EP4688646A1

EP4688646A1 - <sup2/>? <sub2/>?3?process for nhreforming using a supported co <ns1:sub>3</ns1:sub>?mo <ns2:sub>3</ns2:sub>?n catalytic material

Info

Publication number: EP4688646A1
Application number: EP24718055.7A
Authority: EP
Inventors: Elias Christopher FREI; Stephan Schunk; Ivana JEVTOVIKJ; 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: WO2024200634A1; KR20250169348A; CN121039052A; JP2026511890A

Abstract

The present invention relates to a process for the reforming of ammonia, wherein the process comprises contacting a feed gas stream comprising NH3 with a catalytic material comprising Co3Mo3N and one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, wherein the one or more first promoter metals M1 are supported on the Co3Mo3N, wherein contacting is performed at a pressure of greater than 5 bara and at a temperature in the range of from 200 to 700 °C.

Description

Process for NH3 reforming using a supported C03M03N catalytic material

TECHNICAL FIELD

The present invention relates to a process for reforming NH3, in particular at a comparatively high pressure, wherein catalysts are used comprising supported C03M03N.

INTRODUCTION

NH3 is seen as an energy vector of the future, able to store chemically significant amounts of H₂. So, sustainable NH3 might be produced on a large scale from regenerative energy sources. The reforming of NH3 (see equation 1 below) on site, where the H₂ is needed, might be the last step in closing an H₂ value chain based on renewable electricity.

(1 ) 2 NH₃ - N₂ + 3 H₂

I. Lucentini et al., Ind. Eng. Chem. Res. 2021 , 60, 18560-18611 as well as T. Le et al., Korean

J. Chem. Eng., 2021 , 38(6), 1087-1103 respectively provide an overview of catalysts which are employed in the decomposition of ammonia. X.-K. Li et al., Journal of Catalysis, 2005, 236, 181- 189 specifically relates to the decomposition of ammonia over Ni and Ru catalysts. Bell et al., Top Catal., 2016, 59,1438-1457 concerns the decomposition of ammonia employing non-noble metal catalysts, wherein mainly Co- and Ni-containing catalysts are discussed. S. Sayas et al. in Catal. Sci. Technol. 2020, 10, 5027-5035 studies high pressure ammonia decomposition on Ru- K/CaO catalysts at pressures of up to 40 bar. A. Srifa et al. disclose in Applied Catalysis B: Environmental 218 (2017), pages 1-8, a study on hydrogen production by ammonia decomposition over Cs-modified C03M03N catalysts at standard pressure.

There, however, remains the need for an improved and cost-efficient process for NH3 reforming, in particular at comparatively high reaction pressures, which particularly allows obtaining an effluent gas stream comprising hydrogen at a comparatively high pressure.

DETAILED DESCRIPTION

Thus, it was surprisingly found that a process for the reforming of NH₃ can be provided yielding an improved ammonia conversion compared to a commonly used industrial catalytic material, in particular at comparatively high reaction pressures.

Therefore, the present invention relates to a process for the reforming of ammonia, wherein the process comprises

(i) providing a reactor containing a catalytic material, wherein the catalytic material comprises C03M03N and one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, wherein the one or more first promoter metals M1 are supported on the C03M03N; (ii) preparing a feed gas stream comprising NH3;

(iii) feeding the feed gas stream prepared in (ii) into the reactor provided in (i) and contacting the feed gas stream with the catalytic material, wherein contacting is performed at a pressure of greater than 5 bara and at a temperature in the range of from 200 to 700 °C;

(iv) removing an effluent gas stream from the reactor, the effluent gas stream comprising H₂ and N₂.

It is preferred that the contacting in (iii) is performed at a pressure in the range of from greater than 5 to 100 bara, more preferably in the range of from 10 to 100 bara, more preferably in the range of from 12 to 100 bara, more preferably in the range of from 14 to 75 bara, more preferably in the range of from 15 to 50 bara, more preferably in the range of from 16 to 45 bara, more preferably in the range of from 17 to 40 bara, more preferably in the range of from 18 to 35 bara, more preferably in the range of from 19 to 28 bara, and more preferably in the range of from 20 to 25 bara.

It is preferred that the contacting in (iii) is performed at a temperature in the range of from 200 to 900 °C, more preferably in the range of from 250 to 750 °C, more preferably in the range of from 250 to 650 °C, more preferably in the range of from 300 to 600 °C, more preferably in the range of from 350 to 550 °C, and more preferably in the range of from 400 to 500 °C.

It is preferred that the feed gas stream is fed into the reactor at a gas hourly space velocity in the range of from 500 to 20,000 IT¹, more preferably of from 700 to 16,000 IT¹, more preferably of from 800 to 12,000 I ¹, more preferably of from 900 to 10,000 IT¹, more preferably of from 1 ,000 to 8,000 IT¹, more preferably of from 3,000 to 5,000 IT¹.

