TECHNICAL FIELD

The present invention relates to a process for the preparation of a supported metal oxide comprising one or more metal oxides supported on a particulate support material, and a supported metal oxide obtainable and/or obtained by said process. Further, the present invention relates to a supported metal oxide as such, use thereof, as well as methods for reforming one or more hydrocarbons, preferably for reforming methane, in the presence of CO2, and for the production of 1 ,4-butynediol, wherein said supported metal oxide is used.

BACKGROUND TECHNOLOGY

Flame spray pyrolysis has been an established method for the manufacture of commodities like carbon black, pigments, silica or alumina. A flame based method has also been developed for the production of catalytic materials. This method aims at the preparation of metal oxides on the nanoscale level by exposing the metals to a pyrolysis zone that is generated by a flame. The metals are preferably provided as organic metal compounds or salts or complexes of metals with an organic acid, alcohol or chelating agent. The liquid precursor is sprayed into the flame and the heat of combustion of the organic compounds contributes to the energy required to maintain the high temperatures in the pyrolysis zone. Particles are formed by nucleation from the gas phase. Characteristic features of this process are short residence times (few milliseconds) and high temperatures. In this regard, WO 2004/005184 A1 discloses the production of metal oxides by spray pyrolysis of a solution containing the precursor compounds.

Narowski et al. in Polish Journal of Chemistry, 77(1), 105 (2003) describe the impact on the activity of a CO and CO2 methanation catalyst by applying flash calcination to an NiO/AhOs compared to fluid-bed calcination.

Katarzyna et al. in Applied catalysis A, 426-424, 114-120 (2012) used a flash calcined alumina support as carrier for K-promoted Co-Mo-comprising catalysts for the water gas shift process.

Patkowski et al. in European Journal of Inorganic Chemistry, 15, 1518-1529 (2021) describe the impact of using flash calcination compared to conventional calcination methods on the properties of resulting cerium and barium promoted cobalt catalysts for the ammonia synthesis starting from hydroxycarbonate precursors. The precursors were dosed into the flash calciner in finegrained solid form. Catalysts synthesized according to the flash calcination route showed advantages with regard to structural properties, e.g. a higher BET surface area, and with regard to catalytic activity in the ammonia formation reaction. Kowalik et al. in European Journal of Inorganic Chemistry, 2019(13), 1792-1798 present a flash reactor for the calcination of a spray-dried CuZnAI catalyst used for low temperature water gas shift reaction. It was found that the conditions in the flash reactor are favorable for the production of better physicochemical properties and high catalytic activities compared to conventional calcination technologies. WO 2017/167622 A1 , on the other hand, concerns a process for the flash calcination of a zeolitic material.

WO 2013/068905 A1 concerns a process for producing a reforming catalyst, wherein the synthesis procedure involves a common calcination step. Similarly, US 9,006,129 B2 relates to a process for producing a catalyst for the ethynylation of formaldehyde to butyndiol, wherein the synthesis procedure also involves a common calcination step.

EP 3 323 510 A1 relates to a process for the preparation of a mixed oxide catalyst by flame pyrolysis, wherein the mixture subject to flame-pyrolysis may also contain a precursor of a carrier material.

Despite the progress achieved in the field of spray-pyrolysis and flash-calcination, there remains the need for a process for the preparation of a supported metal oxide comprising one or more metal oxides supported on a particulate support material, wherein the process comprises a comparatively reduced number of process steps. Further, there was a need for providing a supported metal oxide having improved chemical and physical properties, in particular when employed as a catalyst or catalyst support.

DETAILED DESCRIPTION

It was the object of the present invention to provide an improved process for the preparation of a supported metal oxide, wherein in particular the process comprises a comparatively reduced number of process steps. Further, it was an object to provide a supported metal oxide having improved mechanical properties, particularly concerning side crushing strength, abrasion resistance, bulk density, adsorption properties, filterability, and/or porosity. Thus, it has surprisingly been found that a novel process for the preparation of a supported metal oxide can be provided particularly comprising a comparatively reduced number of process steps, and wherein in particular a solid particulate support material may be directly used as starting material. Further, it has surprisingly been found that the process can be carried out in a continuous manner. Therefore, it has surprisingly been found that production costs can be reduced due the reduced process complexity. Furthermore, it has surprisingly been found that the supported metal oxides of the present invention show an improved catalytic activity.

Therefore, the present invention relates to a process for the preparation of a supported metal oxide comprising one or more metal oxides supported on a particulate support material, said process comprising (i) preparing a suspension comprising a liquid solvent system and one or more solid particulate support materials, wherein the liquid solvent system comprises one or more metal oxide precursor compounds, wherein the one or more metal oxide precursor compounds are dissolved in the liquid solvent system;

(ii) atomization of the suspension obtained in (i) in a gas stream for obtaining an aerosol;

(iii) drying or calcination of the aerosol obtained in (ii) for obtaining a powder of a supported metal oxide.

It is preferred that the one or more solid particulate support materials are selected from the group consisting of oxidic compounds and mixtures of two or more thereof, more preferably from the group consisting of oxides, hydroxides, carbonates, and mixtures of two or more thereof, more preferably from the group consisting of oxides, hydroxides, and carbonates of metals and/or metalloids of groups II, III, IV, XIII, XIV, lanthanides, and mixtures of two or more thereof, wherein the metals and/or metalloids are preferably selected from the group consisting of Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, B, Al, Ga, In, Si, Ge, Sn, Pb, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ca, Ba, Y, La, Ce, Pr, Nd, Sm, Ti, Zr, B, Al, Ga, Si, Ge, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ca, Ce, Pr, Nd, Ti, Zr, Al, Ga, Si, Ge, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ce, Zr, Al, Si, and mixtures of two or more thereof, and more preferably from the group consisting of Mg, Al, Si, and mixtures of two or more thereof.

It is preferred that the metal of the one or more metal oxide precursor compounds is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof.

According to a first alternative, it is preferred that the metal of the one or more metal oxide precursor compounds comprises Cu and/or Bi, more preferably Cu and Bi, wherein more preferably the metal of the one or more metal oxide precursor compounds consists of Cu and/or Bi, preferably of Cu and Bi.

In the case where the metal of the one or more metal oxide precursor compounds comprises Cu and/or Bi, it is preferred that the one or more solid particulate support materials comprise aluminium magnesium hydroxy carbonate, more preferably aluminium magnesium hydroxy carbonate and boehmite, wherein more preferably the one or more solid particulate support materials in (i) is aluminium magnesium hydroxy carbonate or a mixture of aluminium magnesium hydroxy carbonate and boehmite. In the case where the one or more solid particulate support materials comprise aluminium magnesium hydroxy carbonate, it is preferred that the aluminium magnesium hydroxy carbonate displays an AI2O3 : MgO weight ratio in the range of from 60:40 to 80:20, more preferably in the range of from 65:35 to 75:25, more preferably in the range of from to 68:32 to 72:28.

According to a second alternative, it is preferred that the metal of the one or more metal oxide precursor compounds comprises Ni, wherein more preferably the metal of the one or more metal oxide precursor compounds consists of Ni.

In the case where the metal of the one or more metal oxide precursor compounds comprises Ni, it is preferred that the one or more solid particulate support materials comprise one or more silicates of magnesium, more preferably magnesium silicate, more preferably talc, and more preferably Mg3Si4Ow(OH)2, wherein more preferably the one or more solid particulate support materials in (i) consists of one or more silicates of magnesium, preferably of magnesium silicate, more preferably of talc, and more preferably of Mg3Si4Ow(OH)2.

It is preferred that the suspension prepared in (i) displays a pH in the range of from 1 to 6, more preferably in the range of from 2 to 5, more preferably in the range of from 2 to 4.

It is preferred that the suspension prepared in (i) displays a solid content in the range of from 1 to 42 volume-%, more preferably in the range of from 10 to 37 volume-%, more preferably in the range of from 17 to 33 volume-%, more preferably in the range of from 22 to 28 volume-%, more preferably in the range of from 24 to 26 volume-%, based on 100 volume-% of the suspension prepared in (i).

It is preferred that the suspension prepared in (i) displays a solid content in the range of from 5 to 50 weight-%, more preferably in the range of from 10 to 40 weight-%, more preferably in the range of from 15 to 30 weight-%, based on 100 weight-% of the suspension prepared in (i).

