Process for preparing an activated catalyst and process for preparing methanol using a co 2-containing feed stream

Abstract

The present invention relates to a process for preparing an activated catalyst using a gas stream comprising H2 and CO2 having a specific molar ratio. The resulting activated catalyst is particularly suitable for use in the preparation of methanol, especially from a CO2-containing feedstock. Thus, the present invention also relates to a process for the preparation of methanol using the activated catalyst.

Description

[0001] Process for preparing an activated catalyst and process for preparing methanol using a CO2- containing feed stream

[0002] TECHNICAL FIELD

[0003] The present invention relates to a process for preparing an activated catalyst using a gas stream comprising H2 and CO2 having a specific molar ratio. The resulting activated catalyst is particularly suitable for use in the preparation of methanol, especially from a CO2-containing feedstock. Thus, the present invention also relates to a process for the preparation of methanol using the activated catalyst.

[0004] INTRODUCTION

[0005] Methanol is known as an important compound with widespread applications, especially for chemicals production and in the energy sector, e.g. as a substitute for gasoline or diesel fuels. The standard method of producing methanol is based on a conversion of conventional syngas with high CO and low CO2 content, such that the main reaction relates to the conversion of CO with hydrogen to methanol according to equation (1):

[0006] CO + 2H2^ CH3OH (1).

[0007] In such typical conversion reactions, the partial pressure of CO2 and of H2O as by-product of CO2 conversion is low. Said scenario typically requires non-demanding conditions enabling a long catalyst lifetime. The conversion of a CO2-rich syngas is generally also possible wherein CO2 is reacted with hydrogen to methanol according to equation (2):

[0008] CO2+ 3H2CH3OH + H2O (2).

[0009] If a CO2-rich syngas is used, CO2 and H2 exhibit a comparatively high partial pressure. However, applying conversion of a CO2-rich syngas is particularly challenging due to the reverse water-gas shift (rWGS) reaction, wherein additional H2O is generated according to equation (3):

[0010] CO2+ H2CO + H2O (3).

[0011] In addition, CO is generated as contribution of the rWGS reaction, which is then present in the process. Thus, even with a CO2-only feedstock, wherein in particular no CO is comprised in the feed gas stream, at least small amounts of CO can be expected to be generated during the process for preparing CH3OH. After reductive activation of a catalyst to be used in the process for preparing CH3OH, the conditions must be adapted to operational mode. Typically, this includes adjusting pressure, temperature, contact time, gas hourly space velocity and feed composition. Generally, introduction of a CC>2-based feedstock has different requirements than introduction of a conventional syngas mixture with CO contents of, e.g., 5 to 15 volume-%.

[0012] WO 2020 / 212681 A1 relates to catalysts containing Cu, ZnO, AI2O3, and SiO2. It is disclosed that said catalysts are suitable for use in carbon oxide conversion reactions, such as water-gas shift reaction and methanol synthesis. In particular, a method is disclosed therein including the steps of (i) activating the catalyst by contacting it with a reducing gas stream and (ii) reacting a carbon oxide containing process gas containing at least one of carbon monoxide and carbon dioxide and additionally containing hydrogen and / or steam, in the presence of a catalyst to form a product stream.

[0013] DE 10 2017 001 520 A1 relates to a reactor and method for maximizing methanol yield by using catalyst layers. In particular, a process for the catalytic production of methanol from synthesis gas is disclosed therein, the process comprising the following steps: providing a reactor; placing at least two catalyst layers in the reactor, wherein the first catalyst layer is placed upstream and the second catalyst layer is placed downstream, and wherein the activity of the downstream, and wherein the activity of the first catalyst layer is higher than the activity of the second catalyst layer, pressurizing the reactor with synthesis gas comprising hydrogen and carbon oxides, reacting the synthesis gas in the reactor under methanol synthesis conditions to form methanol, discharging the produced methanol and the unreacted synthesis gas from the reactor.

[0014] CN 101386564 B discloses a process for synthesizing methanol from hydrogen and carbon dioxide, particularly including the step of converting a gas stream comprising H2 and CO2 in a specific molar ratio in the presence of a catalyst comprising Cu, Zn and Al having specific molar ratios to obtain CH3OH, H2O and CO. As reaction conditions, a temperature in the range of from 230 to 280 °C, a pressure in the range of from 5.0 to 8.5 MPa or in the range of from 0.2 to 2.0 MPa, and a gas hourly space velocity in the range of from 10,000 to 20,000 h’1or in the range of from 8,000 to 18,000 h-1are disclosed.

[0015] WO 2023 / 088893 A1 relates to a process for preparing methanol by the conversion of CO2-con- taining syngas, comprising a step of contacting the syngas with a supported copper catalyst comprising Cu, Zn, Al, Zr, Si, and O at a temperature in the range of from 200 to 350 °C. The catalyst is reduced beforehand in an H2 atmosphere at a temperature in the range of from 150 to 350 °C.

[0016] However, none of the prior art discloses particular conditions for switching from the activation phase of the catalyst to the operational phase for preparing methanol.

[0017] Thus, there was a need for a novel process for preparing an activated catalyst, in particular for use in the preparation of methanol, wherein a CO2-containing feed gas stream is used. DETAILED DESCRIPTION

[0018] Surprisingly, it was found that, after a reduction phase using H2, subjecting the catalyst to a CO2-containing gas atmosphere having a comparatively small CO2-content leads to a more active catalyst compared to the situation, wherein the catalyst is subjected to a gas stream comprising a comparatively high CO2 content. It was further found that subjecting the catalyst after reduction with a conventional syngas feedstock and switching then to a CO2-based feedstock showed even worse performance with respect to the preparation of CH3OH. This was found for catalysts comprising Cu supported on a support material.

[0019] Therefore, the present invention relates to a process for preparing an activated catalyst, the process comprising

[0020] (i) preparing a catalyst comprising one or more salts of Cu, one or more oxides of Cu, or one or more salts and one or more oxides of Cu supported on a support material;

[0021] (ii) contacting the catalyst prepared in (i) with a first gas stream comprising H2, optionally comprising an inert gas, and optionally further comprising CO2, wherein the first gas stream comprises a CO2 to H2 molar ratio in the range of from 0:1 to 0.001 :1 ;

[0022] (iii) contacting the catalyst obtained in (ii) with a second gas stream comprising CO2 and H2, wherein the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.001 :1 to 0.075:1 , obtaining an activated catalyst.

[0023] It is preferred that the first gas stream comprises a CO2 to H2 molar ratio in the range of from 0:1 to 0.0001 :1 , more preferably in the range of from 0:1 to 0.00001 :1 , more preferably in the range of from 0: 1 to 0.000001 : 1 .

[0024] It is preferred that the first gas stream comprises from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume-%, of CO2.

[0025] It is preferred that the first gas stream comprises from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume-%, of CO.

[0026] It is preferred that the first gas stream comprises from 1 to 99 volume-%, more preferably from 50 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 vol- ume-%, of H2.

[0027] It is preferred that the first gas stream further comprises an inert gas, wherein the first gas stream more preferably comprises from 1 to 40 volume-%, more preferably from 10 to 30 vol- ume-%, more preferably from 15 to 25 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2. It is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the first gas stream consists of H2, optionally an inert gas, optionally CO2, and optionally CO.