It is preferred that the feed gas stream prepared in (ii) comprises from 1 to 100 vol.-% of NH3, more preferably from 3 to 99.99 vol.-%, more preferably from 5 to 99.95 vol.-%, more preferably from 10 to 99.9 vol.-%, more preferably from 15 to 99.9 vol.-%, more preferably from 20 to 99.8 vol.-%, more preferably from 30 to 99.7 vol.-%, more preferably from 40 to 99.6 vol.-%, more preferably from 50 to 99.5 vol.-%, more preferably from 60 to 99.5 vol.-%, more preferably from 70 to 99.5 vol.-%, more preferably from 80 to 99.5 vol.-%, more preferably from 90 to 99.5 vol.- 0 //o.

It is preferred that the feed gas stream prepared in (ii) comprises from 0 to 50 vol.-% of one or more inert gases, more preferably from 0.01 to 30 vol.-%, more preferably from 0.03 to 15 vol.- %, more preferably from 0.05 to 5 vol.-%, more preferably from 0.1 to 1 vol.-%, more preferably from 0.12 to 0.5 vol.-%, and more preferably from 0.14 to 0.16 vol.-%, wherein the one or more inert gases are preferably selected from N₂, Ar, and mixtures thereof.

It is preferred that the feed gas stream prepared in (ii) comprises from 0 to 75 vol.-% of H₂, more preferably from 0 to 60 vol.-%, more preferably from 0 to 50 vol.-%, more preferably from 0 to 40 vol.-%, more preferably from 0 to 35 vol.-%, and more preferably from 0 to 30 vol.-%. It is preferred that the feed gas stream prepared in (ii) comprises from 100 to 50,000 ppmv of H2O, more preferably from 200 to 30,000 ppmv, more preferably from 500 to 25,000 ppmv, more preferably from 500 to 20,000 ppmv, more preferably from 500 to 15,000 ppmv, more preferably from 750 to 15,000 ppmv, more preferably from 1 ,000 to 11 ,000 ppmv, more preferably from 1 ,000 to 10,000 ppmv, more preferably from 2,000 to 8,000 ppmv, more preferably from 3,000 to 7,500 ppmv, more preferably from 3,100 to 7,400 ppmv, more preferably from 3,500 to 7,200 ppmv, more preferably from 4,000 to 7,100 ppmv, more preferably from 4,500 to 7,000 ppmv, more preferably from 5,000 to 6,500 ppmv.

It is preferred that the feed gas stream prepared in (ii) further comprises one or more inert gases and H₂, wherein the total amount of NH3, inert gas, and H₂ comprised in the feed gas stream prepared in (ii) is in the range from 90 to 100 wt.-%, more preferably from 95 to 99.95 vol.-%, more preferably from 98 to 99.9 vol.-%, more preferably from 99 to 99.85 vol.-%, and more preferably from 99.7 to 99.8 vol.-%, wherein the one or more inert gases are preferably selected from the group consisting of N₂, Ar, and mixtures thereof.

It is preferred that the process is for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) further comprises one or more hydrocarbons, and one or more of CO₂ and H₂O, and wherein the effluent gas stream removed in (iv) further comprises CO.

In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises CO₂ and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5 vol.-% or less of H₂O, more preferably 3 vol.-% or less, more preferably 1 vol.-% or less, more preferably 0.5 vol.-% or less, more preferably 0.1 vol.-% or less, more preferably 0.05 vol.-% or less, and more preferably 0.01 vol.-% or less of H₂O.

In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises H₂O, and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5 vol.-% or less of CO₂, more preferably 3 vol.-% or less, more preferably 1 vol.-% or less, more preferably 0.5 vol.-% or less, more preferably 0.1 vol.-% or less, more preferably 0.05 vol.-% or less, and more preferably 0.01 vol.-% or less of CO₂.

In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) further comprises CO₂, H₂O, and one or more hydrocarbons.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the one or more hydrocarbons are selected from the group consisting of alkanes and mixtures thereof, more preferably of C1-C10 alkanes and mixtures thereof, more preferably of C3-C9 alkanes and mixtures thereof, more preferably of C4-C8 alkanes and mixtures thereof, more preferably of C5-C7 alkanes and mixtures thereof, more preferably of C6 alkanes and mixtures thereof.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the contacting is performed at a pressure in the range of from 10 to 50 bara, more preferably of from 12 to 45 bara, more preferably of from 15 to 40 bara, more preferably of from 18 to 35 bara, and more preferably of from 20 to 30 bara.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) comprises from 0.1 to 75 vol.-% of NH3, more preferably from 0.3 to 60 voL-%, more preferably from 0.5 to 50 voL-%, more preferably from 0.8 to 40 voL-%, more preferably from 1 to 30 vol.-%, more preferably from 12 to 25 voL-%.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) comprises from 10 to 70 vol.-% of the one or more hydrocarbons, more preferably from 12 to 60 vol.-%, more preferably from 15 to 50 voL-%, more preferably from 20 to 40 vol.-%, more preferably from 22 to 29 voL-%.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) comprises from 0 to 75 voL-% of H₂O, more preferably from 0.5 to 70 voL-%, more preferably from 1 to 68 vol.-%, more preferably from 3 to 66 vol.-%, more preferably from 5 to 64 voL-%, more preferably from 8 to 62 voL-%, more preferably from 10 to 60 voL-%, more preferably from 25 to 50 voL-%, more preferably from 33 to 44 vol.-%.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed gas stream prepared in (ii) comprises from 0 to 60 voL-% of CO₂, more preferably from 1 to 58 voL-%, more preferably from 3 to 56 voL-%, more preferably from 5 to 54 vol.-%, more preferably from 8 to 52 voL-%, more preferably from 10 to 50 voL-%, more preferably from 12 to 20 voL-%.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed stream displays an H₂O : C molar ratio of H₂O to carbon contained in the one or more hydrocarbons in the range of from 0 to 4, more preferably of from 0.1 to 3, more preferably of from 0.2 to 3, more preferably of from 0.3 to 2.5, more preferably of from 0.4 to 2, and more preferably of from 0.5 to 1 .6.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed stream displays a CO₂ : C molar ratio of CO₂ to carbon contained in the one or more hydrocarbons in the range of from 0 to 4, more preferably of from 0.1 to 3, more preferably of from 0.2 to 2, more preferably of from 0.3 to 1.5, more preferably of from 0.4 to 0.8. Further In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the feed stream displays an NHs : C molar ratio of NH₃ to carbon contained in the one or more hydrocarbons in the range of from 0 to 5, more preferably of from 0 to 4, more preferably of from 0.001 to 3, more preferably of from 0.005 to 2, and more preferably of from 0.01 to 1.