It is preferred that preparing the suspension in (i) comprises

(i.a) preparing a solution of one or more metal oxide precursor compounds in a liquid solvent system for obtaining a solution;

(i.b) adjusting the pH of the solution obtained in (i.a) to a value in the range of from 0 to 4, more preferably in the range of from 0 to 3, more preferably in the range of from 0 to 2, more preferably in the range of from 0 to 1 ;

(i.c) suspending one or more solid particulate support materials in a liquid solvent system for obtaining a suspension;

(i.d) adding the solution obtained in (i.b) to the suspension obtained in (i.c) for obtaining a suspension.

It is preferred that independently from one another, the liquid solvent system in (i), (i.a), and/or (i.c) comprises water and/or one or more organic solvents, and more preferably comprises one or more solvents selected from the group consisting of water, monohydric alcohols, polyhydric alcohols, and combinations of two or more thereof, more preferably selected from the group consisting of water, methanol, ethanol, propanol, butanol, pentanol, ethane-1 ,2-diol, propane- 1 ,2-diol, propane-1 , 2, 3-triol, butane-1 ,2,3,4-tetraol, pentane-1 ,2,3,4, 5-pentol, and combinations of two or more thereof, more preferably from the group consisting of water, methanol, ethanol, 2-propanol, and mixtures of two or more thereof, wherein more preferably the liquid solvent system comprises water, preferably deionized water, wherein more preferably the liquid solvent system in (i), (i.a), and/or (i.c) consists of deionized water.

It is preferred that independently from one another, the concentration of the one or more metal oxide precursor compounds in the liquid solvent system of the suspension obtained in (i) or (i.d), and/or in the solution obtained in (i.a), is in the range of from 1 to 5 mol/L, more preferably in the range of from 1 to 4 mol/L, more preferably in the range of from 1 to 3 mol/L, more preferably in the range of from 1 to 2 mol/L.

It is preferred that independently from one another, the one or more solid particulate support materials contained in the suspension obtained in (i), (i.c), and/or (i.d) display an average particle size D50 in the range of from 0.5 to 500 pm, more preferably of from 1 to 300 pm, preferably of from 5 to 200 pm, more preferably of from 10 to 100 pm, more preferably of from 15 to 80 pm, more preferably of from 20 to 60 pm, more preferably of from 25 to 40 pm, and more preferably of from 30 to 35 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

It is preferred that the one or more metal oxide precursor compounds are selected from the group consisting of metals salts and mixtures thereof, wherein the metal salts are more preferably selected from the group consisting of metal halides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphites, cyanides, and mixtures of two or more thereof, preferably from the group consisting fluorides, chlorides, bromides, nitrates, sulfates, hydrogensulfates, dihydrogensulfates, cyanides, and mixtures of two or more thereof, more preferably from the group consisting of chloride, bromide, nitrate, and mixtures of two or more thereof, wherein more preferably the one or more metal oxide precursor compounds comprises the chloride and/or nitrate salt of the one or more metals, preferably the nitrate salt of the one or more metals, wherein more preferably the one or more metal oxide precursor compounds consist of the chloride and/or nitrate salt of the one or more metals, preferably of the nitrate salt of the one or more metals.

It is preferred that the average particle size D50 of the droplets in the aerosol obtained in (ii) is in the range of from 10 to 250 pm, more preferably in the range of from 10 to 200 pm, more preferably in the range of from 10 to 150 pm, more preferably in the range of from 10 to 100 pm, more preferably in the range of from 10 to 50 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

It is preferred that the average particle size D50 of the powder particles obtained in (iii) is in the range of from 1 to 250 pm, more preferably in the range of from 2.5 to 100 pm, more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

It is preferred that atomization of the suspension of the zeolitic material in (ii) is conducted with a spray nozzle.

It is preferred that atomization of the suspension of the zeolitic material in (ii) is conducted by introducing the suspension into a gas stream, preferably with a peristaltic pump.

It is preferred that the gas stream comprises one or more of the gases selected from the group consisting of oxygen, nitrogen, carbon dioxide, carbon monoxide, helium, neon, argon, steam, air, and combinations of two or more thereof, more preferably from the group consisting of oxygen, nitrogen, carbon dioxide, argon, steam, air, and combinations of two or more thereof.

It is preferred that drying the aerosol according to (iii) comprises heating the aerosol obtained in (ii) to a temperature in the range of from 60 to 250 °C, more preferably of from 90 to 190 °C, more preferably of from 100 to 140 °C, more preferably of from 110 to 130 °C.

In the case where drying the aerosol according to (iii) comprises heating the aerosol obtained in (ii) to a temperature in the range of from 60 to 250 °C, it is preferred that the duration of drying the aerosol according to (iii) is in the range of from 1 to 48 h, more preferably of from 6 to 20 h, more preferably of from 10 to 14 h.

Further in the case where drying the aerosol according to (iii) comprises heating the aerosol obtained in (ii) to a temperature in the range of from 60 to 250 °C, it is preferred that drying the aerosol according to (iii) is conducted in a gas atmosphere comprising one or more of oxygen, and nitrogen, more preferably air.

It is preferred that the temperature of the calcination in (iii) is in the range of from 200 to 1 ,300 °C, more preferably of from 250 to 1 ,250 °C, more preferably of from 250 to 1 ,200 °C.

According to a first alternative, it is preferred that the temperature of the calcination in (iii) is in the range of from 300 to 1 ,000 °C, more preferably of from 350 to 850 °C, more preferably of from 400 to 750 °C, more preferably of from 450 to 700 °C, more preferably from 500 to 650 °C, and more preferably of from 550 to 600 °C.

According to a second alternative, it is preferred that the temperature of the calcination in (iii) is in the range of from 275 to 900 °C, more preferably of from 300 to 600 °C, more preferably of from 325 to 500 °C, more preferably of from 350 to 450 °C. According to a third alternative, it is preferred that the temperature of the calcination in (iii) is in the range of from 600 to 1 ,200 °C, more preferably of from 850 to 1 , 150 °C, more preferably of from 950 to 1 , 100 °C, more preferably of from 1 ,025 to 1 ,075 °C.

It is preferred that the duration of the calcination in (iii) is in the range of from 5 ms to 30 s, more preferably of from 20 ms to 15 s, more preferably of from 50 ms to 10 s, more preferably of from 80 ms to 5 s, more preferably of from 0.1 to 2 s, more preferably of from 0.3 to 1 s, and more preferably of from 0.5 to 0.8 s.

It is preferred that calcination in (iii) is at least in part or entirely conducted in an oxygen containing atmosphere, wherein the oxygen content of the atmosphere in vol.-% based on the total volume of the gases therein is more preferably in the range of from 1 to 100 vol.-%, more preferably from 3 to 80 vol.-%, more preferably from 5 to 50 vol.-%, more preferably from 8 to 35 vol.-%, more preferably from 10 to 25 vol.-%, more preferably from 12 to 22 vol.-%, and more preferably from 14 to 16 vol.-%.

It is preferred that calcination in (iii) is at least in part or entirely conducted in an inert gas atmosphere, wherein the inert gas atmosphere more preferably comprises nitrogen and/or one or more noble gases, wherein more preferably the inert gas atmosphere comprises one or more gases selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, and mixtures of two or more thereof, more preferably from the group consisting of nitrogen, helium, argon, and mixtures of two or more thereof, more preferably from the group consisting of nitrogen, argon, and mixtures thereof, wherein more preferably the inert gas atmosphere comprises nitrogen, and wherein more preferably the inert gas atmosphere consists of nitrogen.

It is preferred that calcination in (iii) is achieved by contacting the aerosol with a hot gas stream, wherein more preferably the hot gas stream is generated by heating a gas stream with a heating element, wherein the heating element is preferably a flame and/or an electrically heating element, more preferably a flame.

It is preferred that the process is not repeated but done in a single pass.

It is preferred that the process further comprises

(iv) optionally mixing the supported metal oxide obtained from (iii) with one or more additives, for obtaining a mixture;

(v) subjecting the supported metal oxide obtained from (iii) or the mixture obtained in (iv) to a shaping process, wherein the shaping preferably comprises tableting or extruding, for obtaining a molding comprising the supported metal oxide.

In the case where the process further comprises optionally (iv) and (v), it is preferred that the one or more additives are selected from the group consisting of graphite, polymeric vinyl compounds, polyalkylene oxides, polyacrylates, polymethacrylates, polyolefins, polyamides, polyes- ters, polystyrenes, polysaccharides, alumina, silica, titania, zirconia, and mixtures of two or more thereof.