[0028] It is preferred that the first gas stream has a temperature in the range of from 145 to 290 °C, more preferably in the range of from 165 to 260 °C, more preferably in the range of from 185 to 250 °C, more preferably in the range of from 200 to 240 °C.

[0029] It is preferred that the first gas stream has a pressure in the range of from 1 to 110 barg, more preferably in the range of from 5 to 80 barg, more preferably in the range of from 20 to 60 barg, more preferably in the range of from 35 to 45 barg.

[0030] It is preferred that the first gas stream has a gas hourly space velocity in the range of from 100 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0031] It is preferred that the first gas stream is contacted with the catalyst for a period of time in the range of from 1 h to 2 weeks, more preferably in the range of from 3 h to 7 d, more preferably in the range of from 6 h to 6.5 d, more preferably of from 12 h to 6 d, more preferably of from 1 to 5.5 d, more preferably of from 2 to 5 d, more preferably of from 3 to 4.5 d, and more preferably of from 3.5 to 4 d.

[0032] It is preferred that the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.002:1 to 0.067:1 , more preferably in the range of from 0.004:1 to 0.053:1 , more preferably in the range of from 0.007:1 to 0.029:1 , more preferably in the range of from 0.010:1 to 0.026:1 , more preferably in the range of from 0.011 :1 to 0.020:1 , more preferably in the range of from 0.012:1 to 0.013:1.

[0033] It is preferred that the second gas stream comprises from 0.1 to 7 volume-%, more preferably from 0.2 to 4.5 volume-%, more preferably from 0.3 to 2.5 volume-%, more preferably from 0.4 to 1 .6 volume-%, more preferably from 0.7 to 1 .3 volume-%, more preferably from 0.9 to 1 .1 vol- ume-%, of CO2.

[0034] It is preferred that the second gas stream comprises from 0 to 5 volume-%, more preferably from 0 to 1 volume-%, more preferably from 0 to 0.5 volume-%, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume- %, of CO.

[0035] It is preferred that the second gas stream comprises from 1 to 99 volume-%, more preferably from 50 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2. It is preferred that the second gas stream further comprises an inert gas, wherein the second gas stream more preferably comprises from 1 to 90 volume-%, more preferably from 5 to 40 vol- ume-%, more preferably from 10 to 30 volume-%, more preferably from 15 to 25 volume-%, of the inert gas, wherein the inert gas is more preferably selected from the group consisting of N2 and Ar, wherein the inert gas more preferably is N2.

[0036] It is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the second gas stream consist of CO2, H2, optionally CO, and optionally an inert gas.

[0037] It is preferred that the second gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0038] It is preferred that the second gas stream has a pressure in the range of from 5 to 120 barg, more preferably in the range of from 20 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0039] It is preferred that the second gas stream has a gas hourly space velocity in the range of from 100 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0040] It is preferred that the second gas stream is contacted with the catalyst for a period of time in the range of from 1 s to 1 week, more preferably of from 1 min to 5 d, more preferably of from 0.5 h to 2 d, more preferably of from 0.5 h to 1 d, more preferably of from 0.5 to 12 h, more preferably of from 0.5 h to 8 h, more preferably of from 0.75 to 5.0 h, more preferably of from 1 .0 to 3.0 h, more preferably in the range of from 1 .5 to 2.5 h.

[0041] It is preferred that the one or more oxides of Cu are selected from the group consisting of Cu(ll)O, Cu(l)2O, and mixtures thereof.

[0042] It is preferred that the one or more salts of Cu are selected from the group consisting of Cu(l)CI, Cu(l)Br, Cu(l)l, Cu(l)CN, Cu(l)2SO4, Cu(l)2S, Cu(l) t-butoxide, Cu(l)SCN, Cu(ll)F2, Cu(ll)CI2, Cu(ll)Br2, CU(I I)OH2, CU(II)(NO3)2, CU(I I)SO4, CU(I I)(OAC)2, CU(I I)2CO3(OH)2, CU(I I)(O2C5H7)2 (Cu(ll) acetylacetonate), Cu3(PO4)2, Cu(SCN)2, and mixtures of two or more thereof, wherein the one or more salts of Cu more preferably comprises, more preferably are, Cu(ll)(NO3)2.

[0043] It is preferred that the catalyst comprises from 30 to 70 weight-%, more preferably from 50 to 70 weight-%, more preferably from 60 to 70 weight-%, of Cu, calculated as CuO, based on the total weight of the catalyst. It is preferred that the catalyst further comprises Zn, wherein the catalyst more preferably comprises from 20 to 30 weight-%, more preferably from 23 to 29 weight-%, of Zn, calculated as ZnO, based on the total weight of the catalyst.

[0044] It is preferred that the support material is selected from the group consisting of non-metal oxides, metal oxides, metal halides, carbon materials, and mixtures of two or more thereof, wherein the support material more preferably is one or more of a non-metal oxide and a metal oxide.

[0045] It is preferred that the support material comprises, more preferably consists of, one or more of AI2O3 and SiC>2, more preferably AI2O3.

[0046] In the case where the support material comprises, more preferably consists of, AI2O3, it is preferred that the catalyst comprises from 5 to 20 weight-%, more preferably from 5 to 15 weight- %, more preferably from 7 to 13 weight-%, more preferably from 8 to 11 weight-%, of AI2O3, based on the total weight of the catalyst.

[0047] Further in the case where the support material comprises, more preferably consists of, AI2O3, it is preferred that the support material comprises SiC>2, wherein the catalyst more preferably comprises from 0.05 to 1 .50 weight-%, more preferably from 0.2 to 1 .20 weight-%, more preferably from 0.3 to 0.8 weight-% of SiC>2, based on the total weight of the catalyst.

[0048] It is preferred that the catalyst is in the form of a molding.

[0049] It is preferred that (i) comprises

[0050] (1.1 ) providing a support material;

[0051] (1.2) supporting Cu and optionally Zn on the support material, wherein supporting is preferably performed by impregnation, more preferably wet impregnation.

[0052] It is preferred that the process further comprises

[0053] (iv) contacting the catalyst obtained in (iii) with a third gas stream comprising CO2 and H2, wherein the third gas stream comprises a CO2 to H2 molar ratio in the range of from 0.005:1 to 0.200:1 , more preferably in the range of from 0.010:1 to 0.040:1 , more preferably in the range of from 0.020:1 to 0.030:1.

[0054] In the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream comprises from 0.5 to 15 volume-%, more preferably from 1.5 to 5.0 vol- ume-%, more preferably from 1 .8 to 2.2 volume-%, of CO2.

[0055] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream comprises from 0 to 5.0 volume-%, more preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume-%, of CO. Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream comprises from 50 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0056] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream comprises an inert gas, wherein the third gas stream more preferably comprises from 1 to 25 volume-%, more preferably from 13 to 23 volume-%, more preferably from 16 to 20 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably N2.

[0057] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the third gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0058] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0059] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0060] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0061] Further in the case where the process further comprises (iv) as defined hereinabove, it is preferred that the third gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0062] It is preferred that the process further comprises

[0063] (v) contacting the catalyst obtained in (iv) with a fourth gas stream comprising CO2 and H2, wherein the fourth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.020:1 to 0.080:1 , more preferably in the range of from 0.040:1 to 0.060:1 , more preferably in the range of from 0.045:1 to 0.055:1. In the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream comprises from 2.0 to 6.0 volume-%, more preferably from 3.0 to 5.0 vol- ume-%, more preferably from 3.5 to 4.5 volume-%, of CO2.