Further In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) further comprises CO2.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) displays a stoichiometry number R in the range of from 0.1 to 3, wherein R is defined according to formula (I): wherein c(H₂), c(CO₂), and c(CO) stand for the molar concentration of H₂, CO₂, and CO in the effluent gas stream, respectively.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) displays a stoichiometry number R in the range of from 1 to 2.5, more preferably of from 1 .3 to 2.2.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) displays a stoichiometry number R > 2.

In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) displays an H₂ : CO molar ratio of >2.

Further In the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the stoichiometry number R is in the range of 0.5 to 3, more preferably of from 1 to 2.2, and more preferably of 1.3 to 1 .7.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) comprises from 10 to 90 vol.-% of H₂, more preferably from 20 to 80 vol.-%, more preferably from 30 to 70 vol.-%, more preferably from 40 to 65 vol.-%, and more preferably from 45 to 60 vol.-%.

Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) comprises from 1 to 70 vol.-% of CO, more preferably from 3 to 50 vol.-%, more preferably from 5 to 40 vol.-%, more preferably from 10 to 35 vol.-%, and more preferably from 15 to 30 vol.-%. Further in the case where the process is for reforming of ammonia and hydrocarbons, it is preferred that the effluent gas stream removed in (iv) comprises from 1 to 50 vol.-% of CO₂, more preferably from 3 to 45 vol.-%, more preferably from 5 to 40 vol.-%, more preferably from 8 to 35 vol.-%, more preferably from 10 to 30 vol.-%, and more preferably from 12 to 25 vol.-%.

It is preferred that the C03M03N employed in the inventive process 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 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 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 employed in the inventive process 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, based on the total weight of the catalytic material 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-%, 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 MoO₄ ²-, MO₂O7^2-, MOSOW²’, M04O13²-, MO₅OI₆ ²-, MoeOig²’, MO7O2 Mos ", and mixtures of two or more thereof.

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

It is preferred that the one or more first promoter metals M1 comprised in the catalytic material contained in the reactor provided according to (i) 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 contained in the reactor provided according to (i) has a molar ratio M1 :Mo, of the one or more first promoter metals M 1 , 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 .0-10³: 1 to 8.5-10’²:1 , more preferably in the range of 2.0-10’³:1 to 8.0-10²:1 , more preferably in the range of 3.0-10"³:1 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 -10’³:1 to 6.2-10²:1 , 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 5.5-10²:1, more preferably in the range of 7.0-10’³:1 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 9.0-10³: 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 3.3-10²:1 , more preferably in the range of 2.0-10²:1 to 3.0-10²:1. It is preferred that the catalytic material contained in the reactor provided according to (i) further comprises one or more second promoter metals M2 supported on the C03M03N, wherein the one or more second promoter 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, Y, La, and mixtures of two or more 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, Y, La, and mixtures of two or more thereof, more 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.

Further in the case where the catalytic material contained in the reactor provided according to (i) further comprises one or more second promoter metals M2 supported on the C03M03N, it is preferred that the one or more second promoter metals M2 are in the form of one or more of hydroxides, and oxides.

Further in the case where the catalytic material contained in the reactor provided according to (i) further comprises one or more second promoter metals M2 supported on the C03M03N, it is preferred that the 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 2.0-10¹:1 , more preferably in the range of 2.0 10-³:1 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 4.0-10’³:1 to 8.0-10²: 1 , more preferably in the range of 4.3-10"³: 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 6.0-10’³:1 to 5.0-1 O’²: 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 9.0-10³:1 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 contained in the reactor provided according to (1) further comprises one or more third 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.

It is preferred that the catalytic material contained in the reactor provided according to (1) 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 sum of the weights of the C03M03N, the one or more first promoter metals M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3.

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 M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3, comprised in the catalytic material contained in the reactor provided in (i) are comprised in a layer supported on the C03M03N, wherein the layer preferably is amorphous.

