USE OF A CATALYST FOR PRODUCTION OF METHANOL FROM METHANE, A METHOD OF PRODUCTION OF METHANOL FROM METHANE, THE CATALYST AND A METHOD OF PRODUCTION THEREOF

Abstract

The present invention relates to the use of a catalyst for production of methanol from methane, wherein the catalyst comprises a zeolite having Al pairs in the skeleton of at least 10 percent, based on the total number of all aluminium atoms in the zeolite, and further comprising a transition metal cation coordinated at beta-cationic positions, selected from the group consisting of Fe, Co, Mn, and Ni, wherein the ratio of the transition metal to Al is in the range of from 0.01 to 0.5; and with the proviso that the zeolite is not ZSM-5 and mordenite. The present invention further relates to the method of production of methanol, the catalyst for production of methanol by direct oxidation of methane, and to a method of production thereof.

Claims

1. A catalyst for the production of methanol from methane, wherein the catalyst comprises a zeolite having at least 10 percent of Al atoms in the skeleton located in pairs, each pair represented by two Al atoms located in one ring of the zeolite, based on the total number of all aluminium atoms in the zeolite, the number of Al pairs determined by a method based on a quantitative analysis of the extent of formation of Co(II) complexes characterized by a combination of chemical analysis, FTIR and UV Vis spectroscopy, and further comprising a divalent transition metal cation M, wherein the distance of two adjacent divalent transition metal cations coordinated at two adjacent cationic positions forming one binuclear centre is in the range of from 6 to 9 Å, determined using DFT model based on X-ray diffraction of the zeolite, wherein M is selected from the group consisting of Mn, Fe, Co, and Ni, wherein the ratio of the transition metal M to Al is in the range of from 0.01 to 0.5, wherein the Si/Al ratio is in the range of from 2 to 9, and wherein the zeolite is selected from the group consisting of ferrierite, beta zeolite and SSZ-13, according to the Nickel-Strunz classification.

2-3. (canceled)

4. A method for production of methanol, characterized in that it comprises the following steps: (i) a catalyst for production of methanol from methane is oxidized with oxygen at a temperature of at most 300° C., wherein the catalyst comprises a zeolite having at least 10 percent of Al atoms in the skeleton located in pairs, each pair represented by two Al atoms located in one ring of the zeolite, based on the total number of aluminium atoms in the zeolite, the number of Al pairs determined by a method based on a quantitative analysis of the extent of formation of Co(II) complexes characterized by a combination of chemical analysis, FTIR and UV Vis spectroscopy, and containing a transition metal cation M, wherein the distance of two adjacent divalent transition metal cations coordinated at two adjacent cationic positions forming one binuclear centre is in the range of from 6 to 9 Å, determined using DFT model based on X-ray diffraction of the zeolite, wherein M is selected from the group consisting of Mn, Fe, Co, and Ni, wherein the ratio of the transition metal M to Al is in the range of from 0.01 to 0.5, wherein the Si to Al ratio is in the range of from 2 to 9, and wherein the zeolite is selected from the group consisting of ferrierite, beta zeolite and SSZ-13, according to the Nickel-Strunz classification; and (ii) the oxidized catalyst is contacted with methane with which it interacts to form methanol at the same temperature as in step (i).

5. The method for production of methanol according to claim 4, wherein the catalyst is activated before step (i) in a stream of oxygen, followed by helium at a temperature of at least 450° C.

6-12. (canceled)

Description

EXAMPLES

[0045] Materials

[0046] Ferrierite, BEA zeolite and SSZ-13 zeolite were used as starting zeolites for the synthesis of catalysts of the present invention.

[0047] If ferrierite was used, it was obtained as follows

[0048] The commercially available ferrierite was obtained from TOSOH or prepared as follows (designated FER (HI)):

[0049] 3.0 g of sodium aluminate, 80 g of water and 0.4 g of NaOH were mixed, and after 15 minutes, 17 g of pyrrolidine was added to the resulting solution, and the mixture was further stirred for another 15 minutes. Then 90 g of colloidal silica, 30 wt. % suspension in water (LUDOX-30) was added and the mixture was stirred until homogenized. The synthesis gel thus prepared was placed in a stainless steel autoclave with a Teflon liner and heated at 145° C. for 15 days. The obtained zeolite was thoroughly washed with water and dried. To remove residual organic templates, the resulting ferrierite was calcined at 450° C. for 5 hours in a stream of air.