[0064] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream comprises from 0.5 to 1 .5 volume-%, more preferably from 0.7 to 1.3 volume-%, more preferably from 0.9 to 1.1 volume-%, of CO.

[0065] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream comprises from 65 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0066] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream comprises an inert gas, wherein the fourth gas stream more preferably comprises from 9 to 21 volume-%, more preferably from 11 to 19 volume-%, more preferably from 13 to 17 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, preferably N2.

[0067] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the fourth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0068] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0069] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0070] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,000 to 7,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0071] Further in the case where the process further comprises (v) as defined hereinabove, it is preferred that the fourth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h. It is preferred that the process further comprises

[0072] (vi) contacting the catalyst obtained in (v) with a fifth gas stream comprising CO2 and H2, wherein the fifth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.050:1 to 0.100:1 , more preferably in the range of from 0.065:1 to 0.085:1 , more preferably in the range of from 0.070:1 to 0.080:1.

[0073] In the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream comprises from 4.0 to 8.0 volume-%, more preferably from 5.0 to 7.0 vol- ume-%, more preferably from 5.5 to 6.5 volume-%, of CO2.

[0074] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream comprises from 1 .0 to 3.0 volume-%, more preferably from 1 .6 to 2.4 volume-%, more preferably from 1 .8 to 2.2 volume-%, of CO.

[0075] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream comprises from 65 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0076] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream comprises an inert gas, wherein the fifth gas stream more preferably comprises from 5 to 19 volume-%, more preferably from 8 to 16 volume-%, more preferably from 10 to 14 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably N2.

[0077] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the fifth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0078] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0079] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0080] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,000 to 7,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0081] Further in the case where the process further comprises (vi) as defined hereinabove, it is preferred that the fifth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0082] It is preferred that the process further comprises

[0083] (vii) contacting the catalyst obtained in (vi) with a sixth gas stream comprising CO2 and H2, wherein the sixth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.100:1 to 0.150:1 , more preferably in the range of from 0.110:1 to 0.140:1 , more preferably in the range of from 0.120:1 to 0.130:1.

[0084] In the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream comprises from 5 to 15 volume-%, more preferably from 7 to 13 volume-%, more preferably from 9 to 11 volume-%, of CO2.

[0085] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream comprises from 1 .0 to 5.0 volume-%, more preferably from 2.0 to 4.0 volume-%, more preferably from 2.5 to 3.5 volume-%, of CO.

[0086] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream comprises from 65 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0087] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream comprises an inert gas, wherein the sixth gas stream more preferably comprises from 3 to 11 volume-%, more preferably from 5 to 9 volume-%, more preferably from 6 to 8 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably N2.

[0088] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the sixth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0089] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C. Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0090] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0091] Further in the case where the process further comprises (vii) as defined hereinabove, it is preferred that the sixth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0092] It is preferred that the process further comprises

[0093] (viii) contacting the catalyst obtained in (vii) with a seventh gas stream comprising CO2 and H2, wherein the seventh gas stream comprises a CO2 to H2 molar ratio in the range of from 0.135:1 to 0.200:1 , more preferably in the range of from 0.150:1 to 0.185:1 , more preferably in the range of from 0.160:1 to 0.175:1.

[0094] In the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream comprises from 9.5 to 17.5 volume-%, more preferably from 11 .5 to

[0095] 15.5 volume-%, more preferably from 12.5 to 14.5 volume-%, of CO2.

[0096] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream comprises from 1 .5 to 5.0 volume-%, more preferably from

[0097] 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 volume-%, of CO.

[0098] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream comprises from 65 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0099] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream comprises an inert gas, wherein the seventh gas stream more preferably comprises from 1 to 5 volume-%, more preferably from 2 to 4 volume-%, more preferably from 2.5 to 3.5 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably N2. Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the seventh gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0100] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0101] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0102] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0103] Further in the case where the process further comprises (viii) as defined hereinabove, it is preferred that the seventh gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0104] It is preferred that the process further comprises

[0105] (ix) contacting the catalyst obtained in (viii) with a eighth gas stream comprising CO2 and H2, wherein the eighth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.150:1 to 0.200:1 , more preferably in the range of from 0.160:1 to 0.190:1 , more preferably in the range of from 0.170:1 to 0.180:1.

[0106] In the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream comprises from 9.5 to 17.5 volume-%, more preferably from 11 .5 to 15.5 volume-%, more preferably from 12.5 to 14.5 volume-%, of CO2.

[0107] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream comprises from 1.5 to 5.0 volume-%, more preferably from 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 volume-%, of CO.

[0108] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream comprises from 60 to 90 volume-%, more preferably from 65 to 85 volume-%, more preferably from 70 to 80 volume-%, of H2. Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream comprises an inert gas, wherein the eighth gas stream more preferably comprises from 4.0 to 9.0 volume-%, more preferably from 5.0 to 8.0 volume-%, more preferably from 6.0 to 7.0 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably Ar.

[0109] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the eighth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0110] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream has a temperature in the range of from 170 to 290 °C, more preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0111] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream has a pressure in the range of from 5 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0112] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 h’1, more preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0113] Further in the case where the process further comprises (ix) as defined hereinabove, it is preferred that the eighth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, more preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0114] The present invention further relates to an activated catalyst obtainable or obtained by the process according to any one of the embodiments defined herein.

[0115] Yet further, the present invention relates to a process for preparing methanol, the process comprising

[0116] (A) preparing an activated catalyst, wherein the activated catalyst is prepared according to the process of any one of the embodiments defined herein;

[0117] (B) contacting the activated catalyst prepared in (A) with a feed gas stream comprising CO2 and H2, wherein the feed gas stream comprises a CO2 to H2 molar ratio in the range of from 0.100:1 to 0.250:1 , preferably in the range of from 0.130:1 to 0.220:1 , more preferably in the range of from 0.150:1 to 0.200:1 , more preferably in the range of from 0.160:1 to 0.190:1 , more preferably in the range of from 0.170:1 to 0.180:1 , obtaining a product gas stream comprising CH3OH.

[0118] It is preferred that the feed gas stream according to (B) comprises from 9.5 to 21 volume-%, more preferably from 10.5 to 17.5 volume-%, more preferably from 11.5 to 15.5 volume-%, more preferably from 12.5 to 14.5 volume-%, of CO2.

[0119] It is preferred that the feed gas stream according to (B) comprises from 0.5 to 8.0 volume-%, more preferably from 1.5 to 5.0 volume-%, more preferably from 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 volume-%, of CO.

[0120] It is preferred that the feed gas stream according to (B) comprises from 60 to 93 volume-%, more preferably from 63 to 90 volume-%, more preferably from 65 to 85 volume-%, more preferably from 70 to 80 volume-%, of H2.