Further in the case where the one or more first promoter metals M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3, comprised in the catalytic material contained in the reactor provided in (i) are comprised in a layer supported on the C03M03N, preferably 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 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 M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3, H, and O.

It is preferred that the catalytic material employed in the inventive process 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 employed in the inventive process 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 employed in the inventive process 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 employed in the inventive process 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 employed in the inventive process 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. It is preferred that the effluent gas stream removed in (iv) is employed in a process for the production of methanol, for the production of dimethyl ether, or for the production of methanol and dimethylether.

It is preferred that the effluent gas stream removed in (iv) is employed in a process for the production of hydrocarbons, preferably according to the Fischer-Tropsch process.

It is preferred that the effluent gas stream removed in (iv) is employed in a process for the production of alcohols, more preferably of alkanols, more preferably of C1 to C10 alkanols, more preferably of C2 to C8 alkanols, more preferably of C2 to C6 alkanols, more preferably of C2 to C4 alkanols, more preferably of C2 alkanols, and more preferably of ethanol.

It is preferred that the feed gas stream prepared in (ii) and fed into the reactor in (iii) further comprises H₂ for reducing the catalytic material.

Further in the case where the feed gas stream prepared in (ii) and fed into the reactor in (iii) further comprises H₂ for reducing the catalytic material, preferably the feed gas stream prepared in (ii) and fed into the reactor in (iii) comprises from 0.5 to 80 vol.-% of H₂, more preferably from 1 to 70 vol.-%, more preferably from 2 to 60 vol.-%, more preferably from 5 to 50 vol.-%, more preferably from 15 to 40 vol.-%.

The unit bara 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 process 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 process 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 process for the reforming of ammonia, wherein the process comprises

(i) providing a reactor containing a catalytic material, wherein the catalytic material comprises C03M03N and one or more first promoter metals M1 selected from the group consisting of alkali metals, and mixtures of two or more thereof, wherein the one or more first promoter metals M1 are supported on the C03M03N;

(ii) preparing a feed gas stream comprising NH3; (iii) feeding the feed gas stream prepared in (ii) into the reactor provided in (i) and contacting the feed gas stream with the catalytic material, wherein contacting is performed at a pressure of greater than 5 bara and at a temperature in the range of from 200 to 700 °C;

(iv) removing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N2. The process of embodiment 1 , wherein contacting in (iii) is performed at a pressure in the range of from greater than 5 to 100 bara, preferably in the range of from 10 to 100 bara, more preferably in the range of from 12 to 100 bara, more preferably in the range of from

14 to 75 bara, more preferably in the range of from 15 to 50 bara, more preferably in the range of from 16 to 45 bara, more preferably in the range of from 17 to 40 bara, more preferably in the range of from 18 to 35 bara, more preferably in the range of from 19 to 28 bara, and more preferably in the range of from 20 to 25 bara. The process of embodiment 1 or 2, wherein contacting in (iii) is performed at a temperature in the range of from 200 to 900 °C, preferably in the range of from 250 to 750 °C, more preferably in the range of from 250 to 650 °C, more preferably in the range of from 300 to 600 °C, more preferably in the range of from 350 to 550 °C, and more preferably in the range of from 400 to 500 °C. The process of any one of embodiments 1 to 3, wherein the feed gas stream is fed into the reactor at a gas hourly space velocity in the range of from 500 to 20,000 h ¹, preferably of from 700 to 16,000 IT¹, more preferably of from 800 to 12,000 IT¹, more preferably of from 900 to 10,000 IT¹, more preferably of from 1 ,000 to 8,000 IT¹, more preferably of from 3,000 to 5,000 IT¹. The process of any one of embodiments 1 to 4, wherein the feed gas stream prepared in (ii) comprises from 1 to 100 vol.-% of NH3, preferably from 3 to 99.99 vol.-%, more preferably from 5 to 99.95 vol.-%, more preferably from 10 to 99.9 vol.-%, more preferably from

15 to 99.9 vol.-%, more preferably from 20 to 99.8 vol.-%, more preferably from 30 to 99.7 vol.-%, more preferably from 40 to 99.6 vol.-%, more preferably from 50 to 99.5 vol.-%, more preferably from 60 to 99.5 vol.-%, more preferably from 70 to 99.5 vol.-%, more preferably from 80 to 99.5 vol.-%, more preferably from 90 to 99.5 vol.-%. The process of any one of embodiments 1 to 5, wherein the feed gas stream prepared in (ii) comprises from 0 to 50 vol.-% of one or more inert gases, preferably from 0.01 to 30 vol.-%, more preferably from 0.03 to 15 vol.-%, more preferably from 0.05 to 5 vol.-%, more preferably from 0.1 to 1 vol.-%, more preferably from 0.12 to 0.5 vol.-%, and more preferably from 0.14 to 0.16 vol.-%, wherein the one or more inert gases are preferably selected from N2, Ar, and mixtures thereof. 7. The process of any one of embodiments 1 to 6, wherein the feed gas stream prepared in (ii) comprises from 0 to 75 vol.-% of H₂, preferably from 0 to 60 vol.-%, more preferably from 0 to 50 vol.-%, more preferably from 0 to 40 vol.-%, more preferably from 0 to 35 vol.-%, and more preferably from 0 to 30 vol.-%.