It is preferred that the process further comprises

(vi) subjecting the supported metal oxide obtained in (iii), the mixture obtained in (iv), or the molding obtained in (v) to a heat treatment in a gas atmosphere having a temperature in the range of from 300 to 1 ,200 °C, preferably in the range of from 800 to 1 ,150 °C, more preferably in the range of from 1 ,000 to 1 ,100 °C, wherein the gas atmosphere comprises one or more of oxygen, nitrogen, air, and steam.

Further, the present invention relates to a supported metal oxide comprising one or more metal oxides supported on a solid particulate support material, wherein said supported metal oxide is obtainable and/or obtained according to the process of any one of the embodiments disclosed herein.

It is preferred that the average particle size D50 of the supported metal oxide is in the range of from 1 to 250 pm, more preferably in the range of from 2.5 to 100 pm, more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

It is preferred that the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof.

In the case where the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, it is preferred according to a first alternative that the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi, wherein more preferably the supported metal oxide consists of one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi.

In the case where the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, it is preferred that the supported metal oxide comprises CuO and/or Bi2O3, more preferably of CuO and Bi20s, wherein more preferably the supported metal oxide consists of CuO and/or Bi20s, preferably of CuO and Bi20s. In the case where the supported metal oxide comprises CuO and/or Bi20s, it is preferred that the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , more preferably in the range of from 5:1 to 25:1 , more preferably in the range of from 8:1 to 22:1 , more preferably in the range of from 10:1 to 20:1 , more preferably in the range of from 12:1 to 18:1 , more preferably in the range of from 14:1 to 16:1.

In the case where the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , it is preferred that the supported metal oxide comprises CuO and Bi20s in an amount in the range of from 25 to 70 wt.-%, more preferably in the range of from 32 to 62 wt.-%, more preferably in the range of from 37 to 57 wt.-%, more preferably in the range of from 42 to 52 wt.-%, more preferably in the range of from 44 to 50 wt.-%, more preferably in the range of from 46 to 48 wt.-%, based on 100 wt.-% of the supported metal oxide.

In the case where the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, it is preferred according to a second alternative that the supported metal oxide comprises one or more metal oxides of Ni, more preferably of NiO, wherein more preferably the supported metal oxide consists of one or more metal oxides of Ni, preferably of NiO.

In the case where the supported metal oxide comprises one or more metal oxides of Ni, it is preferred that the supported metal oxide comprises Ni in an amount in the range of from 5 to 25 wt.-%, more preferably in the range of from 8 to 22 wt.-%, more preferably in the range of from 10 to 20 wt.-%, more preferably in the range of from 11 to 18 wt.-%, more preferably in the range of from 12 to 16 wt.-%, more preferably in the range of from 13 to 15 wt.-%, based on 100 wt.-% of the supported metal oxide.

It is preferred that the supported metal oxide displays a pore volume in the range of from 0.05 to 0.40 ml/g, more preferably in the range of from 0.100 to 0.350 ml/g, more preferably in the range of from 0.150 to 0.300 ml/g, more preferably in the range of from 0.160 to 0.290 ml/g, more preferably in the range of from 0.170 to 0.280 ml/g, more preferably in the range of from 0.180 to 0.270 ml/g, more preferably in the range of from 0.190 to 0.260 ml/g, more preferably in the range of from 0.200 to 0.250 ml/g, more preferably in the range of from 0.210 to 0.240 ml/g, more preferably in the range of from 0.220 to 0.230 ml/g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

It is preferred that the supported metal oxide is in the form of a shaped body, more preferably in the form of a tablet or an extrudate, more preferably in the form of a tablet.

In the case where the supported metal oxide is in the form of a tablet, it is preferred that the tablet has a four-hole cross-section and more preferably four flutes, wherein the tablet more preferably has a four-hole cross-section having a diameter in the range of from 13 to 18 mm, more preferably in the range of from 14.5 to 16 mm, more preferably in the range of from 15.0 to 15.5 mm, and a height in the range of from 7 to 11 mm, more preferably in the range of from 8.2 to 9.4 mm, more preferably in the range of from 8.6 to 9.0 mm.

In the case where the supported metal oxide is in the form of a tablet, and where the tablet has a four-hole cross-section, it is preferred that the tablet has a side crushing strength 1 (SCSI ) of at least 375 N, more preferably in the range of from 375 to 450 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 1 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on two cylindrical segments sided by a flute.

Further in the case where the supported metal oxide is in the form of a tablet, and where the tablet has a four-hole cross-section, it is preferred that the tablet has a side crushing strength 2 (SCS2) of at least 150 N, more preferably in the range of from 150 to 250 N, more preferably in the range of from 175 to 215 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 2 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on a cylindrical segment.

Further in the case where the supported metal oxide is in the form of a tablet, and where the tablet has a four-hole cross-section, it is preferred that the tablet has a side crushing strength 3 (SCS3) of at least 325 N, more preferably in the range of from 325 to 475 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 3 is preferably determined according to Reference Example 1 in a condition wherein the area of the cylindrical segments is perpendicular to the direction of the force applied on the tablet.

Yet further, the present invention relates to a supported metal oxide comprising one or more metal oxides supported on a solid particulate support material, wherein said supported metal oxide is preferably obtainable and/or obtained according to the process of any one of the embodiments disclosed herein, wherein the supported metal oxide displays a pore volume in the range of from 0.05 to 0.40 ml/g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

It is preferred that the supported metal oxide displays a pore volume in the range of from 0.100 to 0.350 ml/g, more preferably in the range of from 0.150 to 0.300 ml/g, more preferably in the range of from 0.160 to 0.290 ml/g, more preferably in the range of from 0.170 to 0.280 ml/g, more preferably in the range of from 0.180 to 0.270 ml/g, more preferably in the range of from 0.190 to 0.260 ml/g, more preferably in the range of from 0.200 to 0.250 ml/g, more preferably in the range of from 0.210 to 0.240 ml/g, more preferably in the range of from 0.220 to 0.230 ml/g.

It is preferred that the average particle size D50 of the supported metal oxide is in the range of from 1 to 250 pm, more preferably in the range of from 2.5 to 100 pm , more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

It is preferred that the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof.

In the case where the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, it is preferred according to a first alternative that the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, more preferably of Cu and Bi, wherein more preferably the supported metal oxide consists of one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi.

In the case where the metal of the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, it is preferred that the supported metal oxide comprises CuO and/or Bi2O3, more preferably of CuO and Bi20s, wherein more preferably the supported metal oxide consists of CuO and/or Bi20s, preferably of CuO and Bi20s.

In the case where the supported metal oxide comprises CuO and/or Bi20s, it is preferred that the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , more preferably in the range of from 5:1 to 25:1 , more preferably in the range of from 8:1 to 22:1 , more preferably in the range of from 10:1 to 20:1 , more preferably in the range of from 12:1 to 18:1 , more preferably in the range of from 14:1 to 16:1.

In the case where the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , it is preferred that the supported metal oxide comprises CuO and Bi20s in an amount in the range of from 25 to 70 wt.-%, more preferably in the range of from 32 to 62 wt.-%, more preferably in the range of from 37 to 57 wt.-%, more preferably in the range of from 42 to 52 wt.-%, more preferably in the range of from 44 to 50 wt.-%, more preferably in the range of from 46 to 48 wt.-%, based on 100 wt.-% of the supported metal oxide. Further in the case where the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, it is preferred according to a second alternative that the supported metal oxide comprises one or more metal oxides of Ni, more preferably of NiO, wherein preferably the supported metal oxide consists of one or more metal oxides of Ni, preferably of NiO.

In the case where the supported metal oxide comprises one or more metal oxides of Ni, it is preferred that the supported metal oxide comprises Ni in an amount in the range of from 5 to 25 wt.-%, more preferably in the range of from 8 to 22 wt.-%, more preferably in the range of from 10 to 20 wt.-%, more preferably in the range of from 11 to 18 wt.-%, more preferably in the range of from 12 to 16 wt.-%, more preferably in the range of from 13 to 15 wt.-%, based on 100 wt.-% of the supported metal oxide.

It is preferred that the supported metal oxide is in the form of a shaped body, more preferably in the form of a tablet or an extrudate, more preferably in the form of a tablet.

In the case where the supported metal oxide is in the form of a tablet, it is preferred that the tablet has a four-hole cross-section and preferably four flutes, wherein the tablet more preferably has a four-hole cross-section having a diameter in the range of from 13 to 18 mm, more preferably in the range of from 14.5 to 16 mm, more preferably in the range of from 15.0 to 15.5 mm, and a height in the range of from 7 to 11 mm, more preferably in the range of from 8.2 to 9.4 mm, more preferably in the range of from 8.6 to 9.0 mm.