[0121] It is preferred that the feed gas stream according to (B) comprises an inert gas, wherein the feed gas stream according to (B) more preferably comprises from 0.001 to 10.0 volume-%, more preferably from 0.01 to 9.5 volume-%, more preferably from 0.1 to 9.0 volume-%, more preferably from 0.5 to 8.5 volume-%, more preferably from 1 .0 to 8.5 volume-%, more preferably from 2.0 to 8.0 volume-%, more preferably from 5.0 to 8.0 volume-%, more preferably from 6.0 to 7.0 volume-%, of the inert gas, wherein the inert gas comprises, more preferably consists of, one or more of Ar and N2, more preferably Ar.

[0122] It is preferred that from 90 to 100 volume-%, more preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the feed gas stream according to (B) consists of H2, CO2, optionally an inert gas, and optionally CO.

[0123] It is preferred that the feed gas stream according to (B) has a temperature in the range of from 180 to 310 °C, more preferably in the range of from 200 to 300 °C, more preferably in the range of from 210 to 270 °C, more preferably in the range of from 230 to 250 °C.

[0124] It is preferred that the feed gas stream according to (B) has a pressure in the range of from 30 to 110 barg, more preferably in the range of from 54 to 88 barg, more preferably in the range of from 64 to 85 barg.

[0125] It is preferred that the feed gas stream according to (B) has a gas hourly space velocity in the range of from 500 to 45,000 IT1, more preferably in the range of from 2,500 to 20,000 IT1, more preferably in the range of from 4,500 to 9,500 IT1, more preferably in the range of from 6,500 to 7,500 IT1. It is preferred that the feed gas stream according to (B) is contacted with the catalyst for a period of time in the range of from 10 h to 6 years, more preferably of from 100 h to 5.5 years, more preferably of from 30 d to 5.5 years, more preferably of from 120 d to 5.5 years, more preferably of from 1 to 5 years, more preferably of from 3 to 5 years, more preferably of from 3.5 to 4.5 years.

[0126] It is preferred that the activated catalyst is comprised in a fixed-bed, wherein the activated catalyst is comprised in a reactor comprising the fixed-bed.

[0127] Within the meaning of the present invention, the term “support material” preferably relates to a solid material with a high surface area, a high thermal and chemical stability, and a capability for dispersing metal particles over the surface.

[0128] Within the meaning of the present invention, the term “inert gas” preferably relates to a gas that does not readily undergo chemical reactions with other chemical substances and therefore does not readily form chemical compounds, wherein more preferably said term relates to a noble gas or a gaseous compound having a strongly negative standard enthalpy of formation.

[0129] 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 represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

[0130] 1 . A process for preparing an activated catalyst, the process comprising

[0131] (i) preparing a catalyst comprising one or more salts of Cu, one or more oxides of Cu, or one or more salts and one or more oxides of Cu supported on a support material;

[0132] (ii) contacting the catalyst prepared in (i) with a first gas stream comprising H2, optionally comprising an inert gas, and optionally further comprising CO2, wherein the first gas stream comprises a CO2 to H2 molar ratio in the range of from 0:1 to 0.001 :1 ;

[0133] (iii) contacting the catalyst obtained in (ii) with a second gas stream comprising CO2 and H2, wherein the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.001 :1 to 0.075:1 , obtaining an activated catalyst.

[0134] 2. The process of embodiment 1 , wherein the first gas stream comprises a CO2 to H2 molar ratio in the range of from 0:1 to 0.0001 :1 , preferably in the range of from 0:1 to 0.00001 :1 , more preferably in the range of from 0:1 to 0.000001 :1 . 3. The process of embodiment 1 or 2, wherein the first gas stream comprises from 0 to 0.1 volume-%, preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume- %, of CO2.

[0135] 4. The process of any one of embodiments 1 to 3, wherein the first gas stream comprises from 0 to 0.1 volume-%, preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume-%, of CO.

[0136] 5. The process of any one of embodiments 1 to 4, wherein the first gas stream comprises from 1 to 99 volume-%, preferably from 50 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0137] 6. The process of any one of embodiments 1 to 5, wherein the first gas stream further comprises an inert gas, wherein the first gas stream preferably comprises from 1 to 40 vol- ume-%, preferably from 10 to 30 volume-%, more preferably from 15 to 25 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2.

[0138] 7. The process of any one of embodiments 1 to 6, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the first gas stream consists of H2, optionally an inert gas, optionally CO2, and optionally CO.

[0139] 8. The process of any one of embodiments 1 to 7, wherein the first gas stream has a temperature in the range of from 145 to 290 °C, preferably in the range of from 165 to 260 °C, more preferably in the range of from 185 to 250 °C, more preferably in the range of from 200 to 240 °C.

[0140] 9. The process of any one of embodiments 1 to 8, wherein the first gas stream has a pressure in the range of from 1 to 110 barg, preferably in the range of from 5 to 80 barg, more preferably in the range of from 20 to 60 barg, more preferably in the range of from 35 to 45 barg.

[0141] 10. The process of any one of embodiments 1 to 9, wherein the first gas stream has a gas hourly space velocity in the range of from 100 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0142] 11 . The process of any one of embodiments 1 to 10, wherein the first gas stream is contacted with the catalyst for a period of time in the range of from 1 h to 2 weeks, preferably in the range of from 3 h to 7 d, more preferably in the range of from 6 h to 6.5 d, more preferably of from 12 h to 6 d, more preferably of from 1 to 5.5 d, more preferably of from 2 to 5 d, more preferably of from 3 to 4.5 d, and more preferably of from 3.5 to 4 d.

[0143] 12. The process of any one of embodiments 1 to 11 , wherein the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.002:1 to 0.067:1 , preferably in the range of from 0.004:1 to 0.053:1 , more preferably in the range of from 0.007:1 to 0.029:1 , more preferably in the range of from 0.010:1 to 0.026:1 , more preferably in the range of from 0.011 :1 to 0.020:1 , more preferably in the range of from 0.012:1 to 0.013:1.

[0144] 13. The process of any one of embodiments 1 to 12, wherein the second gas stream comprises from 0.1 to 7 volume-%, preferably from 0.2 to 4.5 volume-%, more preferably from 0.3 to 2.5 volume-%, more preferably from 0.4 to 1 .6 volume-%, more preferably from 0.7 to 1 .3 volume-%, more preferably from 0.9 to 1 .1 volume-%, of CO2.

[0145] 14. The process of any one of embodiments 1 to 13, wherein the second gas stream comprises from 0 to 5 volume-%, preferably from 0 to 1 volume-%, more preferably from 0 to 0.5 volume-%, more preferably from 0 to 0.1 volume-%, more preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 volume-%, of CO.

[0146] 15. The process of any one of embodiments 1 to 14, wherein the second gas stream comprises from 1 to 99 volume-%, preferably from 50 to 95 volume-%, more preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0147] 16. The process of any one of embodiments 1 to 15, wherein the second gas stream further comprises an inert gas, wherein the second gas stream preferably comprises from 1 to 90 volume-%, preferably from 5 to 40 volume-%, more preferably from 10 to 30 volume-%, more preferably from 15 to 25 volume-%, of the inert gas, wherein the inert gas is more preferably selected from the group consisting of N2 and Ar, wherein the inert gas more preferably is N2.

[0148] 17. The process of any one of embodiments 1 to 16, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the second gas stream consist of CO2, H2, optionally CO, and optionally an inert gas.

