EA041593B1 - METHOD FOR DIRECT PRODUCTION OF DIMETHYL ETHER FROM SYNTHESIS GAS - Google Patents

Description

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a process for the direct production of dimethyl ether from synthesis gas.

State of the art of the present invention

Dimethyl ether (CH ₃ OCH ₃ , DME) is a non-toxic, harmless and non-corrosive chemical compound. Due to its high cetane number, the absence of nitrogen and sulfur in the composition, good compatibility with diesel fuel and other advantages, dimethyl ether is a very promising and clean diesel fuel additive. In terms of its physical and chemical properties, dimethyl ether is very close to liquefied petroleum gas and is widely used as a domestic fuel. In recent years, coal-to-ethanol technology, such as coal-to-dimethyl ether conversion followed by carbonylation and hydrogenation to produce anhydrous ethanol, has always been a hot topic of research in the coal chemical industry. Thus, dimethyl ether will find wide application in the technology of ethanol synthesis as a fuel in the future. At present, dimethyl ether is produced commercially, mainly through the reaction of methanol dehydration with solid acid catalysts. As is known, methanol is synthesized using mainly synthesis gas and copper zinc aluminum complex oxide (CuZnAlOx) as the methanol synthesis catalyst. In order to save on capital investment and reduce energy consumption, attempts are being made to directly convert syngas to dimethyl ether. According to numerous reports on the direct production of dimethyl ether from synthesis gas, the basis of most research is a solid acid composite catalyst containing CuZnAlOx/acid molecular sieve or γ-Α12Ο ₃ . Methanol synthesis catalysts are generally used at temperatures below 250°C, but the solid acid catalyst for the methanol dehydration reaction must be used at temperatures above 250°C in order to exhibit good performance. Thus, the usual operating temperature of composite catalysts is in the range from 250 to 300°C. Under high-temperature reaction conditions, the stability of the composite catalyst becomes unsatisfactory, it becomes impossible to regenerate CuZnAlOx, and as a result, the direct synthesis of dimethyl ether from synthesis gas has not been realized on an industrial scale so far.

Brief summary of the present invention

In order to solve the problems of the prior art, the authors of the present application have conducted a thorough study. As a result, it has been found that spinel type zinc alumina double oxide is very suitable as a catalyst for the direct production of dimethyl ether from synthesis gas. By using this catalyst, the process for directly producing dimethyl ether from synthesis gas can convert the resulting synthesis gas into dimethyl ether with high selectivity. This catalyst is not only stable, but can also be regenerated to thereby reduce the high energy consumption resulting from multi-stage production. The inventors have completed the present invention based on the above findings.

Thus, one object of the present invention is to provide a process for the direct production of dimethyl ether from synthesis gas, wherein the synthesis gas is passed through a reaction zone containing a catalyst and reacted under conditions sufficient to convert at least a portion of synthesis gas as a starting material and obtaining a reaction product containing dimethyl ether; and dimethyl ether is isolated from the reaction product;

moreover, the catalyst is a double oxide of zinc and aluminum type spinel.

According to one embodiment, the reaction zone comprises one fixed bed reactor or a plurality of fixed bed reactors connected in series and/or in parallel.

According to one embodiment, the reaction is carried out under the following conditions: reaction temperature in the range of 300 to 450°C, reaction pressure in the range of 0.5 to 10.0 MPa, molar ratio of hydrogen and carbon monoxide in the synthesis gas in the range of 1: 9 to 9:1 and space hourly rate of supply of synthesis gas under standard conditions in the range from 1000 to 20000 h ^-1 .

Description of Preferred Embodiments

The present invention provides a process for the direct production of dimethyl ether from synthesis gas, wherein the synthesis gas is passed through a reaction zone containing a catalyst and reacted under conditions sufficient to convert at least a portion of the synthesis gas as a feedstock and obtain a reaction product containing dimethyl ether; and dimethyl ether is isolated from the reaction product, the catalyst being a double oxide of zinc and aluminum of the spinel type.