Further in the case where the supported metal oxide is in the form of a tablet, it is preferred that the tablet has a side crushing strength 1 (SCSI) of at least 375 N, more preferably in the range of from 375 to 450 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole crosssection and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 1 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on two cylindrical segments sided by a flute.

Further in the case where the supported metal oxide is in the form of a tablet, it is preferred that the tablet has a side crushing strength 2 (SCS2) of at least 150 N, more preferably in the range of from 150 to 250 N, more preferably in the range of from 175 to 215 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole crosssection and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 2 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on a cylindrical segment.

Further in the case where the supported metal oxide is in the form of a tablet, it is preferred that the tablet has a side crushing strength 3 (SCS3) of at least 325 N, more preferably in the range of from 325 to 475 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross- section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 3 is preferably determined according to Reference Example 1 in a condition wherein the area of the cylindrical segments is perpendicular to the direction of the force applied on the tablet.

Yet further, the present invention relates to a method for the production of 1 ,4-butynediol comprising

(1 ) optionally activating the supported metal oxide according to any one of the embodiments disclosed herein, preferably the supported metal oxide of any one of the embodiments disclosed herein according to which the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, for obtaining an activated supported metal oxide,

(2) providing the activated supported metal oxide obtained in (1) or the supported metal oxide of any one of the embodiments disclosed herein in an inert gas atmosphere in a reactor, and contacting a feed stream comprising acetylene with the activated supported metal oxide obtained in (1) or the supported metal oxide of any one of the embodiments disclosed herein, wherein the gas atmosphere has a temperature in the range of from 65 to 95 °C, preferably in the range of from 75 to 85 °C, for obtaining a product mixture comprising butynediol.

It is preferred that activating the supported metal oxide according to (1) comprises

(1.1) preparing a mixture in an inert gas atmosphere, the mixture comprising the supported metal oxide, formaldehyde, and water;

(1 .2) optionally adjusting the pH of the mixture obtained in (1 .1) to a value in the range of from 8.0 to 9.0, preferably in the range of from 7.5 to 9.5, for obtaining an activated supported metal oxide;

(1 .3) contacting a stream comprising acetylene with the supported metal oxide comprised in the mixture obtained in (1.1) or (1 .2), for obtaining an activated supported metal oxide;

(1 .4) optionally separating the activated supported metal oxide from the mixture obtained in (1 .3), preferably by one or more of decanting and centrifuging;

(1 .5) optionally drying the activated supported metal oxide obtained in (1 .4).

It is preferred that the inert gas atmosphere according to (2) or (1 .1 ) independently from one another comprises, preferably consists of, one or more of nitrogen and argon, preferably nitrogen.

It is preferred that the feed stream comprising acetylene has a flow rate in the range of from 35 to 65 ml/min, more preferably in the range of from 45 to 55 ml/min.

It is preferred that the method further comprises

(3) separating the activated supported metal oxide from the product mixture obtained in (2), wherein separating preferably comprises filtration. Yet further, the present invention relates to a method for reforming one or more hydrocarbons, more preferably for reforming methane, in the presence of CO2 to a synthesis gas comprising hydrogen and carbon monoxide, the method comprising

(a) optionally activating the supported metal oxide of any one of the embodiments disclosed herein, for obtaining an activated supported metal oxide;

(b) providing a reactor comprising a reaction zone which comprises the activated supported metal oxide obtained in (a) or the supported metal oxide of any one of the embodiments disclosed herein, preferably a supported metal oxide according to any one of the embodiments according to which the supported metal oxide comprises one or more metal oxides of Ni;

(c) passing a reactant gas stream into the reaction zone obtained in (a), wherein the reactant gas stream passed into the reaction zone comprises one or more hydrocarbons, carbon dioxide, and water, subjecting said reactant gas stream to reforming conditions in said reaction zone, and removing a product stream from said reaction zone, said product stream comprising hydrogen and carbon monoxide.

It is preferred that activating according to (a) comprises heating the supported metal oxide of any one of the embodiments disclosed herein in a gas atmosphere comprising hydrogen and nitrogen, wherein the gas atmosphere has a temperature in the range of from 420 to 480 °C, more preferably in the range of from 440 to 460 °C.

It is preferred that the reforming conditions in (c) comprise a temperature in the range of from 800 to 1000 °C, more preferably in the range of from 850 to 950 °C.

Yet further, the present invention relates to a use of a supported metal oxide according to any one of the embodiments disclosed herein as a catalyst and/or as a catalyst support, preferably as a catalyst, more preferably as a catalyst for the production of 1 ,4-butynediol or for reforming one or more hydrocarbons, preferably for reforming methane.

Yet further, the present invention relates to a use of a supported metal oxide according to any one of the embodiments disclosed herein as an adsorbent, more preferably for the purification of olefins, oxygen, and/or carbon monoxide.

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 preparation of a supported metal oxide comprising one or more metal oxides supported on a particulate support material, said process comprising

(i) preparing a suspension comprising a liquid solvent system and one or more solid particulate support materials, wherein the liquid solvent system comprises one or more metal oxide precursor compounds, wherein the one or more metal oxide precursor compounds are dissolved in the liquid solvent system;

(ii) atomization of the suspension obtained in (i) in a gas stream for obtaining an aerosol;

(iii) drying or calcination of the aerosol obtained in (ii) for obtaining a powder of a supported metal oxide.

2. The process of embodiment 1 , wherein the one or more solid particulate support materials are selected from the group consisting of oxidic compounds and mixtures of two or more thereof, preferably from the group consisting of oxides, hydroxides, carbonates, and mixtures of two or more thereof, more preferably from the group consisting of oxides, hydroxides, and carbonates of metals and/or metalloids of groups II, III, IV, XIII, XIV, lanthanides, and mixtures of two or more thereof, wherein the metals and/or metalloids are preferably selected from the group consisting of Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Hf, B, Al, Ga, In, Si, Ge, Sn, Pb, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ca, Ba, Y, La, Ce, Pr, Nd, Sm, Ti, Zr, B, Al, Ga, Si, Ge, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ca, Ce, Pr, Nd, Ti, Zr, Al, Ga, Si, Ge, and mixtures of two or more thereof, more preferably from the group consisting of Mg, Ce, Zr, Al, Si, and mixtures of two or more thereof, and more preferably from the group consisting of Mg, Al, Si, and mixtures of two or more thereof.

3. The process of embodiment 1 or 2, wherein the metal of the one or more metal oxide precursor compounds is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof.

4. The process of embodiment 3, wherein the metal of the one or more metal oxide precursor compounds comprises Cu and/or Bi, preferably Cu and Bi, wherein more preferably the metal of the one or more metal oxide precursor compounds consists of Cu and/or Bi, preferably of Cu and Bi.

5. The process of embodiment 4, wherein the one or more solid particulate support materials comprise aluminium magnesium hydroxy carbonate, preferably aluminium magnesium hydroxy carbonate and boehmite, wherein more preferably the one or more solid particulate support materials in (i) is aluminium magnesium hydroxy carbonate or a mixture of aluminium magnesium hydroxy carbonate and boehmite.

6. The process of embodiment 5, wherein the aluminium magnesium hydroxy carbonate displays an AI2O3 : MgO weight ratio in the range of from 60:40 to 80:20, preferably in the range of from 65:35 to 75:25, more preferably in the range of from to 68:32 to 72:28.

7. The process of embodiment 3, wherein the metal of the one or more metal oxide precursor compounds comprises Ni, wherein more preferably the metal of the one or more metal oxide precursor compounds consists of Ni.

8. The process of embodiment 7, wherein the one or more solid particulate support materials comprise one or more silicates of magnesium, preferably magnesium silicate, more preferably talc, and more preferably Mg3Si40io(OH)2, wherein more preferably the one or more solid particulate support materials in (i) consists of one or more silicates of magnesium, preferably of magnesium silicate, more preferably of talc, and more preferably of Mg3Si4Ow(OH)2.

9. The process of any one of embodiments 1 to 8, wherein the suspension prepared in (i) displays a pH in the range of from 1 to 6, preferably in the range of from 2 to 5, more preferably in the range of from 2 to 4.