[0149] 18. The process of any one of embodiments 1 to 17, wherein the second gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0150] 19. The process of any one of embodiments 1 to 18, wherein the second gas stream has a pressure in the range of from 5 to 120 barg, preferably in the range of from 20 to 75 barg, more preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg. 20. The process of any one of embodiments 1 to 19, wherein the second gas stream has a gas hourly space velocity in the range of from 100 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0151] 21 . The process of any one of embodiments 1 to 20, wherein the second gas stream is contacted with the catalyst for a period of time in the range of from 1 s to 1 week, preferably of from 1 min to 5 d, more preferably of from 0.5 h to 2 d, more preferably of from 0.5 h to 1 d, more preferably of from 0.5 to 12 h, more preferably of from 0.5 h to 8 h, more preferably of from 0.75 to 5.0 h, more preferably of from 1.0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0152] 22. The process of any one of embodiments 1 to 21 , wherein the one or more oxides of Cu are selected from the group consisting of Cu(ll)O, Cu(l)2O, and mixtures thereof.

[0153] 23. The process of any one of embodiments 1 to 22, wherein the one or more salts of Cu are selected from the group consisting of Cu(l)CI, Cu(l)Br, Cu(l)l, Cu(l)CN, Cu(l)2SO4, Cu(l)2S, Cu(l) t-butoxide, Cu(l)SCN, Cu(ll)F2, Cu(ll)CI2, Cu(ll)Br2, Cu(ll)OH2, Cu(ll)(NO3)2, Cu(ll)SO4, CU(I I)(OAC)2, CU(I I)2CO3(OH)2, CU(II)(O2C5H7)2 (CU(II) acetylacetonate), Cu3(PO4)2, CU(SCN)2, and mixtures of two or more thereof, wherein the one or more salts of Cu preferably comprises, more preferably is, Cu(ll)(NO3)2.

[0154] 24. The process of any one of embodiments 1 to 23, wherein the catalyst comprises from 30 to 70 weight-%, preferably from 50 to 70 weight-%, more preferably from 60 to 70 weight- %, of Cu, calculated as CuO, based on the total weight of the catalyst.

[0155] 25. The process of any one of embodiments 1 to 24, wherein the catalyst further comprises Zn, wherein the catalyst preferably comprises from 20 to 30 weight-%, preferably from 23 to 29 weight-%, of Zn, calculated as ZnO, based on the total weight of the catalyst.

[0156] 26. The process of any one of embodiments 1 to 25, wherein the support material is selected from the group consisting of non-metal oxides, metal oxides, metal halides, carbon materials, and mixtures of two or more thereof, wherein the support material preferably is one or more of a non-metal oxide and a metal oxide.

[0157] 27. The process of any one of embodiments 1 to 26, wherein the support material comprises, preferably consists of, one or more of AhO3and SiO2, preferably AhO3.

[0158] 28. The process of embodiment 27, wherein the support material comprises AhO3, wherein the catalyst preferably comprises from 5 to 20 weight-%, preferably from 5 to 15 weight-%, more preferably from 7 to 13 weight-%, more preferably from 8 to 11 weight-%, of AhO3, based on the total weight of the catalyst. 29. The process of embodiment 27 or 28, wherein the support material comprises SiC>2, wherein the catalyst preferably comprises from 0.05 to 1 .50 weight-%, preferably from 0.2 to 1 .20 weight-%, more preferably from 0.3 to 0.8 weight-% of SiC>2, based on the total weight of the catalyst.

[0159] 30. The process of any one of embodiments 1 to 29, wherein the catalyst is in the form of a molding.

[0160] 31 . The process of any one of embodiments 1 to 30, wherein (i) comprises

[0161] (1.1 ) providing a support material;

[0162] (1.2) supporting Cu and optionally Zn on the support material, wherein supporting is preferably performed by impregnation, more preferably wet impregnation.

[0163] 32. The process of any one of embodiments 1 to 31 , further comprising

[0164] (iv) contacting the catalyst obtained in (iii) with a third gas stream comprising CO2 and H2, wherein the third gas stream comprises a CO2 to H2 molar ratio in the range of from 0.005:1 to 0.200:1 , preferably in the range of from 0.010:1 to 0.040:1 , more preferably in the range of from 0.020:1 to 0.030:1.

[0165] 33. The process of embodiment 32, wherein the third gas stream comprises from 0.5 to 15 volume-%, preferably from 1 .5 to 5.0 volume-%, more preferably from 1.8 to 2.2 volume- %, of CO2.

[0166] 34. The process of embodiment 32 or 33, wherein the third gas stream comprises from 0 to 5.0 volume-%, preferably from 0 to 0.01 volume-%, more preferably from 0 to 0.001 vol- ume-%, of CO.

[0167] 35. The process of any one of embodiments 32 to 34, wherein the third gas stream comprises from 50 to 95 volume-%, preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0168] 36. The process of any one of embodiments 32 to 35, wherein the third gas stream comprises an inert gas, wherein the third gas stream preferably comprises from 1 to 25 volume-%, preferably from 13 to 23 volume-%, more preferably from 16 to 20 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2.

[0169] 37. The process of any one of embodiments 32 to 36, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the third gas stream consists of H2, CO2, optionally an inert gas, and optionally CO. 38. The process of any one of embodiments 32 to 37, wherein the third gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0170] 39. The process of any one of embodiments 32 to 38, wherein the third gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0171] 40. The process of any one of embodiments 32 to 39, wherein the third gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0172] 41 . The process of any one of embodiments 32 to 40, wherein the third gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0173] 42. The process of any one of embodiments 1 to 41 , further comprising

[0174] (v) contacting the catalyst obtained in (iv) with a fourth gas stream comprising CO2 and H2, wherein the fourth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.020:1 to 0.080:1 , preferably in the range of from 0.040:1 to 0.060:1 , more preferably in the range of from 0.045:1 to 0.055:1.

[0175] 43. The process of embodiment 42, wherein the fourth gas stream comprises from 2.0 to 6.0 volume-%, preferably from 3.0 to 5.0 volume-%, more preferably from 3.5 to 4.5 volume- %, of CO2.

[0176] 44. The process of embodiment 42 or 43, wherein the fourth gas stream comprises from 0.5 to 1 .5 volume-%, preferably from 0.7 to 1 .3 volume-%, more preferably from 0.9 to 1 .1 vol- ume-%, of CO.

[0177] 45. The process of any one of embodiments 42 to 44, wherein the fourth gas stream comprises from 65 to 95 volume-%, preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0178] 46. The process of any one of embodiments 42 to 45, wherein the fourth gas stream comprises an inert gas, wherein the fourth gas stream preferably comprises from 9 to 21 vol- ume-%, preferably from 11 to 19 volume-%, more preferably from 13 to 17 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2. 47. The process of any one of embodiments 42 to 46, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the fourth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0179] 48. The process of any one of embodiments 42 to 47, wherein the fourth gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0180] 49. The process of any one of embodiments 42 to 48, wherein the fourth gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0181] 50. The process of any one of embodiments 42 to 49, wherein the fourth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,000 to 7,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0182] 51 . The process of any one of embodiments 42 to 50, wherein the fourth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0183] 52. The process of any one of embodiments 1 to 51 , further comprising

[0184] (vi) contacting the catalyst obtained in (v) with a fifth gas stream comprising CO2 and H2, wherein the fifth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.050:1 to 0.100:1 , preferably in the range of from 0.065:1 to 0.085:1 , more preferably in the range of from 0.070:1 to 0.080:1.