[0050] Ferrierite (TOSOH) had the following parameters: Si/Al 8.5; 66 percent of the number of all Al present was in the form of Al pairs; 45 percent of the number of all Al present in the form of a pair of adjacent Al pairs. A pair of adjacent Al pairs is defined as a pair of Al pairs that form two adjacent cationic sites in which, after being occupied by a pair of cations, this pair of cations is spaced 4.5 to 12 Å apart.

[0051] The ferrierite prepared by the above procedure (designated FER (HI)) had the following parameters:

[0052] Si/Al 9; 56 percent of the number of all Al present in the form of Al pairs; 35 percent of the number of all Al present in the form of a pair of adjacent Al pairs.

[0053] If BEA zeolite was used, it was synthesized as follows

[0054] 10 g of NaAlO.sub.2 was dissolved in 1000 ml of deionized water, followed by addition of 42 g of NaOH and stirring for 40 minutes, addition of 96 g of micronized silica (Cabosil), stirring for 10 minutes and addition of 5 g of beta zeolite nuclei. The mixture was then homogenized for 5 minutes. The synthesis was performed in a 2500 ml unstirred autoclave at 120° C. for 125 hours under autogenous pressure. The zeolite product was washed with deionized water and dried at 80° C. for 6 hours. The dried synthesized zeolite was calcined for 8 hours in a stream of air at 540° C.

[0055] BEA zeolite had the following parameters: Si/Al 4.5; 30 percent of the number of all Al present in the form of Al pairs; 30 percent of the number of all Al present in the form of a pair of adjacent Al pairs.

[0056] If SSZ-13 zeolite was used, it was synthesized as follows

[0057] SSZ-13 Si/Al 4.5

[0058] 5 g of sodium silicate (26.5 percent by weight of SiO.sub.2) (SIGMA-Aldrich) were added to 60 g of deionized water and stirred for 15 minutes, then 1 g of zeolite Y (in the form of Na, Si/Al=2.5) was added and further stirred for 30 minutes. 13.15 g of 20 percent by weight of TMAdOH (tetramethylammonium hydroxide, Chinese supplier) were added and stirred for another 30 minutes and then the synthetic mixture was placed in an autoclave for 6 days at 140° C. with rotation.

[0059] The synthesized SSZ-13 had the following parameters: Si/Al 4.5; 50 percent of the number of all Al present in the form of Al pairs; 40 percent of the number of all Al present in the form of a pair of adjacent Al pairs.

[0060] SSZ-13 Si/Al 5.5

[0061] 5 g of sodium silicate (26.5 percent by weight of SiO.sub.2) (SIGMA-Aldrich) was added to 60 g of deionized water and stirred for 15 minutes, then 2.1 g of zeolite Al.sub.2(SO.sub.4).sub.3 was added and further stirred for 30 minutes. 13.15 g of 20 percent by weight of TMAdOH (Chinese supplier) were added and stirred for another 30 minutes, and then the synthetic mixture was placed in an autoclave for 6 days at 140° C. with rotation.

[0062] The synthesized SSZ-13 had the following parameters: Si/Al 5.5: 40 percent of the number of all Al present in the form of Al pairs; 35 percent of the number of all Al present in the form of a pair of adjacent Al pairs.

[0063] Characteristics of Catalysts

[0064] The number of Al pairs for the zeolites used was determined by a method based on a quantitative analysis of the extent of formation of Co(II) complexes characterized by a combination of chemical analysis, FTIR and UV Vis spectroscopy. Details of the method are described in the publication J. Dědeček, Z. Sobalik, B. Wichterlová, Siting and Distribution of Framework Aluminium Atoms in Silicon-Rich Zeolites and Impact on Catalysis, Catalysis Reviews: Science and Engineering 54 (2012) 135-223.