10. The process of any one of embodiments 1 to 9, wherein the suspension prepared in (i) displays a solid content in the range of from 1 to 42 volume-%, preferably in the range of from 10 to 37 volume-%, more preferably in the range of from 17 to 33 volume-%, more preferably in the range of from 22 to 28 volume-%, more preferably in the range of from 24 to 26 volume-%, based on 100 volume-% of the suspension prepared in (i).

11 . The process of any one of embodiments 1 to 10, wherein the suspension prepared in (i) displays a solid content in the range of from 5 to 50 weight-%, more preferably in the range of from 10 to 40 weight-%, more preferably in the range of from 15 to 30 weight-%, based on 100 weight-% of the suspension prepared in (i).

12. The process of any one of embodiments 1 to 11 , wherein preparing the suspension in (i) comprises

(i.a) preparing a solution of one or more metal oxide precursor compounds in a liquid solvent system for obtaining a solution;

(i.b) adjusting the pH of the solution obtained in (i.a) to a value in the range of from 0 to 4, preferably in the range of from 0 to 3, more preferably in the range of from 0 to 2, more preferably in the range of from 0 to 1 ;

(i.c) suspending one or more solid particulate support materials in a liquid solvent system for obtaining a suspension;

(i.d) adding the solution obtained in (i.b) to the suspension obtained in (i.c) for obtaining a suspension.

13. The process of any one of embodiments 1 to 12, wherein independently from one another, the liquid solvent system in (i), (i.a), and/or (i.c) comprises water and/or one or more organic solvents, and preferably comprises one or more solvents selected from the group consisting of water, monohydric alcohols, polyhydric alcohols, and combinations of two or more thereof, more preferably selected from the group consisting of water, methanol, ethanol, propanol, butanol, pentanol, ethane-1 ,2-diol, propane-1 ,2-diol, propane-1 , 2, 3-triol, butane-1 ,2,3,4-tetraol, pentane-1 ,2,3,4, 5-pentol, and combinations of two or more thereof, more preferably from the group consisting of water, methanol, ethanol, 2-propanol, and mixtures of two or more thereof, wherein more preferably the liquid solvent system comprises water, preferably deionized water, wherein more preferably the liquid solvent system in (i), (i.a), and/or (i.c) consists of deionized water.

14. The process of any one of embodiments 1 to 13, wherein independently from one another, the concentration of the one or more metal oxide precursor compounds in the liquid solvent system of the suspension obtained in (i) or (i.d), and/or in the solution obtained in (i.a), is in the range of from 1 to 5 mol/L, preferably in the range of from 1 to 4 mol/L, more preferably in the range of from 1 to 3 mol/L, more preferably in the range of from 1 to 2 mol/L.

15. The process of any one of embodiments 1 to 14, wherein independently from one another, the one or more solid particulate support materials contained in the suspension obtained in (i), (i.c), and/or (i.d) display an average particle size D50 in the range of from 0.5 to 500 pm, preferably of from 1 to 300 pm, preferably of from 5 to 200 pm, more preferably of from 10 to 100 pm, more preferably of from 15 to 80 pm, more preferably of from 20 to 60 pm, more preferably of from 25 to 40 pm, and more preferably of from 30 to 35 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020. 16. The process of any one of embodiments 1 to 15, wherein the one or more metal oxide precursor compounds are selected from the group consisting of metals salts and mixtures thereof, wherein the metal salts are preferably selected from the group consisting of metal halides, nitrates, nitrites, sulfates, sulfites, phosphates, phosphites, cyanides, and mixtures of two or more thereof, preferably from the group consisting fluorides, chlorides, bromides, nitrates, sulfates, hydrogensulfates, dihydrogensulfates, cyanides, and mixtures of two or more thereof, more preferably from the group consisting of chloride, bromide, nitrate, and mixtures of two or more thereof, wherein more preferably the one or more metal oxide precursor compounds comprises the chloride and/or nitrate salt of the one or more metals, preferably the nitrate salt of the one or more metals, wherein more preferably the one or more metal oxide precursor compounds consist of the chloride and/or nitrate salt of the one or more metals, preferably of the nitrate salt of the one or more metals.

17. The process of any one of embodiments 1 to 16, wherein the average particle size D50 of the droplets in the aerosol obtained in (ii) is in the range of from 10 to 250 pm, preferably in the range of from 10 to 200 pm, more preferably in the range of from 10 to 150 pm, more preferably in the range of from 10 to 100 pm, more preferably in the range of from 10 to 50 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

18. The process of any one of embodiments 1 to 17, wherein the average particle size D50 of the powder particles obtained in (iii) is in the range of from 1 to 250 pm, preferably in the range of from 2.5 to 100 pm, more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

19. The process of any one of embodiments 1 to 18, wherein atomization of the suspension of the zeolitic material in (ii) is conducted with a spray nozzle.

20. The process of any one of embodiments 1 to 19, wherein atomization of the suspension of the zeolitic material in (ii) is conducted by introducing the suspension into a gas stream, preferably with a peristaltic pump.

21 . The process of any one of embodiments 1 to 20, wherein the gas stream comprises one or more of the gases selected from the group consisting of oxygen, nitrogen, carbon dioxide, carbon monoxide, helium, neon, argon, steam, air, and combinations of two or more thereof, preferably from the group consisting of oxygen, nitrogen, carbon dioxide, argon, steam, air, and combinations of two or more thereof. 22. The process of any one of embodiments 1 to 21 , wherein drying the aerosol according to (iii) comprises heating the aerosol obtained in (ii) to a temperature in the range of from 60 to 250 °C, preferably of from 90 to 190 °C, more preferably of from 100 to 140 °C, more preferably of from 110 to 130 °C.

23. The process of embodiment 22, wherein the duration of drying the aerosol according to (iii) is in the range of from 1 to 48 h, preferably of from 6 to 20 h, more preferably of from 10 to 14 h.

24. The process of embodiment 22 or 23, wherein drying the aerosol according to (iii) is conducted in a gas atmosphere comprising one or more of oxygen, and nitrogen, preferably air.

25. The process of any one of embodiments 1 to 20, wherein the temperature of the calcination in (iii) is in the range of from 200 to 1 ,300 °C, preferably of from 250 to 1 ,250 °C, more preferably of from 250 to 1 ,200 °C, more preferably of from 300 to 1 ,000 °C, more preferably of from 350 to 850 °C, more preferably of from 400 to 750 °C, more preferably of from 450 to 700 °C, more preferably from 500 to 650 °C, and more preferably of from 550 to 600 °C.

26. The process of embodiment 25, wherein the temperature of the calcination in (iii) is in the range of from 275 to 900 °C, preferably of from 300 to 600 °C, more preferably of from 325 to 500 °C, more preferably of from 350 to 450 °C.

27. The process of embodiment 25, wherein the temperature of the calcination in (iii) is in the range of from 600 to 1 ,200 °C, preferably of from 850 to 1 ,150 °C, more preferably of from 950 to 1 ,100 °C, more preferably of from 1 ,025 to 1 ,075 °C.

28. The process of any one of embodiments 1 to 27, wherein the duration of the calcination in (iii) is in the range of from 5 ms to 30 s, preferably of from 20 ms to 15 s, more preferably of from 50 ms to 10 s, more preferably of from 80 ms to 5 s, more preferably of from 0.1 to 2 s, more preferably of from 0.3 to 1 s, and more preferably of from 0.5 to 0.8 s.