[0185] 53. The process of embodiment 52, wherein the fifth gas stream comprises from 4.0 to 8.0 volume-%, preferably from 5.0 to 7.0 volume-%, more preferably from 5.5 to 6.5 volume- %, of CO2.

[0186] 54. The process of embodiment 52 or 53, wherein the fifth gas stream comprises from 1 .0 to 3.0 volume-%, preferably from 1 .6 to 2.4 volume-%, more preferably from 1 .8 to 2.2 vol- ume-%, of CO.

[0187] 55. The process of any one of embodiments 52 to 54, wherein the fifth gas stream comprises from 65 to 95 volume-%, preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0188] 56. The process of any one of embodiments 52 to 55, wherein the fifth gas stream comprises an inert gas, wherein the fifth gas stream preferably comprises from 5 to 19 volume-%, preferably from 8 to 16 volume-%, more preferably from 10 to 14 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2.

[0189] 57. The process of any one of embodiments 52 to 56, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the fifth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0190] 58. The process of any one of embodiments 52 to 57, wherein the fifth gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0191] 59. The process of any one of embodiments 52 to 58, wherein the fifth gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0192] 60. The process of any one of embodiments 52 to 59, wherein the fifth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,000 to 7,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0193] 61 . The process of any one of embodiments 52 to 60, wherein the fifth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1 .5 to 2.5 h.

[0194] 62. The process of any one of embodiments 1 to 61 , further comprising

[0195] (vii) contacting the catalyst obtained in (vi) with a sixth gas stream comprising CO2 and H2, wherein the sixth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.100:1 to 0.150:1 , preferably in the range of from 0.110:1 to 0.140:1 , more preferably in the range of from 0.120:1 to 0.130:1.

[0196] 63. The process of embodiment 62, wherein the sixth gas stream comprises from 5 to 15 vol- ume-%, preferably from 7 to 13 volume-%, more preferably from 9 to 11 volume-%, of CO2.

[0197] 64. The process of embodiment 62 or 63, wherein the sixth gas stream comprises from 1.0 to 5.0 volume-%, preferably from 2.0 to 4.0 volume-%, more preferably from 2.5 to 3.5 vol- ume-%, of CO. 65. The process of any one of embodiments 62 to 64, wherein the sixth gas stream comprises from 65 to 95 volume-%, preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0198] 66. The process of any one of embodiments 62 to 65, wherein the sixth gas stream comprises an inert gas, wherein the sixth gas stream preferably comprises from 3 to 11 volume-%, preferably from 5 to 9 volume-%, more preferably from 6 to 8 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2.

[0199] 67. The process of any one of embodiments 62 to 66, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the sixth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0200] 68. The process of any one of embodiments 62 to 67, wherein the sixth gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0201] 69. The process of any one of embodiments 62 to 68, wherein the sixth gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0202] 70. The process of any one of embodiments 62 to 69, wherein the sixth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0203] 71 . The process of any one of embodiments 62 to 70, wherein the sixth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1 .0 to 3.0 h, more preferably in the range of from 1 .5 to 2.5 h.

[0204] 72. The process of any one of embodiments 1 to 71 , further comprising

[0205] (viii) contacting the catalyst obtained in (vii) with a seventh gas stream comprising CO2 and H2, wherein the seventh gas stream comprises a CO2 to H2 molar ratio in the range of from 0.135:1 to 0.200:1 , preferably in the range of from 0.150:1 to 0.185:1 , more preferably in the range of from 0.160:1 to 0.175:1.

[0206] 73. The process of embodiment 72, wherein the seventh gas stream comprises from 9.5 to 17.5 volume-%, preferably from 11.5 to 15.5 volume-%, more preferably from 12.5 to 14.5 volume-%, of CO2. 74. The process of embodiment 72 or 73, wherein the seventh gas stream comprises from 1 .5 to 5.0 volume-%, preferably from 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 vol- ume-%, of CO.

[0207] 75. The process of any one of embodiments 72 to 74, wherein the seventh gas stream comprises from 65 to 95 volume-%, preferably from 70 to 90 volume-%, more preferably from 75 to 85 volume-%, of H2.

[0208] 76. The process of any one of embodiments 72 to 75, wherein the seventh gas stream comprises an inert gas, wherein the seventh gas stream preferably comprises from 1 to 5 vol- ume-%, preferably from 2 to 4 volume-%, more preferably from 2.5 to 3.5 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably N2.

[0209] 77. The process of any one of embodiments 72 to 76, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the seventh gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0210] 78. The process of any one of embodiments 72 to 77, wherein the seventh gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0211] 79. The process of any one of embodiments 72 to 78, wherein the seventh gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0212] 80. The process of any one of embodiments 72 to 79, wherein the seventh gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0213] 81 . The process of any one of embodiments 72 to 80, wherein the seventh gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1.0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0214] 82. The process of any one of embodiments 1 to 81 , further comprising

[0215] (ix) contacting the catalyst obtained in (viii) with a eighth gas stream comprising CO2 and H2, wherein the eighth gas stream comprises a CO2 to H2 molar ratio in the range of from 0.150:1 to 0.200:1 , preferably in the range of from 0.160:1 to 0.190:1 , more preferably in the range of from 0.170:1 to 0.180:1. 83. The process of embodiment 82, wherein the eighth gas stream comprises from 9.5 to 17.5 volume-%, preferably from 11.5 to 15.5 volume-%, more preferably from 12.5 to 14.5 vol- ume-%, of CO2.

[0216] 84. The process of embodiment 82 or 83, wherein the eighth gas stream comprises from 1 .5 to 5.0 volume-%, preferably from 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 vol- ume-%, of CO.

[0217] 85. The process of any one of embodiments 82 to 84, wherein the eighth gas stream comprises from 60 to 90 volume-%, preferably from 65 to 85 volume-%, more preferably from 70 to 80 volume-%, of H2.

[0218] 86. The process of any one of embodiments 82 to 85, wherein the eighth gas stream comprises an inert gas, wherein the eighth gas stream preferably comprises from 4.0 to 9.0 volume-%, preferably from 5.0 to 8.0 volume-%, more preferably from 6.0 to 7.0 volume- %, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably Ar.

[0219] 87. The process of any one of embodiments 82 to 86, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the eighth gas stream consists of H2, CO2, optionally an inert gas, and optionally CO.

[0220] 88. The process of any one of embodiments 82 to 87, wherein the eighth gas stream has a temperature in the range of from 170 to 290 °C, preferably in the range of from 200 to 260 °C, more preferably in the range of from 220 to 240 °C.

[0221] 89. The process of any one of embodiments 82 to 88, wherein the eighth gas stream has a pressure in the range of from 5 to 75 barg, preferably in the range of from 30 to 50 barg, more preferably in the range of from 35 to 45 barg.