[0065] The frequency of optimal local arrangements, comprising two pairs of adjacent pairs always with a total of four Al atoms and necessary for the formation of binuclear metal ion centres, was derived for each zeolite from the Si/Al value, the frequency of Al pairs and the known zeolite topology.

Example 1: Catalytic Test (Same for all Samples)

[0066] The products of the catalytic reaction were monitored by mass spectrometry. Uniform distribution of the catalyst particles in the range of 600 to 300 μm was achieved by pressing, crushing and sieving the powders. In a quartz reactor, 0.25 to 0.50 g of catalyst sample was used for the test. A tube furnace with temperature controlled by a thermocouple was used for the reaction. Prior to the first reaction cycle, the catalyst sample was heated in a stream of oxygen (25 ml/min) at 450° C. for 1 h, and then in a stream of helium (25 ml/min) for another 2 hours at the same temperature. Then, the temperature was reduced in a stream of inert gas (ramp 10° C./min) to 200° C.

[0067] Subsequently, catalytic cycles of methane oxidation were performed. The sample was exposed to a stream of oxygen (25 ml/min) for 10 minutes, purged with argon (25 ml/min) for 1 min. The interaction with CH.sub.4 (25 ml/min) lasted for 5 minutes and then the reactor was purged with a stream of inert gas for 1 minute. Signals were detected for m/z=31 for methanol, m/z=29 for other possible oxidation products, such as formaldehyde, formic acid, dimethyl ether and m/z=44 for CO.sub.2. The signal m/z=31 was integrated and compared with the calibration data for methanol to quantify the methanol yield. The cycles were repeated five times without the observed decrease in methanol yield.

Example 2: Fe-FER (TOSOH) Catalyst (Fe/Al 0.03)

[0068] Fe-FER zeolite, Si/Al 8.5, Fe/Al 0.03 was prepared by impregnation with a solution of FeCl.sub.3 in acetylacetone (AcAc). For this purpose, a granulated sample of NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). To 1 g of dehydrated zeolite an impregnation solution composed of 0.10 g of FeCl.sub.3 and 1.70 g of AcAc was added and left overnight at room temperature. The next day, the excess impregnation solution was removed by filtration. The sample thus prepared was heated under dynamic vacuum as follows: 1 h at 100° C. and then 3 h at 350° C. (heating rate 4° C./min). After cooling to room temperature, the sample was filtered off and washed with distilled water, then dried at room temperature.

[0069] The material thus prepared was calcined in air at 450° C. for 24 hours.

[0070] In the reaction test according to Example 1, 170 μmol of methanol per gram of catalyst per hour were obtained, and at the same time 20 μmol of a mixture of formaldehyde and dimethyl ether (i.e. oxygenates) per gram of catalyst per hour.

Example 3: Fe-FER (TOSOH) Catalyst (Fe/Al 0.25)

[0071] Fe-ferrierite, Fe/Al 0.25 was prepared by impregnation with a solution of FeCl.sub.3 in acetylacetone (AcAc). For this purpose, a granulated sample of NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). To 1 g of dehydrated zeolite an impregnation solution composed of 0.82 g of FeCl.sub.3 and 14.20 g of AcAc was added and left overnight at room temperature. The next day, the excess impregnation solution was removed by filtration. The sample thus prepared was heated under dynamic vacuum as follows: 1 h at 100° C. and then 3 h at 350° C. (heating rate 4° C./min). After cooling to room temperature, the sample was filtered off and washed with distilled water, then dried at room temperature.

[0072] The material thus prepared was calcined in air at 450° C. for 24 hours.

[0073] In the reaction test according to Example 1, 1600 μmol of methanol per gram of catalyst per hour were obtained, and at the same time 400 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour.