29. The process of any one of embodiments 1 to 28, wherein calcination in (iii) is at least in part or entirely conducted in an oxygen containing atmosphere, wherein the oxygen content of the atmosphere in vol.-% based on the total volume of the gases therein is preferably in the range of from 1 to 100 vol.-%, more preferably from 3 to 80 vol.-%, more preferably from 5 to 50 vol.-%, more preferably from 8 to 35 vol.-%, more preferably from 10 to 25 vol.-%, more preferably from 12 to 22 vol.-%, and more preferably from 14 to 16 vol.- 0 //o. The process of any one of embodiments 1 to 29, wherein calcination in (iii) is at least in part or entirely conducted in an inert gas atmosphere, wherein the inert gas atmosphere preferably comprises nitrogen and/or one or more noble gases, wherein more preferably the inert gas atmosphere comprises one or more gases selected from the group consisting of nitrogen, helium, neon, argon, krypton, xenon, and mixtures of two or more thereof, more preferably from the group consisting of nitrogen, helium, argon, and mixtures of two or more thereof, more preferably from the group consisting of nitrogen, argon, and mixtures thereof, wherein more preferably the inert gas atmosphere comprises nitrogen, and wherein more preferably the inert gas atmosphere consists of nitrogen. The process of any one of embodiments 1 to 30, wherein calcination in (iii) is achieved by contacting the aerosol with a hot gas stream, wherein preferably the hot gas stream is generated by heating a gas stream with a heating element, wherein the heating element is preferably a flame and/or an electrically heating element, more preferably a flame. The process of any one of embodiments 1 to 31 , wherein the process is not repeated but done in a single pass. The process of any one of embodiments 1 to 32, wherein the process further comprises

(iv) optionally mixing the supported metal oxide obtained from (iii) with one or more additives, for obtaining a mixture;

(v) subjecting the supported metal oxide obtained from (iii) or the mixture obtained in (iv) to a shaping process, wherein the shaping preferably comprises tableting or extruding, for obtaining a molding comprising the supported metal oxide. The process of embodiment 33, wherein the one or more additives are selected from the group consisting of graphite, polymeric vinyl compounds, polyalkylene oxides, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, polystyrenes, polysaccharides, alumina, silica, titania, zirconia, and mixtures of two or more thereof. The process of any one of embodiments 1 to 34, wherein the process further comprises

(vi) subjecting the supported metal oxide obtained in (iii), the mixture obtained in (iv), or the molding obtained in (v) to a heat treatment in a gas atmosphere having a temperature in the range of from 300 to 1 ,200 °C, preferably in the range of from 800 to 1 ,150 °C, more preferably in the range of from 1 ,000 to 1 ,100 °C, wherein the gas atmosphere comprises one or more of oxygen, nitrogen, air, and steam. A supported metal oxide comprising one or more metal oxides supported on a solid particulate support material, wherein said supported metal oxide is obtainable and/or obtained according to the process of any one of embodiments 1 to 35. The supported metal oxide of embodiment 36, wherein the average particle size D50 of the supported metal oxide is in the range of from 1 to 250 pm, preferably in the range of from 2.5 to 100 pm, more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020. The supported metal oxide of embodiment 36 or 37, wherein the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof. The supported metal oxide of embodiment 38, wherein the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi, wherein more preferably the supported metal oxide consists of one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi. The supported metal oxide of embodiment 39, wherein the supported metal oxide comprises CuO and/or Bi2O3, preferably of CuO and Bi2O3, wherein more preferably the supported metal oxide consists of CuO and/or Bi20s, preferably of CuO and Bi20s. The supported metal oxide of embodiment 40, wherein the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , preferably in the range of from 5:1 to 25:1 , more preferably in the range of from 8:1 to 22:1 , more preferably in the range of from 10:1 to 20:1 , more preferably in the range of from 12:1 to 18:1 , more preferably in the range of from 14:1 to 16:1. The supported metal oxide of embodiment 41 , wherein the supported metal oxide comprises CuO and Bi20s in an amount in the range of from 25 to 70 wt.-%, preferably in the range of from 32 to 62 wt.-%, more preferably in the range of from 37 to 57 wt.-%, more preferably in the range of from 42 to 52 wt.-%, more preferably in the range of from 44 to 50 wt.-%, more preferably in the range of from 46 to 48 wt.-%, based on 100 wt.-% of the supported metal oxide. 43. The supported metal oxide of embodiment 42, wherein the supported metal oxide comprises one or more metal oxides of Ni, preferably of NiO, wherein preferably the supported metal oxide consists of one or more metal oxides of Ni, preferably of NiO.

44. The supported metal oxide of embodiment 43, wherein the supported metal oxide comprises Ni in an amount in the range of from 5 to 25 wt.-%, preferably in the range of from 8 to 22 wt.-%, more preferably in the range of from 10 to 20 wt.-%, more preferably in the range of from 11 to 18 wt.-%, more preferably in the range of from 12 to 16 wt.-%, more preferably in the range of from 13 to 15 wt.-%, based on 100 wt.-% of the supported metal oxide.

45. The supported metal oxide of any one of embodiments 36 to 44, wherein the supported metal oxide displays a pore volume in the range of from 0.05 to 0.40 ml/g, preferably in the range of from 0.100 to 0.350 ml/g, more preferably in the range of from 0.150 to 0.300 ml/g, more preferably in the range of from 0.160 to 0.290 ml/g, more preferably in the range of from 0.170 to 0.280 ml/g, more preferably in the range of from 0.180 to 0.270 ml/g, more preferably in the range of from 0.190 to 0.260 ml/g, more preferably in the range of from 0.200 to 0.250 ml/g, more preferably in the range of from 0.210 to 0.240 ml/g, more preferably in the range of from 0.220 to 0.230 ml/g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

46. The supported metal oxide of any one of embodiments 36 to 45, being in the form of a shaped body, preferably in the form of a tablet or an extrudate, more preferably in the form of a tablet.

47. The supported metal oxide of embodiment 46, wherein the tablet has a four-hole crosssection and preferably four flutes, wherein the tablet more preferably has a four-hole cross-section having a diameter in the range of from 13 to 18 mm, more preferably in the range of from 14.5 to 16 mm, more preferably in the range of from 15.0 to 15.5 mm, and a height in the range of from 7 to 11 mm, more preferably in the range of from 8.2 to 9.4 mm, more preferably in the range of from 8.6 to 9.0 mm.

48. The supported metal oxide of embodiment 47, wherein the tablet has a side crushing strength 1 (SCSI) of at least 375 N, preferably in the range of from 375 to 450 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 1 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on two cylindrical segments sided by a flute.

49. The supported metal oxide of embodiment 47 or 48, wherein the tablet has a side crushing strength 2 (SCS2) of at least 150 N, preferably in the range of from 150 to 250 N, more preferably in the range of from 175 to 215 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 2 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on a cylindrical segment.

50. The supported metal oxide of any one of embodiments 47 to 49, wherein the tablet has a side crushing strength 3 (SCS3) of at least 325 N, preferably in the range of from 325 to 475 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 3 is preferably determined according to Reference Example 1 in a condition wherein the area of the cylindrical segments is perpendicular to the direction of the force applied on the tablet.

51 . A supported metal oxide comprising one or more metal oxides supported on a solid particulate support material, wherein said supported metal oxide is preferably obtainable and/or obtained according to the process of any one of embodiments 1 to 35, wherein the supported metal oxide displays a pore volume in the range of from 0.05 to 0.40 ml/g, wherein the pore volume is preferably determined according to ISO 15901-2:2022.

52. The supported metal oxide of embodiment 51 , wherein the supported metal oxide displays a pore volume in the range of from 0.100 to 0.350 ml/g, preferably in the range of from 0.150 to 0.300 ml/g, more preferably in the range of from 0.160 to 0.290 ml/g, more preferably in the range of from 0.170 to 0.280 ml/g, more preferably in the range of from 0.180 to 0.270 ml/g, more preferably in the range of from 0.190 to 0.260 ml/g, more preferably in the range of from 0.200 to 0.250 ml/g, more preferably in the range of from 0.210 to 0.240 ml/g, more preferably in the range of from 0.220 to 0.230 ml/g.

53. The supported metal oxide of embodiment 51 or 52, wherein the average particle size D50 of the supported metal oxide is in the range of from 1 to 250 pm, preferably in the range of from 2.5 to 100 pm , more preferably in the range of from 5 to 60 pm, more preferably in the range of from 8 to 35 pm, more preferably in the range of from 11 to 20 pm, more preferably in the range of from 13 to 17 pm, wherein the average particle size D50 is preferably determined according to ISO 13320:2020.

54. The supported metal oxide of any one of embodiments 51 to 53, wherein the metal of the supported metal oxide is selected from the group consisting of the elements of groups VIII, IX, X, XI, XII, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Cd, Os, Ir, Pt, Au, Hg, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Ag, Ge, Sn, Pb, Sb, Bi, and mixtures of two or more thereof, more preferably selected from the group consisting of Fe, Co, Ni, Cu, Zn, Pd, Sb, Bi, and mixtures of two or more thereof, and more preferably selected from the group consisting of Ni, Cu, Bi, and mixtures of two or more thereof.

55. The supported metal oxide of embodiment 54, wherein the supported metal oxide comprises one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi, wherein more preferably the supported metal oxide consists of one or more metal oxides of Cu and/or Bi, preferably of Cu and Bi.

56. The supported metal oxide of embodiment 55, wherein the supported metal oxide comprises CuO and/or Bi2O3, preferably of CuO and Bi2O3, wherein more preferably the supported metal oxide consists of CuO and/or Bi20s, preferably of CuO and Bi20s.