[0222] 90. The process of any one of embodiments 82 to 89, wherein the eighth gas stream has a gas hourly space velocity in the range of from 500 to 20,000 IT1, preferably in the range of from 500 to 17,000 IT1, more preferably in the range of from 1 ,000 to 14,000 IT1, more preferably in the range of from 2,000 to 11 ,000 IT1, more preferably in the range of from 3,000 to 9,000 IT1, more preferably in the range of from 5,500 to 6,500 IT1.

[0223] 91 . The process of any one of embodiments 82 to 90, wherein the eighth gas stream is contacted with the catalyst for a period of time in the range of from 0.5 to 5.0 h, preferably in the range of from 1.0 to 3.0 h, more preferably in the range of from 1.5 to 2.5 h.

[0224] 92. An activated catalyst obtainable or obtained by the process according to any one of embodiments 1 to 91 . 93. A process for preparing methanol, the process comprising

[0225] (A) preparing an activated catalyst, wherein the activated catalyst is prepared according to the process of any one of embodiments 1 to 91 ;

[0226] (B) contacting the activated catalyst prepared in (A) with a feed gas stream comprising CO2 and H2, wherein the feed gas stream comprises a CO2 to H2 molar ratio in the range of from 0.100:1 to 0.250:1 , preferably in the range of from 0.130:1 to 0.220:1 , more preferably in the range of from 0.150:1 to 0.200:1 , more preferably in the range of from 0.160:1 to 0.190:1 , more preferably in the range of from 0.170:1 to 0.180:1 , obtaining a product gas stream comprising CH3OH.

[0227] 94. The process of embodiment 93, wherein the feed gas stream according to (B) comprises from 9.5 to 21 volume-%, preferably from 10.5 to 17.5 volume-%, more preferably from

[0228] 11.5 to 15.5 volume-%, more preferably from 12.5 to 14.5 volume-%, of CO2.

[0229] 95. The process of embodiment 93 or 94, wherein the feed gas stream according to (B) comprises from 0.5 to 8.0 volume-%, preferably from 1 .5 to 5.0 volume-%, more preferably from 2.5 to 4.5 volume-%, more preferably from 3.0 to 4.0 volume-%, of CO.

[0230] 96. The process of any one of embodiments 93 to 95, wherein the feed gas stream according to (B) comprises from 60 to 93 volume-%, preferably from 63 to 90 volume-%, more preferably from 65 to 85 volume-%, more preferably from 70 to 80 volume-%, of H2.

[0231] 97. The process of any one of embodiments 93 to 96, wherein the feed gas stream according to (B) comprises an inert gas, wherein the feed gas stream according to (B) preferably comprises from 0.001 to 10.0 volume-%, preferably from 0.01 to 9.5 volume-%, more preferably from 0.1 to 9.0 volume-%, more preferably from 0.5 to 8.5 volume-%, more preferably from 1 .0 to 8.5 volume-%, more preferably from 2.0 to 8.0 volume-%, more preferably from 5.0 to 8.0 volume-%, more preferably from 6.0 to 7.0 volume-%, of the inert gas, wherein the inert gas comprises, preferably consists of, one or more of Ar and N2, preferably Ar.

[0232] 98. The process of any one of embodiments 93 to 97, wherein from 90 to 100 volume-%, preferably from 95 to 100 volume-%, more preferably from 99 to 100 volume-%, of the feed gas stream according to (B) consists of H2, CO2, optionally an inert gas, and optionally CO.

[0233] 99. The process of any one of embodiments 93 to 98, wherein the feed gas stream according to (B) has a temperature in the range of from 180 to 310 °C, preferably in the range of from 200 to 300 °C, more preferably in the range of from 210 to 270 °C, more preferably in the range of from 230 to 250 °C. 100. The process of any one of embodiments 93 to 99, wherein the feed gas stream according to (B) has a pressure in the range of from 30 to 110 barg, preferably in the range of from 54 to 88 barg, more preferably in the range of from 64 to 85 barg.

[0234] 101 . The process of any one of embodiments 93 to 100, wherein the feed gas stream according to (B) has a gas hourly space velocity in the range of from 500 to 45,000 IT1, preferably in the range of from 2,500 to 20,000 IT1, more preferably in the range of from 4,500 to 9,500 IT1, more preferably in the range of from 6,500 to 7,500 IT1.

[0235] 102. The process of any one of embodiments 93 to 101 , wherein the feed gas stream according to (B) is contacted with the catalyst for a period of time in the range of from 10 h to 6 years, preferably of from 100 h to 5.5 years, more preferably of from 30 d to 5.5 years, more preferably of from 120 d to 5.5 years, more preferably of from 1 to 5 years, more preferably of from 3 to 5 years, more preferably of from 3.5 to 4.5 years.

[0236] 103. The process of any one of embodiments 93 to 102, wherein the activated catalyst is comprised in a fixed-bed, wherein the activated catalyst is comprised in a reactor comprising the fixed-bed.

[0237] The abbreviation “barg” indicates a gauge pressure.

[0238] The present invention is further illustrated by the following examples and comparative examples.

[0239] EXPERIMENTAL SECTION

[0240] Reference Example 1 : Preparation of a catalyst and activation of the catalyst

[0241] A common Cu / Zn / AI-containing catalyst was used. The catalyst contains the elements in the oxdic state in the ratio of 63 weight-% CuO, 26 weight-% ZnO and 11 weight-% AI2O3.

[0242] The catalysts were molded to full shaped tablets.

[0243] The catalyst was activated in the reactor under a reducing atmosphere consisting of H2 and inert gas, here N2. Generally, it is known that activation can be carried out starting at a temperature below 200 °C under an atmosphere comprising 2 to 5 volume-% of H2. Presently, the temperature was set to 200 °C. Then, the hydrogen concentration was stepwise increased until a content of 80 volume-% H2 in N2 was reached. The activation was performed at a pressure below 10 barg and a gas hourly space velocity (GHSV) below 1 ,000 IT1. The resulting activated catalyst comprised Cu in metallic form, whereas Zn and Al were present mainly in their oxidic forms. Example 2: Catalytic testing

[0244] The activated catalyst prepared according to Reference Example 1 was used for each test.

[0245] The catalytic tests were conducted in a tubular reactor with 25 mm inner diameter and a length of 2 m. The temperature was controlled with an oil bath. The catalytic performance was monitored via online gas chromatography (GC). a) Stepwise increase of CO2 content in gas stream

[0246] The activated catalyst prepared according to Reference Example 1 was used.

[0247] After activation of the catalyst, the temperature was increased to 230 °C, the pressure was increased to 40 barg and the gas hourly space velocity (GHSV) to 6000 IT1. The gas mixture still consisted of 80 volume-% H2 in N2. N2 was stepwise substituted by CO2 and CO as follows. After dosing 1 volume-% of CO2 the conditions were kept constant for 2 h. After the dwell time, the CO2 content was increased to 2 volume-% of CO2, then 4 volume-% of CO2, then 6 volume-% of CO2, then 10 volume-% of CO2 and finally to 13.5 volume-% of CO2. After each content increase the conditions were kept constant for a dwell time of 2 h. At content increases of 4, 6 and 10 volume-% CO2, the CO content was increased stepwise to 1 volume-%, then to 2 vol- ume-%, and finally to 3.5 volume-%. Finally, the rest of N2 (3 volume-%) and 3.5 volume-% of H2 were substituted by Ar to give a content of 6.5 volume-% Ar.

