnations were performed as co-im- pregnations of promotor and co-promotor.

For this, the solvent uptake of the sample obtained from Reference Example 2 was determined to 0.6 mL g ¹ and the promoting solutions were prepared with a total volume of 7.8 mL, blended with CoMoO^nFW. The resulting wet material was dried at 80 °C for 16 h in synthetic air.

For co-promoting with one or more of Ta and Re, a sequential wetness incipient impregnation was applied, were the promotor was added first, according to the above described procedure. Afterwards, the co-promotor being one or more of Ta and Re was added similarly. The resulting material was dried at 80 °C for 16 h in synthetic air. In case of a co-promotion with Re, diluted perrhenic acid was used.

The applied metal salts were used without prior purification for impregnation and are listed in table 1. Table 2 contains the impregnated amounts of promotors and co-promotors given in weight-% based on the ammonolyzed catalyst as well as the molar ratio of alkali metal to Mo. In order to relate the desired weight loading of the promotors and co-promotors in the finished catalyst to the sample of CoMoO^nFW obtained from Reference Example 2, the loss of ignition (LOI) of that CoMoO₄-nH₂O sample during the ammonolysis into C03M03N was determined to be 50.8 weight-% and the LOI of that CoMoO4-nH2O sample during the calcination in synthetic air at 600 °C into C0M004 was determined to be 31 .0 weight-%. These LOIs were considered when calculating the necessary quantities.

Table 1 : Metal salts used for impregnation.

Table 2: Promoter loadings on CoMoO4-nH2O obtained from Reference Example 2, wherein the loading is given in weight-% based on the ammonolyzed catalyst.

The obtained supported CoMoC^-ntW were subjected to ammonolysis as outlined in the following. A sample of each of the supported CoMoC^-ntW was subjected to ammonolysis. The sample was charged into a fused silica tube with an inner diameter of approximately 15 mm. The fused silica tube was approximately 800 mm in length and was divided in the middle with a fused silica frit to hold the applied sample in place. The tube was set up in a tubular furnace (HTM Reetz GmbH LK 1100-60-350-1 -V), attached to the gas supply, leak tested and flushed with gaseous, anhydrous ammonia. An ammonia flow of approximately 300 to 350 mL min ¹ was set before the sample was heated up to 750 °C with a heating rate of 5 K min ¹. After a dwell time of 8 h, the furnace was turned off, the ammonia flow was replaced with a nitrogen flow of approximately 350 mL min ¹ and the sample was allowed to cool down naturally. After cooling down, the sample was transferred into an Ar filled glovebox, ground to a fine powder and passivated with 10 volume-% air in Ar before handling of the powder in ambient air to avoid sudden ignition. The obtained powder was tableted with a hydraulic press equipped with a 40 mm tablet die, a pres- sure of 1.51 cm ², crushed and sieved into a 250 to 315 pm split fraction in ambient air.

Table 3: Analytical data for catalytic materials according to Examples 4-7, 9, 14-17, and 21 as well as according to Comparative Example 22.

Example 24: Catalytic testing

Catalytic tests were carried out in a 16-fold solid-gas reactor system at the hte GmbH, (Germany). The reactor system used was in accordance with the reactor systems described in (DOI: 10.1002/14356007.s13_s01 ; Chemie Ingenieur Technik, 2002, 74, 557; DE10036633A1). The reactors (stainless steel 1.4841 , 4 mm inner diameter, 450 mm length) were filled with 0.5 mL of a catalytic material according to Examples 4-21 and Comparative Exampels 22-23 (250 to 315 pm) with a pre-/post-bed of silicon carbide (SiC). Before starting with the reaction, each cat- alyst was heated at 500 °C for 10 h at 60 bar, GHSV = 35000 IT¹, 69.8 volume-% H2, 23.2 vol- ume-% N2, 7.0 volume-% Ar. The activated catalysts were then tested according to the test program, reported in table 5. Table 5: Experimental reaction conditions tested for the catalytic materials according to Examples 4-21 and Comparative Examples 22-23. Each experimental condition was kept for 8 h for each catalytic material. The tests were conducted one after the other, without intermission. Experiment number (Exp. n.) 2, 11 & 26 are reference points to determine the catalyst deactivation during the tests.