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Catalyst for the production of dimethyl ether

As mentioned above, the catalyst used in the process of the present invention is a spinel-type zinc-aluminum double oxide.

The molar ratio of Zn/Al in the spinel zinc-alumina double oxide of the present invention is any ratio, preferably Zn/Al is 1:9 to 1:1, for example, Zn/Al is 1:1, 1:2, 1 :4.5 or 1:9.

In some embodiments, the crystal size of the zinc-aluminum spinel in spinel-type zinc-aluminum double oxide is less than or equal to 30 nm.

In some embodiments, the spinel-type zinc-alumina double oxide further comprises at least one additional element selected from chromium, zirconium, copper, manganese, indium, gallium, and silicon. At least one additional element is added to the spinel-type zinc-alumina double oxide by impregnation and/or co-precipitation using a salt solution of at least one additional element. Preferably, the weight fraction of at least one additional element in the spinel-type zinc-alumina double oxide is less than or equal to 10%, for example 1, 3, 5, 7, 9 or 10%.

In one embodiment, a spinel-type zinc/aluminum double oxide is produced by a precipitation and calcination process. For example, a spinel-type zinc-aluminum double oxide is obtained by carrying out the steps in which a zinc salt and an aluminum salt are brought into a mixed aqueous solution of metal salts; the mixed aqueous metal salt solution is brought into contact with the aqueous solution of the precipitating agent so as to co-precipitate the metal ions from the mixed aqueous metal salt solution, followed by aging; the resulting precipitate is washed, followed by drying, and then calcined to obtain spinel-type zinc-aluminum double oxide. Examples of the precipitating agent are, but are not limited to, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide, and mixtures thereof.

In one embodiment, the temperature during coprecipitation is in the range of 20 to 95°C, the pH during coprecipitation is in the range of 7.0 to 9.0, the holding time is at least 1 hour, and the calcination temperature is in the range of 450 to 800°C.

According to a specific embodiment, a spinel-type zinc-aluminum double oxide is prepared as follows: a zinc salt and an aluminum salt in any ratio are dissolved in deionized water to form a mixed aqueous solution of metal salts, and the concentration of the mixed aqueous solution of metal salts can be any concentration, and the mixture metal salts are completely dissolved in deionized water at room temperature; the precipitant is dissolved in deionized water to form an aqueous solution of the precipitant, and the concentration of the aqueous solution of the precipitant may be any concentration at which the precipitant is completely dissolved in the deionized water at room temperature; the mixed aqueous solution of metal salts is brought into contact with the aqueous solution of the precipitating agent so as to co-precipitate metal ions from the mixed aqueous solution of metal salts at a temperature in the range from 20 to 95°C, the pH being adjusted in the range from 7.0 to 9 .0 by adjusting the flow rate of the mixed aqueous solution of metal salts and the aqueous solution of the precipitant during co-precipitation; after co-precipitation is complete, a holding step is carried out at a temperature in the range of 20 to 95°C for a time in the range of 1 to 24 hours, followed by centrifugal separation, washing with deionized water, drying at 100°C for 24 hours, and finally , calcining at a temperature in the range from 450 to 800°C for a time in the range from 2 to 10 hours to obtain double oxide of zinc and aluminum type spinel.

According to the present invention, there are no particular restrictions on the types of zinc salt, aluminum salt and salt of at least one additional element, provided that they are soluble in water. For example, any of them has a solubility in water above 1 g/l at 25°C. Examples of zinc salts, aluminum salts, and salts of at least one additional element are, but are not limited to, chloride, sulfate, and nitrate.

In the method according to the present invention, there are no particular restrictions on methods for contacting a mixed aqueous solution of metal salts with an aqueous solution of a precipitant. According to a particular embodiment, contact can be achieved by parallel injection, direct injection, or countercurrent injection.

Method for producing dimethyl ether from synthesis gas

As mentioned above, the synthesis gas is contacted with the catalyst in the reaction zone under reaction conditions sufficient to convert at least a portion of the synthesis gas feed and produce a reaction product containing dimethyl ether.