[0248] After setting the conditions to a temperature of 230 °C, a pressure of 40 barg, a GHSV of 6000 h’1and a feed gas stream composition of 13.5 volume-% CO2, 3.5 volume-% CO, 76.5 vol- ume-% H2 and 6.5 volume-% Ar, the temperature was increased to 240 °C, the GHSV changed to 6950 h’1and the pressure was raised to 69 barg. The latter conditions were kept constant for several hundred hours time-on stream.

[0249] Table 1

[0250] Settings for stepwise increase of CO2 content in feed gas stream. b) Directly feeding CC>2-containing gas stream into the reactor

[0251] The activated catalyst prepared according to Reference Example 1 was used.

[0252] After activation of the catalyst, the temperature was increased to 230 °C, the pressure was increased to 40 barg and the GHSV to 6000 IT1. The gas mixture still consisted of 80 volume-% H2 in N2. N2 was substituted within 30 minutes by 13.5 volume-% of CO2 and 3.5 volume-% of CO. Finally, the rest of N2 (3 volume-%) and 3.5 volume-% of H2 were substituted by Ar to give a content of 6.5 volume-% Ar.

[0253] After setting the conditions to a temperature of 230 °C, a pressure of 40 barg, a GHSV of 6000 h’1and a feed gas stream composition of 13.5 volume-% CO2, 3.5 volume-% CO, 76.5 vol- ume-% H2 and 6.5 volume-% Ar, the temperature was increased to 240 °C, the GHSV changed to 6590 h’1and the pressure was raised to 69 barg. The latter conditions were kept constant for several hundred hours time-on stream.

[0254] Table 2

[0255] Settings for feeding CO2 directly into the reactor. c) Firstly feeding syngas into the reactor and secondly CO2-containing gas stream

[0256] The activated catalyst prepared according to Reference Example 1 was used.

[0257] After activation of the catalyst, the temperature was kept at 200 °C, the pressure was increased to 40 barg and the GHSV to 6000 IT1. The gas mixture still consisted of 80 volume-% H2 in N2. N2 was substituted within 30 minutes by 7.5 volume-% of CO2 and 12 volume-% of CO. Finally, the rest of N2 (0.5 volume-%) and 7.5 volume-% of H2 were substituted by Ar to give a content of 8 volume-% Ar. Then, the temperature was increased to 240 °C, the pressure was increased to 69 barg, the GHSV was set to 9000 IT1, and the process was conducted for 400 h time-on- stream (TOS).

[0258] After 400 h TOS, the conditions were switched to a feed gas stream composition of 13.5 vol- ume-% CO2, 3.5 volume-% CO, 76.5 volume-% H2 and 6.5 volume-% Ar, the temperature was kept at 240 °C and the GHSV was changed to 6590 IT1.

[0259] Table 3

[0260] Settings for directly feeding syngas into the reactor and later the CO2. d) Results

[0261] The three different ways of bringing the activated catalyst under operation, as detailed under items a), b) and c) above, allowed to investigate the impact of different gas atmospheres and the impact of the dosing velocity of the CO2-enriched feed on the catalysts and their final performance.

[0262] Table 4 shows the relative weight-time-yield (WTY) values as average values of 200 h TOS. Therein, the GHSV is shown to monitor the comparability of the measurement. A feed gas stream comprising 13.5 volume-% CO2, 3.5 volume-% CO, 76.5 volume-% H2 and 6.5 volume- % Ar was applied. The pressure was fixed at 69 barg.

[0263] Table 4

[0264] Results from catalytic testing. As it can be gathered from the results shown in table 4 a higher activity of the slowly activated catalyst (see example a)) can be achieved in comparison to the quickly added feeds (see examples b) and c)). In addition, Figure 1 shows the faster deactivation of the catalysts according to b) and c). Thus, it was found that introducing CO2 comparatively slowly leads to a more active catalyst which performs more stable in the preparation of methanol already within the first hours of time-on-stream.

[0265] DESCRIPTION OF FIGURES

[0266] Figure 1 : shows the CH3OH outlet concentration in volume-% as function of time for Examples 2. a), 2.b) and 2.c), respectively. The time-on stream is noted on the abscissa in arbitrary units and the CH3OH concentration of the reactor outlet is noted on the ordinate in volume-%.

[0267] CITED LITERATURE

[0268] - WO 2020 / 212681 A1

[0269] - CN 101386564 B

[0270] - DE 10 2017 001 520 A1

[0271] - WO 2023 / 088893 A1

Claims

Claims1 . A process for preparing an activated catalyst, the process comprising(i) preparing a catalyst comprising one or more salts of Cu, one or more oxides of Cu, or one or more salts and one or more oxides of Cu supported on a support material;(ii) contacting the catalyst prepared in (i) with a first gas stream comprising H2, optionally comprising an inert gas, and optionally further comprising CO2, wherein the first gas stream comprises a CO2 to H2 molar ratio in the range of from 0:1 to 0.001 :1 ;(iii) contacting the catalyst obtained in (ii) with a second gas stream comprising CO2 and H2, wherein the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.001 :1 to 0.075:1 , obtaining an activated catalyst.

2. The process of claim 1 , wherein the first gas stream comprises from 0 to 0.1 volume-% of CO2.

3. The process of claim 1 or 2, wherein the first gas stream comprises from 1 to 99 volume- % of H2.

4. The process of any one of claims 1 to 3, wherein the first gas stream has a temperature in the range of from 145 to 290 °C.

5. The process of any one of claims 1 to 4, wherein the second gas stream comprises a CO2 to H2 molar ratio in the range of from 0.002:1 to 0.067:1.

6. The process of any one of claims 1 to 5, wherein the second gas stream comprises from 0.1 to 7 volume-% of CO2.

7. The process of any one of claims 1 to 6, wherein the second gas stream comprises from 1 to 99 volume-% of H2.

8. The process of any one of claims 1 to 7, wherein the second gas stream has a temperature in the range of from 170 to 290 °C.

9. The process of any one of claims 1 to 8, wherein the catalyst comprises from 30 to 70 weight-% of Cu, calculated as CuO, based on the total weight of the catalyst.

10. The process of any one of claims 1 to 9, wherein the catalyst further comprises Zn.11 . The process of any one of claims 1 to 10, wherein the support material comprises one or more of AI2O3 and SiC>2.

12. The process of any one of claims 1 to 11 , wherein (i) comprises(1.1 ) providing a support material;(1.2) supporting Cu and optionally Zn on the support material.

13. The process of any one of claims 1 to 12, further comprising(iv) contacting the catalyst obtained in (iii) with a third gas stream comprising CO2 and H2, wherein the third gas stream comprises a CO2 to H2 molar ratio in the range of from 0.005:1 to 0.200:1.

14. An activated catalyst obtainable or obtained by the process according to any one of claims 1 to 13.

15. A process for preparing methanol, the process comprising(A) preparing an activated catalyst, wherein the activated catalyst is prepared according to the process of any one of claims 1 to 13;(B) contacting the activated catalyst prepared in (A) with a feed gas stream comprising CO2 and H2, wherein the feed gas stream comprises a CO2 to H2 molar ratio in the range of from 0.100:1 to 0.250:1 , obtaining a product gas stream comprising CH3OH.

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