57. The supported metal oxide of embodiment 56, wherein the supported metal oxide displays a CuO : Bi20s weight ratio in the range of from 1 :1 to 50:1 , preferably in the range of from 5:1 to 25:1 , more preferably in the range of from 8:1 to 22:1 , more preferably in the range of from 10:1 to 20:1 , more preferably in the range of from 12:1 to 18:1 , more preferably in the range of from 14:1 to 16:1.

58. The supported metal oxide of embodiment 57, wherein the supported metal oxide comprises CuO and Bi20s in an amount in the range of from 25 to 70 wt.-%, preferably in the range of from 32 to 62 wt.-%, more preferably in the range of from 37 to 57 wt.-%, more preferably in the range of from 42 to 52 wt.-%, more preferably in the range of from 44 to 50 wt.-%, more preferably in the range of from 46 to 48 wt.-%, based on 100 wt.-% of the supported metal oxide.

59. The supported metal oxide of embodiment 54, wherein the supported metal oxide comprises one or more metal oxides of Ni, preferably of NiO, wherein preferably the supported metal oxide consists of one or more metal oxides of Ni, preferably of NiO.

60. The supported metal oxide of embodiment 59, wherein the supported metal oxide comprises Ni in an amount in the range of from 5 to 25 wt.-%, preferably in the range of from 8 to 22 wt.-%, more preferably in the range of from 10 to 20 wt.-%, more preferably in the range of from 11 to 18 wt.-%, more preferably in the range of from 12 to 16 wt.-%, more preferably in the range of from 13 to 15 wt.-%, based on 100 wt.-% of the supported metal oxide.

61 . The supported metal oxide of any one of embodiments 51 to 60, being in the form of a shaped body, preferably in the form of a tablet or an extrudate, more preferably in the form of a tablet. 62. The supported metal oxide of embodiment 61 , wherein the tablet has a four-hole crosssection and preferably four flutes, wherein the tablet more preferably has a four-hole cross-section having a diameter in the range of from 13 to 18 mm, more preferably in the range of from 14.5 to 16 mm, more preferably in the range of from 15.0 to 15.5 mm, and a height in the range of from 7 to 11 mm, more preferably in the range of from 8.2 to 9.4 mm, more preferably in the range of from 8.6 to 9.0 mm.

63. The supported metal oxide of embodiment 61 or 62, wherein the tablet has a side crushing strength 1 (SCSI) of at least 375 N, preferably in the range of from 375 to 450 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 1 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on two cylindrical segments sided by a flute.

64. The supported metal oxide of any one of embodiments 61 to 63, wherein the tablet has a side crushing strength 2 (SCS2) of at least 150 N, preferably in the range of from 150 to 250 N, more preferably in the range of from 175 to 215 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 2 is preferably determined according to Reference Example 1 in a condition wherein the tablet stands on a cylindrical segment.

65. The supported metal oxide of any one of embodiments 61 to 64, wherein the tablet has a side crushing strength 3 (SCS3) of at least 325 N, preferably in the range of from 325 to 475 N, more preferably in the range of from 395 to 425 N, determined as described in Reference Example 1 , wherein the tablet more preferably has a four-hole cross-section and four flutes, wherein four cylindrical segments are located in an area each between two flutes, wherein the side crushing strength 3 is preferably determined according to Reference Example 1 in a condition wherein the area of the cylindrical segments is perpendicular to the direction of the force applied on the tablet.

66. A method for the production of 1 ,4-butynediol comprising

(1 ) optionally activating the supported metal oxide according to any one of embodiments 36 to 65, preferably the supported metal oxide of any one of embodiments 39 to 42 and 55 to 58, for obtaining an activated supported metal oxide,

(2) providing the activated supported metal oxide obtained in (1) or the supported metal oxide of any one of embodiments 36 to 65 in an inert gas atmosphere in a reactor, and contacting a feed stream comprising acetylene with the activated supported metal oxide obtained in (1 ) or the supported metal oxide of any one of embodiments 36 to 65, wherein the gas atmosphere has a temperature in the range of from 65 to 95 °C, preferably in the range of from 75 to 85 °C, for obtaining a product mixture comprising butynediol. The method of embodiment 66, wherein activating the supported metal oxide according to

(1) comprises

(1.1) preparing a mixture in an inert gas atmosphere, the mixture comprising the supported metal oxide, formaldehyde, and water;

(1 .2) optionally adjusting the pH of the mixture obtained in (1 .1 ) to a value in the range of from 8.0 to 9.0, preferably in the range of from 7.5 to 9.5, for obtaining an activated supported metal oxide;

(1 .3) contacting a stream comprising acetylene with the supported metal oxide comprised in the mixture obtained in (1 .1 ) or (1.2), for obtaining an activated supported metal oxide;

(1 .4) optionally separating the activated supported metal oxide from the mixture obtained in (1.3), preferably by one or more of decanting and centrifuging;

(1 .5) optionally drying the activated supported metal oxide obtained in (1 .4). The method of embodiment 66 or 67, wherein the inert gas atmosphere according to (2) or (1.1) independently from one another comprises, preferably consists of, one or more of nitrogen and argon, preferably nitrogen. The method of any one of embodiments 66 to 68, wherein the feed stream comprising acetylene has a flow rate in the range of from 35 to 65 ml/min, preferably in the range of from 45 to 55 ml/min. The method of any one of embodiments 66 to 69, the method further comprising

(3) separating the activated supported metal oxide from the product mixture obtained in

(2), wherein separating preferably comprises filtration. A method for reforming one or more hydrocarbons, preferably for reforming methane, in the presence of CO2 to a synthesis gas comprising hydrogen and carbon monoxide, the method comprising

(a) optionally activating the supported metal oxide of any one of embodiments 36 to 65, for obtaining an activated supported metal oxide;

(b) providing a reactor comprising a reaction zone which comprises the activated supported metal oxide obtained in (a) or the supported metal oxide of any one of embodiments 36 to 65, preferably a supported metal oxide according to any one of embodiments 43, 44, 59 and 60;

(c) passing a reactant gas stream into the reaction zone obtained in (a), wherein the reactant gas stream passed into the reaction zone comprises one or more hydrocarbons, carbon dioxide, and water, subjecting said reactant gas stream to reforming conditions in said reaction zone, and removing a product stream from said reaction zone, said product stream comprising hydrogen and carbon monoxide. The method of embodiment 71 , wherein activating according to (a) comprises heating the supported metal oxide of any one of embodiments 36 to 65 in a gas atmosphere compris- ing hydrogen and nitrogen, wherein the gas atmosphere has a temperature in the range of from 420 to 480 °C, preferably in the range of from 440 to 460 °C.

73. The method of embodiment 71 or 72, wherein the reforming conditions in (c) comprise a temperature in the range of from 800 to 1000 °C, preferably in the range of from 850 to 950 °C.

74. Use of a supported metal oxide according to any one of embodiments 36 to 65 as a catalyst and/or as a catalyst support, preferably as a catalyst, more preferably as a catalyst for the production of 1 ,4-butynediol or for reforming one or more hydrocarbons, preferably for reforming methane.

75. Use of a supported metal oxide according to any one of embodiments 36 to 65 as an adsorbent, preferably for the purification of olefins, oxygen, and/or carbon monoxide.

DESCRIPTION OF THE FIGURES

Figure 1 : displays an image of the supported metal oxide of example 1 determined via Scanning Electron Microscopy coupled with Energy-Dispersive Spectroscopy (SEM- EDS), wherein the grey colored area of the supported metal oxide shows the magnesia silicate carrier and the white colored area shows copper and bismuth oxides.

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

EXPERIMENTAL SECTION

Reference Example 1 : Determination of the side crushing strength

The determination of the side crushing strength was according the method described in

WO 2020/157202 Reference Example 1. Details about the various orientations SCSI , SCS2 and SCS3 can be found in Figure 1 of WO 2020/157202. The relative standard deviations for the various side crushing strengths were in the range of 7 to 13 %.

Reference Example 2: Determination of the porosity

The porosity was determined by mercury intrusion porosity using an AutoPore V purchased by Micromeritics according to DIN 66133.

Example 1 : Preparation of a supported metal oxide comprising Cu and Bi The method of the invention was applied to prepare a copper catalyst used for the ethynylation of formaldehyde to butynediol. The catalyst was prepared with the reagents presented in table 1.

Table 1

Overview of the composition of a supported metal oxide comprising Cu and Bi, and of the used reagents for the preparation thereof.