8. The process of any one of embodiments 1 to 7, wherein the feed gas stream prepared in

(ii) comprises from 100 to 50,000 ppmv of H₂O, preferably from 200 to 30,000 ppmv, more preferably from 500 to 25,000 ppmv, more preferably from 500 to 20,000 ppmv, more preferably from 500 to 15,000 ppmv, more preferably from 750 to 15,000 ppmv, more preferably from 1 ,000 to 11 ,000 ppmv, more preferably from 1 ,000 to 10,000 ppmv, more preferably from 2,000 to 8,000 ppmv, more preferably from 3,000 to 7,500 ppmv, more preferably from 3,100 to 7,400 ppmv, more preferably from 3,500 to 7,200 ppmv, more preferably from 4,000 to 7,100 ppmv, more preferably from 4,500 to 7,000 ppmv, more preferably from 5,000 to 6,500 ppmv.

9. The process of any one of embodiments 1 to 8, wherein the feed gas stream prepared in (ii) further comprises one or more inert gases and H₂, wherein the total amount of NH3, inert gas, and H₂ comprised in the feed gas stream prepared in (ii) is in the range from 90 to 100 wt.-%, preferably from 95 to 99.95 vol.-%, more preferably from 98 to 99.9 vol.-%, more preferably from 99 to 99.85 vol.-%, and more preferably from 99.7 to 99.8 vol.-%, wherein the one or more inert gases are preferably selected from the group consisting of N₂, Ar, and mixtures thereof.

10. The process of any one of embodiments 1 to 9, wherein the process is for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) further comprises one or more hydrocarbons, and one or more of CO₂ and H₂O, and wherein the effluent gas stream removed in (iv) further comprises CO.

11 . The process of embodiment 10, wherein the feed gas stream prepared in (ii) further comprises CO₂ and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5 vol.-% or less of H₂O, more preferably 3 vol.-% or less, more preferably 1 vol.-% or less, more preferably 0.5 vol.-% or less, more preferably 0.1 vol.-% or less, more preferably 0.05 vol.-% or less, and more preferably 0.01 vol.-% or less of H₂O.

12. The process of embodiment 10, wherein the feed gas stream prepared in (ii) further comprises H₂O, and one or more hydrocarbons, and wherein the feed gas stream preferably comprises 5 vol.-% or less of CO₂, more preferably 3 vol.-% or less, more preferably 1 vol.-% or less, more preferably 0.5 vol.-% or less, more preferably 0.1 vol.-% or less, more preferably 0.05 vol.-% or less, and more preferably 0.01 vol.-% or less of CO₂.