Without intending to be bound by any particular theory, the authors believe that in the direct synthesis of dimethyl ether from synthesis gas, a number of reaction processes have been carried out, such as

1) methanol synthesis reaction: CO + 2H ₂ = CH ₃ OH;

2) the reaction of dehydration of methanol into dimethyl ether: 2CH ₃ OH = DME +H ₂ O;

3) water gas shift reaction: CO + H ₂ O = CO ₂ + H ₂ .

The term synthesis gas as used herein means a mixed gas containing hydrogen and carbon monoxide. In the feed synthesis gas, the molar ratio of hydrogen and carbon monoxide may be in the range of 1:9 to 9:1, preferably in the range of 1:9 to 1:1.

Since the main side reaction in the direct synthesis of dimethyl ether from syngas is the water gas shift reaction, which is a typical equilibrium reaction, the addition of carbon dioxide is beneficial for inhibiting the water gas shift reaction and improving the carbon monoxide utilization rate. Thus, the synthesis gas in the process according to the present invention may also contain carbon dioxide. The molar concentration of carbon dioxide in the synthesis gas is in the range from 1.0 to 20.0%. For example, the molar concentration of carbon dioxide in the synthesis gas may be 1, 3, 5, 8, 10, 13, 15, 17, or 20%.

In the method according to the present invention, the reaction zone may contain one or more fixed bed reactors. The fixed bed reactor(s) can be operated continuously. When a plurality of fixed bed reactors are in operation, these reactors may be connected in series, in parallel, or in a combination of series and parallel connections.

According to one embodiment, the reaction is carried out under the following conditions: reaction temperature in the range of 300 to 450°C, reaction pressure in the range of 0.5 to 10.0 MPa, molar ratio of hydrogen and carbon monoxide in the synthesis gas in the range of 1: 9 to 9:1, and the volumetric flow rate of synthesis gas under standard conditions in the range from 1000 to 20000 h ^-1 .

According to one preferred embodiment, the reaction conditions are carried out under the following conditions: reaction temperature in the range of 310 to 360° C., reaction pressure in the range of 1.0 to 4.0 MPa, molar ratio of hydrogen and carbon monoxide in the synthesis gas in the range of 3:1 to 6:1, and the volumetric flow rate of synthesis gas under standard conditions in the range from 3000 to 8000 h ^-1 .

Separation of the reaction product

In the method according to the present invention, the separation of dimethyl ether from the reaction product containing dimethyl ether can be carried out in a well-known manner.

According to the present invention, the following beneficial effects are achieved.

1) According to the present invention, a single catalyst is used, which is spinel-type zinc-alumina dioxide, by which dimethyl ether can be obtained from synthesis gas with high selectivity, and this catalyst has good stability and can be regenerated.

2) By adding carbon dioxide, the water gas shift reaction can be effectively inhibited and a high utilization rate of carbon monoxide can be ensured.

3) The method according to the present invention provides a single-stage production of dimethyl ether from synthesis gas, thereby reducing the large energy consumption associated with multi-stage production.

Brief description of the figures

In FIG. 1 is an x-ray diffraction pattern of material A according to Example 1 of the present application, FIG. 2 is a transmission electron microscopy (TEM) image of material A according to example 1 of the present application.

Detailed disclosure of the present invention

The present invention is described in detail in the following examples, but the present invention is not limited to these examples.

Unless otherwise stated, the raw materials used in the examples of this application were purchased on a commercial basis.

In the examples, automatic analysis was performed using an Agilent 7890 gas chromatograph containing a gas sampler, a catalytic thermal detector attached to a packed TDX-1 column, and a flame ionization detector attached to a PLOT-Q capillary column.