The results for the catalytic testing are noted in table 6 below. The activity of the catalytic materials of the present invention is given in weight-based time yield (WTY) and the volumetric fraction of ammonia in the product gas stream is given in volume-% NH3. Table 6. Activities from catalytic materials according to Examples 4-21 and Comparative Examples 22-23 given in weight-based time yield (WTY) and the volumetric fraction of ammonia in the product gas stream (volume-% NH3). As can be gathered from the results of catalytic testing, all catalytic materials have shown a better performance than the catalytic material according to Comparative Example 22 which is not promoted by any metal. Further, it has been shown that the catalytic material according to Example 4 achieves a higher weight-based time yield and a higher volume-% of NH3 than the catalytic material of Comparative Example 24 which does not comprise a second promoter. Similarly, the catalytic material according to Example 5, which comprises less Fe than that of Example 4, achieves a higher weight-based time yield than the catalytic material of Comparative Example 24. Further, it has been shown that the performance of the catalytic material according to Comparative Example 25 severely decreased when applying the conditions of Exp. n. 6, whereas the catalytic material according to Example 9, being further promoted with Fe, showed a good performance even for subsequent Exp. n. 14, 21 and 26.

Cited literature:

D. Moszyhski et al. “Katalizatory kobaltowo-molibdenowe domieszkowane cezem do syntezy amoniaku”, Przemysl Chemiczny, 2015, 94, 1399-1403; doi: 10.15199/62.2015.8.31

D. Moszyhski et al. “Surface and catalytic properties of potassium-modified cobalt molybdenum catalysts for ammonia synthesis", AppL Surf. ScL, 2010, 256, 5581-5584 D. Moszyhski et al. “Cobalt molybdenum nitrides co-promoted by chromium and potassium as catalysts for ammonia synthesis" in Chem. Pap., 2018, 72, 425-430 D. Moszyhski et al. “ Thermal Stability of Potassium-Promoted Cobalt Molybdenum Nitride Catalysts for Ammonia Synthesis” in Catalysts, 2022, 12, 100

C. J. H. Jacobsen et al. “Novel class of ammonia synthesis catalysts”, Chem. Commun., 2000, 1057-1058

- US 6235676 B1

R. Kojima et al. “Cobalt molybdenum bimetallic nitride catalysts for ammonia synthesis: Part 1. Preparation and characterization” in AppL CataL, A, 2001 , 215, 149-160 P. Adamski et al. “Thermal stability of potassium-promoted cobalt molybdenum nitride catalysts for ammonia synthesis” in Catalysts 2022, 12, 100

Claims

1 . A catalytic material for the synthesis of NH3, the catalytic material comprising

C03M03N, one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, and one or more second promoter 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 promoter metals M1 and the one or more second promoter metals M2 are supported on the C03M03N.

2. The catalytic material of claim 1 , wherein the C03M03N comprises one or more crystalline C03M03N phases.

3. The catalytic material of claim 1 or 2, wherein the one or more first promoter metals M 1 are in the form of one or more of hydroxides and oxides.

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

5. The catalytic material of any one of claims 1 to 4, having a molar ratio M1 :Mo, of the one or more first promoter metals M1 , calculated as sum of molar amounts of the one or more first promoter metals M1 as elements, to Mo, calculated as element, in the range of 1 .0-

10³:1 to 8.5-1 O’²: 1 .

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

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

8. The catalytic material of any one of claims 1 to 7, having a molar ratio M2:Mo, of the one or more second promoter metals M2, calculated as sum of molar amounts of the one or more second promoter metals M2 as elements, to Mo, calculated as element, in the range of 1.0-10’³:1 to 2.0-10’¹:1.

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

10. The catalytic material of any one of claims 1 to 9, comprising from 0 to 1 weight-% of Cr, calculated as element, based on the total weight of the catalytic material.

11 . The catalytic material of any one of claims 1 to 10, wherein from 90 to 100 weight-% of the catalytic material consist of Co, Mo, N, the one or more first promoter metals M1 , the one or more second promoter metals M2, optionally the one or more co-promoter metals M3, H, and O.

12. A process for the preparation of a catalytic material, the process comprising

(iii) mixing the support material obtained in (ii) with an aqueous mixture comprising one or more sources of one or more first promoter metals M 1 , wherein M 1 is selected from the group consisting of alkali metals, and mixtures of two or more thereof, and one or more sources of one or more second promoter metals M2, wherein 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 mixtures of two or more thereof, for obtaining a supported material;

13. A catalytic material obtained or obtainable by the process of claim 12.

14. A process for the synthesis of NH3, the process comprising

(A) providing a reactor comprising a reaction zone, wherein the reaction zone comprises the catalytic material of any one of claims 1 to 11 and 13, wherein the catalytic material has a temperature in the range of 200 to 600 °C;

15. Use of the catalytic material according to any one of claims 1 to 11 and 13 for the synthesis of NH3.