13. The process of embodiment 10, wherein the feed gas stream prepared in (ii) further comprises CO₂, H₂O, and one or more hydrocarbons. The process of 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 of C1- C10 alkanes and mixtures thereof, more preferably of C3-C9 alkanes and mixtures thereof, more preferably of C4-C8 alkanes and mixtures thereof, more preferably of C5-C7 alkanes and mixtures thereof, more preferably of C6 alkanes and mixtures thereof. The process of any one of embodiments 10 to 14, wherein contacting is performed at a pressure in the range of from 10 to 50 bara, preferably of from 12 to 45 bara, more preferably of from 15 to 40 bara, more preferably of from 18 to 35 bara, and more preferably of from 20 to 30 bara. The process of any one of embodiments 10 to 15, wherein the feed gas stream prepared in (ii) comprises from 0.1 to 75 vol.-% of NH3, preferably from 0.3 to 60 vol.-%, more preferably from 0.5 to 50 vol.-%, more preferably from 0.8 to 40 vol.-%, more preferably from 1 to 30 vol.-%, more preferably from 12 to 25 vol.-%. The process of any one of embodiments 10 to 16, wherein the feed gas stream prepared in (ii) comprises from 10 to 70 vol.-% of the one or more hydrocarbons, preferably from 12 to 60 vol.-%, more preferably from 15 to 50 vol.-%, more preferably from 20 to 40 vol.-%, more preferably from 22 to 29 vol.-%. The process of any one of embodiments 10 to 17, wherein the feed gas stream prepared in (ii) comprises from 0 to 75 vol.-% of H2O, preferably from 0.5 to 70 vol.-%, more preferably from 1 to 68 vol.-%, more preferably from 3 to 66 vol.-%, more preferably from 5 to 64 vol.-%, more preferably from 8 to 62 vol.-%, more preferably from 10 to 60 vol.-%, more preferably from 25 to 50 vol.-%, more preferably from 33 to 44 vol.-%. The process of any one of embodiments 10 to 18, wherein the feed gas stream prepared in (ii) comprises from 0 to 60 vol.-% of CO₂, preferably from 1 to 58 vol.-%, more preferably from 3 to 56 vol.-%, more preferably from 5 to 54 vol.-%, more preferably from 8 to 52 vol.-%, more preferably from 10 to 50 vol.-%, more preferably from 12 to 20 vol.-%. The process of any one of embodiments 10 to 19, wherein the feed stream displays an H2O : C molar ratio of H₂O to carbon contained in the one or more hydrocarbons in the range of from 0 to 4, preferably of from 0.1 to 3, more preferably of from 0.2 to 3, more preferably of from 0.3 to 2.5, more preferably of from 0.4 to 2, and more preferably of from 0.5 to 1.6. The process of any one of embodiments 10 to 20, wherein the feed stream displays a CO₂ : C molar ratio of CO₂ to carbon contained in the one or more hydrocarbons in the range of from 0 to 4, preferably of from 0.1 to 3, more preferably of from 0.2 to 2, more preferably of from 0.3 to 1 .5, more preferably of from 0.4 to 0.8. The process of any one of embodiments 10 to 21 , wherein the feed stream displays an NHs : C molar ratio of NH3 to carbon contained in the one or more hydrocarbons in the range of from 0 to 5, preferably of from 0 to 4, more preferably of from 0.001 to 3, more preferably of from 0.005 to 2, and more preferably of from 0.01 to 1 . The process of any one of embodiments 10 to 22, wherein the effluent gas stream removed in (iv) further comprises CO₂. The process of any one of embodiments 10 to 23, wherein the effluent gas stream removed in (iv) displays a stoichiometry number R in the range of from 0.1 to 3, wherein R is defined according to formula wherein c(H₂), c(CO₂), and c(CO) stand for the molar concentration of H₂, CO₂, and CO in the effluent gas stream, respectively. The process of embodiment 24, wherein the stoichiometry number R is in the range of from 1 to 2.5, preferably of from 1 .3 to 2.2. The process of embodiment 24, wherein R is > 2. The process of any one of embodiments 10 to 23 and 26, wherein the effluent gas stream removed in (iv) displays an H₂ : CO molar ratio of >2. The process of embodiment 24, wherein the stoichiometry number R is in the range of 0.5 to 3, preferably of from 1 to 2.2, and more preferably of 1.3 to 1 .7. The process of any one of embodiments 10 to 28, wherein the effluent gas stream removed in (iv) comprises from 10 to 90 vol.-% of H₂, preferably from 20 to 80 vol.-%, more preferably from 30 to 70 vol.-%, more preferably from 40 to 65 vol.-%, and more preferably from 45 to 60 vol.-%. The process of any one of embodiments 10 to 29, wherein the effluent gas stream removed in (iv) comprises from 1 to 70 vol.-% of CO, preferably from 3 to 50 vol.-%, more preferably from 5 to 40 voL-%, more preferably from 10 to 35 vol.-%, and more preferably from 15 to 30 vol.-%. The process of any one of embodiments 10 to 30, wherein the effluent gas stream removed in (iv) comprises from 1 to 50 vol.-% of CO₂, preferably from 3 to 45 voL-%, more preferably from 5 to 40 vol.-%, more preferably from 8 to 35 voL-%, more preferably from 10 to 30 voL-%, and more preferably from 12 to 25 voL-%. 32. The process of any one of embodiments 1 to 31 , 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.

33. The process of embodiment 32, 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.

34. The process of embodiment 32 or 33, wherein the C03M03N comprises one or more primary particles.

35. The process of embodiment 34, 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.

36. The process of 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, wherein the average particle size D50 is preferably determined according to Reference Example 1.b.

37. The process of any one of embodiments 34 to 36, wherein the primary particles comprise one or more agglomerates of one or more C03M03N nano-crystallites.

38. The process of embodiment 37, 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.

39. The process of any one of embodiments 1 to 38, wherein the catalytic material comprises 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.

40. The process of embodiment 39, 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.

41 . The process of any one of embodiments 1 to 40, wherein the catalytic material comprises 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.

42. The process of any one of embodiments 1 to 41 , wherein the catalytic material comprises from 0 to 1 weight-%, preferably from 0 to 0.1 weight-%, more preferably from 0 to 0.01 weight-%, of (MI^MoCU based on the total weight of the catalytic material.

43. The process of any one of embodiments 1 to 42, wherein the catalytic material comprises 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 MoO4²’, Mo2Oz^2-, MosC ', MO₄O₁3^2-, Mo₅Oi6^2-, MO₆O₁₉ ²-, MO7O24⁶', MosC ', and mixtures of two or more thereof.

44. The process of any one of embodiments 1 to 43, wherein the one or more first promoter metals M1 are in the form of one or more of hydroxides, and oxides.

45. The process of any one of embodiments 1 to 44, wherein the one or more first promoter metals M1 comprised in the catalytic material contained in the reactor provided according to (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, 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.