The carrier particles had an average diameter of from 5 to 60 micrometers. The carrier material was first suspended in water in a continuously stirred vessel. An acidic solution was made up of copper and bismuth nitrate in water and nitrous acid in a separate vessel. The acid mixture was added to the vessel containing water and the carrier material. The temperature of the suspension was held constant at ambient conditions from about 15 °C to 30 °C.

The resulting precursor suspension was fed to the nozzle of the flash reactor with a peristaltic pump with a flow rate of 17 g/min. The nozzle was an air assisted nozzle with a diameter of 2 mm. The atomization was assisted with pressurized air (2...4 bar) with a flow rate of 6...8 m ³ /hr (stp). The precursor was sprayed into a hot flue gas stream provided by a gas burner. The hot flue gas was obtained by the combustion of natural gas having a flow rate of 2.5 m ³ /h (stp) and an air flow of 34 m ³ /h (stp). The precursor was injected downstream of the flame. The temperature in the reactor was held constant at about 450 °C, the pressure was controlled at about -3mbarg. The residence time in the hot section was about 0.8 seconds. After the reactor the gas stream containing the catalyst particles was cooled by addition of quench air to 170 °C and then fed into a cyclone where the solid particles were removed from the gas stream. At the bottom of the cyclone the particles were collected in a glass bottle. The thus obtained mixed oxide catalyst showed a composition according to table 1. The powder was further cooled and submitted to the following test procedures.

Catalytic Testing Procedure

Catalytic performance testing was carried out in two steps. First the catalyst powder was activated to form the active copper acetylide on the surface of catalyst. It was then transferred to the reaction vessel for ethynylation. Detailed procedure is shown as following. The activation was conducted in the reactor containing 100 mL 37 weight-% formaldehyde aqueous solution.

1 .5 M sodium hydroxide solution was added to formalin to adjust initial pH to about 8.5 and 15 g of catalyst was then added to formalin after the adjust of pH. Inertization of the reactor was conducted by purging nitrogen and then gas flow was exchanged to acetylene with 80mL/min. Start stirring at controlled pH of 8.0 and start heating up to 80 °C. The reaction was kept for 5 hours. Afterwards, the reactor was cooled down to room temperature under gas flow of acetylene. Nitrogen was purged into reactor for inertization, and the slurry was removed, centrifuged, and decanted, leaving wet catalyst ready for activity testing. 0.8 g (dry basis) of catalyst was added into reactor with formaldehyde aqueous solution. Similarly, the initial pH of formalin was adjusted to 8.0 by sodium hydroxide solution. The flow rate of acetylene was kept constant at 50 mL/min and the reaction temperature was 80 °C. After 5 hours, the reactor was cooled down under gas flow of acetylene followed by purging of nitrogen for inertization. The slurry was removed and centrifuged. The product mixture is analyzed by gas chromatography in which butynediol was quantified. A sodium sulfite titration method is used to determine the amount of formaldehyde remaining in the product. Thereafter, the activity of catalyst is evaluated by the formation rate of butynediol and the conversion of formaldehyde, which is calculated on the basis of reaction time of 300 min and catalyst mass of 0.8 g.

Filterability Testing Procedure

For the ethynylation process in plant, a filter is used for separation of spent catalysts and reaction products. In this way, spent catalysts are recycled, mixed with fresh catalyst and fed back into reactors. Therefore, the filtration speed of spent catalysts is critical to the recycling efficiency. The filtration rate is measured by a lab-simulated test for the catalyst after attrition. In detail, 4 g of fresh catalyst powder is added to 40 mL DI H2O and stirred at room temperature for 24 hours. Afterwards, the slurry is filtered, and the time used for filtration is recorded to calculate the filtration rate accordingly.

Activity and filterability comparison

A comparison of the catalytic activity and the filterability of the inventive catalyst (Catalyst 1) was made with a commercial BASF catalyst prepared according to US 99006129 B2. The results are presented in table 2.

Table 2

Overview on the results for catalytic testing.

The catalyst of the said invention exhibits a filterability twice as high as the commercial catalyst.

The high filterability improves significantly the handling of the catalyst in the BDO process.

Characterization of the Catalyst In order to characterize the deposition of the metal oxides on the magnesia silica carrier Scanning Electron Microscopy coupled with Energy-Dispersive Spectroscopy (SEM-EDS) was applied. Figure 1 shows an image of catalyst 1 . The grey portion of the catalyst shows the magnesia silicate carrier, whereas the white color indicates the copper and bismuth oxides. As can be seen from Figure 1 the copper and bismuth oxides form a layer around the carrier particle.

Comparative Example 2: Preparation of a supported metal oxide comprising Ni according to the prior art

The catalyst comprising Ni was prepared following the process described in example E1 of WO 2013/068905 A1.

An aqueous solution of Nickel nitrate (14 % Ni concentration) was used instead of the pulverulent nickel nitrate hexahydrate. The various ingredients were mixed to a paste which was extruded. The extrudates were crushed and sieved to a target fraction having a particle size of from 200 to 900 pm after drying and low temperature calcination.

The sieved powder was then mixed with graphite 2.8 weight- % (Asbury Graphite 3160) and 5.5 weight- % cellulose (Arbocel BWW 40). The resulting mixture was tableted to moldings having a four-hole cross-section as shown in Figure 1 of WO 2020/157202 A. Tableting was done on a E150 type tableting press purchased by Kilian applying a tableting force of 60 kN yielding tablets with a four-hole cross-section as shown in Figure 1 of WO 2020/157202. For calcination, the resulting moldings were heated in an annealing furnace to a temperature of 1050 °C which was held constant for 1 hour.

The Nickel content of the calcined moldings was 15.1 weight-%, the Magnesium content 13.3 weight-%, the Aluminum content was 31.0 weight-%.

Example 3: Preparation of a supported metal oxide comprising Ni according to the invention

The method of the invention was applied to prepare a catalyst comprising Ni. The catalyst was prepared with the reagents presented in table 3.

Table 3

Overview of the used reagents for the preparation of a supported metal oxide comprising Ni. The suspension was prepared by mixing the various reagents in a continuously stirred vessel. The suspension was prepared and stored at ambient pressure and temperature in the range of about 15 °C to 30 °C.

The resulting precursor suspension was fed to the nozzle of the flash reactor with a peristaltic pump with a flow rate of 50 g/min. The nozzle was an air assisted nozzle with a diameter of 2 mm. The atomization was assisted with pressurized air (ca. 2 bar) with a flow rate of 6 m ³ /hr (stp). The precursor was sprayed into a hot flue gas stream provided by a gas burner. The hot flue gas was obtained by the combustion of natural gas having a flow rate of 4 m ³ /h (stp) and an air flow of 41 m ³ /h (stp). The precursor was injected downstream of the flame. The temperature in the reactor was held constant at 700 °C, the pressure was controlled at -3mbarg. The residence time in the hot section was about 0.5 seconds. After the reactor the gas stream containing the catalyst particles was cooled by addition of quench air to 170 °C and then fed into a cyclone where the solid particles were removed from the gas stream. At the bottom of the cyclone the particles were collected in a glass bottle. The Nickel content of the thus obtained powder was 13.4 weight-%.

In a subsequent step, the powder was mixed with 1 .48 weight-% of graphite (Asbury Graphite 3160) and the resulting mixture was granulated using a compactor (Typ RCC 100x20, powtec GmbH). The resulting compacted molding was crushed and sieved to 200-1000 pm particles and further processed according to comparative example 2 while the amount of graphite in the mixture was 1.38 weight-%.

The Nickel content of the calcined moldings was 14.5 weight-%, the Magnesium content 13.4 weight-%, the Aluminum content was 31.0 weight-%.

Table 4 compares the mechanical strength (SCSI , SCS2, SCS3) and the porosity of the samples prepared according to state of the art (Example 2) and according to invention (Example 3).

Table 4

Overview of mechanical properties of the supported metal oxides according to comparative example 2 and example 3.

Cited literature:

- WO 2004/005184 A1

- Narowski et al. in Polish Journal of Chemistry, 77(1), 105 (2003) - Katarzyna et al. in Applied catalysis A, 426-424, 114-120 (2012)

- Patkowski et al. in European Journal of Inorganic Chemistry, 15, 1518-1529 (2021)

- Kowalik et al. in European Journal of Inorganic Chemistry, 2019(13), 1792-1798

- WO 2017/167622 A1 - WO 2013/068905 A1

- US 9,006,129 B2

- EP 3 323 510 A1