Example 4: Fe-FER (TOSOH) Catalyst (Fe/Al 0.30)

[0074] Fe-ferrierite, Fe/Al 0.30 was prepared by ion exchange with aqueous FeSO.sub.4 solution. 1 g of the sample was changed twice for 12 h with 100 ml of 0.05 M FeSO.sub.4 solution. Before preparing the solution, oxygen was removed from the distilled water used by bubbling with a stream of nitrogen for 1 hour. The ion exchange took place in a closed vessel and under a nitrogen atmosphere. The sample was then centrifuged under nitrogen and dried in a stream of nitrogen at room temperature. In the reaction test according to Example 1, 1800 μmol of methanol per gram of catalyst per hour and 500 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 5: Fe-FER (TOSOH) Catalyst (Fe/Al 0.45)

[0075] Fe-FER zeolite, Si/Al 8.5, Fe/Al 0.45 was prepared by impregnation with a solution of FeCl.sub.3 in acetylacetone (AcAc). For this purpose, a granulated sample of NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). To 1 g of dehydrated zeolite an impregnation solution composed of 1.48 g of FeCl.sub.3 and 25.56 g of AcAc was added and left overnight at room temperature. The next day, the excess impregnation solution was removed by filtration. The sample thus prepared was heated under dynamic vacuum as follows: 1 h at 100° C. and then 3 h at 350° C. (heating rate 4° C./min). After cooling to room temperature, the sample was filtered off and washed with distilled water, then dried at room temperature and calcined in air at 450° C. for 24 hours.

[0076] In the reaction test according to Example 1, 680 μmol of methanol per gram of catalyst per hour and 90 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 6: Co-FER (TOSOH) Catalyst (Co/Al 0.15)

[0077] Co-FER zeolite, Si/Al 8.5, Co/Al 0.15 was prepared by ion exchange of a powder sample of NH.sub.4-FER (TOSOH) with a 0.05 M aqueous solution of Co(NO.sub.3).sub.2.6H.sub.2O at 60° C. (1×12 h, 50 ml solution/1 g zeolite). After ion exchange, the zeolite was thoroughly washed and air dried at room temperature.

[0078] In the reaction test according to Example 1, 150 μmol of methanol per gram of catalyst per hour and ˜20 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 7: Co-FER (TOSOH) Catalyst Co/Al 0.30

[0079] Co-FER zeolite, Si/Al 8.5, Co/Al 0.15 was prepared by ion exchange with 0.05 M aqueous cobalt acetate solution at 60° C. (3×24 h, 100 ml solution/1 g zeolite). The sample was then washed thoroughly and air dried at room temperature.

[0080] In the reaction test according to Example 1, 900 μmol of methanol per gram of catalyst per hour and 60 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 8: Co-FER (TOSOH) Catalyst (Co/Al 0.35)

[0081] Co-FER zeolite, Si/Al 8.5, Co/Al 0.35 was prepared by ion exchange with CoAc.sub.2. 1.0 g of NH.sub.4-FER (TOSOH) was added to 100 ml of 0.05 M aqueous CoAc.sub.2 solution and stirred at 70° C. for 12 hours. This procedure was repeated three times. Subsequently, the obtained material was filtered off and washed thoroughly with distilled water and then dried at room temperature. The dried sample was heated to 450° C. in a stream of air for 24 hours.

[0082] In the reaction test according to Example 1, 1900 μmol of methanol per gram of catalyst per hour were obtained, and at the same time 200 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour.

Example 9: Co-FER (TOSOH) Catalyst (Co/Al 0.44)

[0083] Co-FER zeolite, Si/Al 8.5, Co/Al 0.44 was prepared by ion exchange with 0.05 M aqueous solution of Co(NO.sub.3).sub.2 at 60° C. (3×12 h, 50 ml solution/1 g zeolite). After ion exchange, the zeolite was thoroughly washed and air dried at room temperature.

[0084] In the reaction test according to Example 1, 550 μmol of methanol per gram of catalyst and 50 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 10: Ni-FER (TOSOH) Catalyst (Ni/Al 0.18)

[0085] Ni-FER zeolite, Si/Al 8.5, Ni/Al 0.18 was prepared by ion exchange with 0.05 M aqueous solution of Ni(NO.sub.3).sub.2.6H.sub.2O at 30° C. (1×12 h, 50 ml solution/1 g zeolite). After ion exchange, the zeolite was thoroughly washed and air dried at room temperature.