46. The process of any one of embodiments 1 to 45, wherein the catalytic material contained in the reactor provided according to (i) has a molar ratio M1 :Mo, of the one or more first promoter metals M 1 , 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 1.0-10³: 1 to 8.5-10²:1 , preferably in the range of 2.0-10³:1 to 8.0-10"²:1 , 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 7.0-10²:1 , more preferably in the range of 4.0-10³:1 to 6.5-10’²:1 , more preferably in the range of 4.1 -10"³:1 to 6.2-10²:1 , more preferably in the range of 5.0-10’³:1 to 6.0-10"²:1 , more preferably in the range of 6.0-10³:1 to 5.5-10²:1 , more preferably in the range of 7.0-10’³:1 to 5.0- 10²: 1 , more preferably in the range of 8.0-10’³:1 to 4.5-10²:1 , more preferably in the range of 9.0-10³:1 to 4.0-10~²:1 , more preferably in the range of 1.0-10²:1 to 3.5-10²:1 , more preferably in the range of 1 .2-10^-2:1 to 3.3-10’²:1 , more preferably in the range of 2.0 10²:1 to 3.0-10'²:1.

47. The process of any one of embodiments 1 to 46, wherein the catalytic material contained in the reactor provided according to (i) further comprises one or more second promoter metals M2 supported on the C03M03N, wherein the one or more second promoter 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, Y, La, and mixtures of two or more thereof, preferably 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, more 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. The process of embodiment 47, wherein the one or more second promoter metals M2 are in the form of one or more of hydroxides, and oxides. The process of embodiment 47 or 48, wherein the 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 , preferably in the range of 2.0-1 ³: 1 to 1.2-10¹:1 , more preferably in the range of 2.2-1 O’³: 1 to 1.0-10’²:1 , more preferably in the range of 3.0-1 O’³: 1 to 9.0-10²:1 , more preferably in the range of 4.0-10’³:1 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 6.0-10’³:1 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 8.0-10³:1 to 3.0- 10²: 1 , more preferably in the range of 9.0-10’³:1 to 2.9-10’²:1 , more preferably in the range of 1 .0-1 O’²: 1 to 2.0-10’²:1 . The process of any one of embodiments 1 to 49, wherein the catalytic material contained in the reactor provided according to (1) further comprises one or more third promoter metals M3, wherein M3 is preferably different to M 1 , 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. The process of any one of embodiments 1 to 50, wherein the catalytic material contained in the reactor provided according to (1) comprises 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 sum of the weights of the C03M03N, the one or more first promoter metals

M 1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3. The process of any one of embodiments 1 to 51 , 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 M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3, comprised in the catalytic material contained in the reactor provided in (i) are comprised in a layer supported on the C03M03N, wherein the layer preferably is amorphous. 53. The process of 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, more preferably in the range of 2 to 5 nm, wherein the layer thickness is preferably determined according to Reference Example 1.b.

54. The process of any one of embodiments 1 to 53, 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 M1 , optionally the one or more second promoter metals M2, and optionally the one or more third promoter metals M3, H, and O.

55. The process of any one of embodiments 1 to 54, wherein the catalytic material has 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.

56. The process of any one of embodiments 1 to 55, wherein the catalytic material is 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.

57. The process of any one of embodiments 1 to 56, wherein the catalytic 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, wherein the tap density is preferably determined according to Reference Example 1.c.

58. The process of any one of embodiments 1 to 57, wherein the catalytic material has 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.

59. The process of any one of embodiments 1 to 58, wherein the catalytic material has 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.

60. The process of any one of embodiments 1 to 59, wherein the effluent gas stream removed in (iv) is employed in a process for the production of methanol, for the production of dimethyl ether, or for the production of methanol and dimethylether.

61 . The process of any one of embodiments 1 to 60, wherein the effluent gas stream removed in (iv) is employed in a process for the production of hydrocarbons, preferably according to the Fischer-Tropsch process. 62. The process of any one of embodiments 1 to 61 , wherein the effluent gas stream removed in (iv) is employed in a process for the production of alcohols, preferably of alkanols, more preferably of C1 to C10 alkanols, more preferably of C2 to C8 alkanols, more preferably of C2 to C6 alkanols, more preferably of C2 to C4 alkanols, more preferably of 02 alkanols, and more preferably of ethanol.

63. The process of any one of embodiments 1 to 62, wherein the feed gas stream prepared in (ii) and fed into the reactor in (iii) further comprises H2 for reducing the catalytic material.

64. The process of embodiment 63, wherein the feed gas stream prepared in (ii) and fed into the reactor in (iii) comprises from 0.5 to 80 vol.-% of H2, preferably from 1 to 70 vol.-%, more preferably from 2 to 60 vol.-%, more preferably from 5 to 50 voL-%, more preferably from 15 to 40 voL-%.

DESCRIPTION OF THE FIGURES

Figure 1 : shows the results from catalytic testing for a Ni catalyst as reference, a C03M03N supporting Cs as reference, and a C03M03N supporting Cs and Re. On the abscissa, the temperature is given in °C, and on the ordinate, the NH3 conversion is noted in %.

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 GieBen, 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 (SiO?), 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 Amt Kern, Z. Kristallogr. 2011 , 226, 944.

The obtained diffraction patterns were analyzed against reference diffraction patterns from the ICSD for CoaMoaN, C02M03N, CoMoO4, CO3O4, CoO, MoO₂, MOO3, MoN, Mo₂N.

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 CoMoO4-nH2O precursor

A CoMoO4-nH2O precursor was prepared as bulk material using (NH4)6Mo7O24-4H2O and CO(NO3)2-6H₂O as starting materials. 40.5 g (NH₄)6Mo7O₂4'4H₂O (32.8 mmol; 1 eq. Mo) and 67.0 g CO(NO3)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 catalytic materials

A 13 g sample of the CoMoO₄-nH₂O precursor as obtained from Reference Example 2 was subject to impregnation with aqueous promoter and co-promotor solutions. Impregnation of the promoter Cs was performed via incipient wetness impregnation. For this, the solvent uptake of the sample obtained from Reference Example 2 was determined to 0.6 mL g ¹ and the promoting solution was prepared with a total volume of 7.8 mL, blended with CoMoO₄ nH₂O. The resulting wet material was dried at 80 °C for 16 h in synthetic air.

For co-promoting with Re, a sequential wetness incipient impregnation was applied, where the promoter was added first, according to the above described procedure. Afterwards, the co-pro- motor being Re was added similarly using diluted perrhenic acid. The resulting material was dried at 80 °C for 16 h in synthetic air.

The applied metal compounds were used without prior purification for impregnation and are listed in table 1 . Table 2 contains the impregnated amounts of promotor and co-promotor 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 promoter and co-promotor in the finished catalyst to the sample of CoMoO₄-nH₂O 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 CoMoO₄ 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 and co-promoter loadings on CoMoC n W obtained from Reference Example 2, wherein the loadings are given in weight-% based on the ammonolyzed catalyst.

The obtained supported CoMoC nl-hO were subjected to ammonolysis as outlined in the following.

A sample of the supported CoMo04-nH₂0 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 pressure of 1 .5 t cm ², crushed and sieved into a 250 to 315 pm split fraction in ambient air.

Table 3

Analytical data for C03M03N supporting Cs and Re.

Example 1 : The feed stream comprised 94.5 volume-% of NH3 and 5 volume-% of an inert gas, and had a pressure of 20 bara, a gas hourly space velocity (GHSV) of 4000 IT¹ and contained 5000 vol- ume-ppm (ppmv) of H2O.

The results from the catalytic testing are shown in Figure 1 and Table 1.

Table 4

Results from comparative testing for a Ni catalyst as reference, and a C03M03N supporting Cs and Re.

As it can be gathered from the results, the process of the present invention achieves a comparatively higher NH3 conversion than the reference Ni catalyst, in particular in the temperature range of 450 to 650 °C.

CITED LITERATURE

- A. Srifa et al. in Applied Catalysis B: Environmental 218 (2017), p. 1-8

I. Lucentini et al. in Ind. Eng. Chem. Res. 2021 , 60, 18560-18611

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Claims

1 . A process for the reforming of ammonia, wherein the process comprises

(ii) preparing a feed gas stream comprising NH3;

(iv) removing an effluent gas stream from the reactor, the effluent gas stream comprising H2 and N₂.

2. The process of claim 1 , wherein the feed gas stream prepared in (ii) comprises from 100 to 50,000 ppmv of H₂O.

3. The process of claim 1 or 2, wherein the feed gas stream prepared in (ii) further comprises one or more inert gases and H₂, wherein the total amount of NH3, inert gas, and H₂ comprised in the feed gas stream prepared in (ii) is in the range from 90 to 100 wt.-%.

4. The process of any one of claims 1 to 3, wherein the process is for the reforming of ammonia and hydrocarbons, wherein the feed gas stream prepared in (ii) further comprises one or more hydrocarbons, and one or more of CO₂ and H₂O, and wherein the effluent gas stream removed in (iv) further comprises CO.

5. The process of any one of claims 1 to 4, wherein the C03M03N comprises one or more crystalline C03M03N phases.

6. The process of claim 5, wherein the C03M03N comprises one or more primary particles.

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

8. The process of any one of claims 1 to 7, wherein the one or more first promoter metals M 1 comprised in the catalytic material contained in the reactor provided according to (i) are selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof.

9. The process of any one of claims 1 to 8, wherein the catalytic material contained in the reactor provided according to (i) has a molar ratio M1 :Mo, of the one or more first promoter metals M 1 , 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 8.5-10’²:1.

10. The process of any one of claims 1 to 9, wherein the catalytic material contained in the reactor provided according to (I) further comprises one or more second promoter metals M2 supported on the C03M03N, wherein the one or more second promoter 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, Y, La, and mixtures of two or more thereof.

11 . The process of claim 10, wherein the 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, calculated as element, in the range of 1.0-1 O’³: 1 to 2.0-10-¹:1.

12. The process of any one of claims 1 to 11 , wherein the catalytic material contained in the reactor provided according to (1) further comprises one or more third promoter metals M3, wherein M3 is selected from the group consisting of alkali metals, alkaline earth metals, and mixtures thereof.

13. The process of any one of claims 1 to 12, wherein the effluent gas stream removed in (iv) is employed in a process for the production of methanol, for the production of dimethyl ether, or for the production of methanol and dimethylether.

14. The process of any one of claims 1 to 13, wherein the effluent gas stream removed in (iv) is employed in a process for the production of hydrocarbons.

15. The process of any one of claims 1 to 14, wherein the effluent gas stream removed in (iv) is employed in a process for the production of alcohols.