[0086] In the reaction test according to Example 1, 100 μmol of methanol per gram of catalyst and ˜30 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 11: Ni-FER (TOSOH) Catalyst (Ni/Al 0.32)

[0087] Ni-FER zeolite, Si/Al 8.5, Ni/Al 0.32 was prepared by impregnation with an aqueous solution of Ni(NO.sub.3).sub.2. A granulated sample of NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). 1 ml of a solution of Ni(NO.sub.3).sub.2. 6H.sub.2O with a concentration of 2.0 wt. % was added dropwise to the zeolite. The sample was then air dried for 24 hours at room temperature and then calcined in air at 450° C. for 4 hours. In the reaction test according to Example 1, 1700 μmol of methanol per gram of catalyst per hour were obtained, and at the same time 550 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour.

Example 12: Ni-FER (TOSOH) Catalyst (Ni/Al 0.45)

[0088] Ni-FER zeolite, Si/Al 8.5, Ni/Al 0.45 was prepared by impregnating granulated NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) being dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). The solution of 0.28 g Ni(NO.sub.3).sub.2.6H.sub.2O in 1 ml of water was added dropwise to the zeolite. The sample was then air dried for 24 hours at room temperature and then calcined in air at 450° C. for 4 hours.

[0089] In the reaction test according to Example 1, 570 μmol of methanol per gram of catalyst and 130 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour per hour were obtained,

Example 13: Mn-FER (TOSOH) Catalyst (Mn/Al 0.16)

[0090] Mn-FER zeolite, Si/Al 8.5, Mn/Al 0.16 was prepared by ion exchange with 0.05 M aqueous solution of Mn(NO.sub.3).sub.2 at 60° C. (1×12 h, 50 ml solution/1 g zeolite). After ion exchange, the zeolite was thoroughly washed and air dried at room temperature.

[0091] In the reaction test according to Example 1, 80 μmol of methanol per gram of catalyst and 15 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 14: Mn-FER (TOSOH) Catalyst (Mn/Al 0.28)

[0092] Mn-FER zeolite, Si/Al 8.5, Mn/Al 0.28, was prepared by ion exchange with 0.05 M aqueous solution of Mn(NO.sub.3).sub.2. 1.0 g of NH.sub.4-FER (TOSOH) was added to 100 ml of a 0.05 M aqueous solution of Mn(NO.sub.3).sub.2 and stirred at 70° C. for 12 hours. This procedure was repeated three times. After ion exchange, the obtained material was filtered off and washed thoroughly with distilled water and then dried at room temperature.

[0093] In the reaction test according to Example 1, 1500 μmol of methanol per gram of catalyst per hour and at the same time 350 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 15: Mn-FER (TOSOH) Catalyst (Mn/Al 0.35)

[0094] Mn-FER zeolite, Si/Al 8.5, Mn/Al 0.35, was prepared by impregnation with an aqueous solution of Mn(NO.sub.3).sub.2. A granulated sample of NH.sub.4-FER (TOSOH) (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min).

[0095] A solution containing 2.0 wt. % of Mn(NO.sub.3).sub.2.4H.sub.2O in an amount of 1 ml per gram of zeolite was added dropwise to the dried zeolite. The sample was then air dried for 24 hours at room temperature and then calcined in air at 450° C. for 4 hours.

[0096] In the reaction test according to Example 1, 1800 μmol of methanol per gram of catalyst per hour and at the same time 600 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 16: Co-*BEA Catalyst (Co/Al 0.30)

[0097] 1.0 g of zeolite NH.sub.4-beta with Si/Al 4.5 was added to 100 ml of a 0.05 M aqueous solution of Co(NO.sub.3).sub.2 and the mixture was stirred at room temperature for 12 hours. The zeolite was then filtered off and washed thoroughly with distilled water and dried at room temperature.

[0098] In the reaction test according to Example 1, 450 μmol of methanol per gram of catalyst per hour and at the same time 40 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 17: Co-*BEA Catalyst (Co/Al 0.50)

[0099] 1.0 g of zeolite NH.sub.4-beta with Si/Al 4.5 was added to 100 ml of a 0.05 M aqueous solution of CoAc.sub.2 and the mixture was stirred at room temperature for 12 hours. This procedure was repeated three times. The zeolite was then filtered off and washed thoroughly with distilled water and dried at room temperature.

[0100] Subsequently, the material was heated to 450° C. in a stream of air for 24 hours.

[0101] In the reaction test according to Example 1, 550 μmol of methanol per gram of catalyst per hour and at the same time 40 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 18: Fe-SSZ-13 Catalyst (Fe/Al 0.1)

[0102] Fe-SSZ-13 zeolite, Si/Al 4.5, Fe/Al 0.1 was prepared by impregnation with acetylacetone. A granulated sample of NH.sub.4-SSZ-13 (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). To 1 g of dehydrated zeolite an impregnation solution composed of 0.10 g of FeCl.sub.3 and 1.70 g of AcAc was added and left overnight at room temperature. The next day, the excess impregnation solution was removed by filtration. The sample thus prepared was heated under dynamic vacuum as follows: 1 h at 100° C. and then 3 h at 350° C. (heating rate 4° C./min). After cooling to room temperature, the sample was filtered off and washed with distilled water, then dried at room temperature and calcined in air at 450° C. for 24 hours.

[0103] In the reaction test according to Example 1, 250 μmol of methanol per gram of catalyst and at the same time ˜30 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 19: Fe-SSZ-13 Catalyst Fe/Al 0.15

[0104] SSZ-13 zeolite, Si/Al 5.5 Fe/Al 0.15 was prepared by impregnation with acetylacetone. A granulated sample of NH.sub.4-SSZ-13 (particle size from 600 to 300 μm) was dehydrated for 4 hours at 120° C. in a stream of air (25 ml/min). To 1 g of dehydrated zeolite an impregnation solution composed of 0.10 g of FeCl.sub.3 and 1.70 g of AcAc was added and left overnight at room temperature. The next day, the excess impregnation solution was removed by filtration. The sample thus prepared was heated under dynamic vacuum as follows: 1 h at 100° C. and then 3 h at 350° C. (heating rate 4° C./min). After cooling to room temperature, the sample was thoroughly filtered off and washed with distilled water, then dried at room temperature and calcined in air at 450° C. for 24 hours.

[0105] In the reaction test according to Example 1, 220 μmol of methanol per gram of catalyst and at the same time ˜30 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 20: Fe-FER (HI) Catalyst (Fe/Al 0.28)

[0106] Fe-ferrierite, Si/Al 9, Fe/Al 0.28 was prepared by ion exchange with aqueous FeSO.sub.4 solution. 1 g of the sample was changed twice for 12 h with 100 ml of 0.05 M FeSO.sub.4 solution. Before preparing the solution, oxygen was removed from the distilled water used by bubbling with a stream of nitrogen for 1 hour. The ion exchange took place in a closed vessel and under a nitrogen atmosphere. The sample was then centrifuged under nitrogen and dried in a stream of nitrogen at room temperature.

[0107] In the reaction test according to Example 1, 800 μmol of methanol per gram of catalyst per hour and 50 μmol of a mixture of formaldehyde and dimethyl ether per gram of catalyst per hour were obtained.

Example 21: Comparison of the Catalysts of the Present Invention with the Cu-FER Catalyst of the Publication Pappas et al., ChemCatChem 2019, 11, 621-627

[0108] The catalysts prepared according to Examples 8 and 11 of the present invention were compared with the Cu-FER catalyst according to the above publication. The test was performed according to Example 1. The Cu-FER catalyst of the prior art had a Cu to Al ratio of 0.2, a Si to Al ratio of 10 and an hourly yield of methanol per gram of this catalyst was very low. In comparison, the production of methanol per cycle for the catalysts according to the present invention was about 10 times higher and with regard to the possibility of repeating the production cycle in the case of the present invention up to 4 times per hour, with regard to the very long cycle in said publication (about 18 hours), the process according to the present invention gives incomparably higher average hourly methanol production.