In the examples, conversion ratio and selectivity are calculated based on the number of moles of carbon. Carbon monoxide conversion ratio = [(moles of carbon monoxide in the feed) - (moles of carbon monoxide in the product)]/(moles of carbon monoxide in the feed) x 100 %;

selectivity to dimethyl ether = (number of carbon moles of dimethyl ether

- 3 041593 in the product) / (total number of moles of carbon of all hydrocarbons, methanol and dimethyl ether in the product) x 100%;

selectivity to methanol ethers = (number of carbon moles of methanol in the product)/(total moles of carbon of all hydrocarbons, methanol and dimethyl ether in the product) x 100%;

selectivity to hydrocarbons = (number of carbon moles of hydrocarbons in the product)/(total moles of carbon of all hydrocarbons, methanol and dimethyl ether in the product) x 100%;

selectivity to carbon dioxide = (number of moles of carbon dioxide produced in the reaction)/(number of moles of carbon monoxide reacted) x 100%.

Obtaining double oxide of zinc and aluminum of spinel type

Example 1

95 g of Zn(NO ₃ ) ₂ -6H2O and 80 g of Al(NO ₃ )y9H ₂ O were dissolved in 200 ml of deionized water to form a salt solution. Dissolve 25 g of ammonium carbonate in 200 ml of deionized water to form an alkaline solution. The salt solution and the alkaline solution were mixed in co-current mode using two peristaltic pumps, respectively, and co-precipitated, the precipitation reaction temperature being set at 60° C., the pH value being 7.2. Then, a holding step at 60° C. for 4 hours was carried out, followed by filtration, washing, drying at 100° C. for 24 hours, and then calcination at 500° C. for 4 hours to obtain spinel-type zinc-aluminum double oxide, which was designated A. X-ray fluorescence spectroscopy (XRF) shows that the Zn/Al molar ratio in A is 1:1, the X-ray diffraction pattern of A is shown in FIG. 1 and the corresponding TEM image is shown in FIG. 2.

Example 2

48 g of Zn(NO ₃ )2-6H2O and 80 g of Α1(ΝΟ ₃ ) ₃ ·9Η ₂ Ο were dissolved in 200 ml of deionized water to form a salt solution. Dissolve 25 g aqueous ammonia (containing 25% NH3) in 200 ml deionized water to form an alkaline solution. The salt solution and the alkaline solution were mixed in co-current mode using two peristaltic pumps, respectively, and co-precipitated, the precipitation reaction temperature being set at 70° C., the pH value being 7.5. Then, a holding step at 70° C. for 6 hours was carried out, followed by filtration, washing, drying at 100° C. for 24 hours, and then calcination at 500° C. for 4 hours to obtain spinel-type zinc-aluminum double oxide, which was denoted by the letter B. XPS showed that the molar ratio of Zn/Al in B is 1:2.

Example 3

10.6 g of Zn(NO ₃ )^6H2O and 80 g of Α1(ΝΟ ₃ ) ₃ ·9Η ₂ Ο were dissolved in 200 ml of deionized water to form a salt solution. Dissolved 25 g of carbonate in 200 ml of deionized water with the formation of an alkaline solution. The salt solution and the alkaline solution were mixed in co-current mode using two peristaltic pumps, respectively, and co-precipitated, the precipitation reaction temperature being set at 80° C., the pH value being 7.8. Then, a holding step at 80° C. for 6 hours was carried out, followed by filtration, washing, drying at 100° C. for 24 hours, and then calcination at 500° C. for 6 hours to obtain spinel-type zinc-aluminum double oxide, which was denoted by the letter C. XPS showed that the molar ratio of Zn/Al in C is 1:9.

Example 4

10.6 g of Zn(NO ₃ ) ₂ ^6H ₂ O and 80 g of Α1(ΝΟ ₃ ) ₃ ·9Η ₂ Ο were dissolved in 200 ml of deionized water to form a salt solution. Dissolved 15 g of carbonate in 200 ml of deionized water with the formation of an alkaline solution. The salt solution and the alkaline solution were mixed in co-current mode using two peristaltic pumps, respectively, and co-precipitated, the precipitation reaction temperature being set at 70° C., the pH value was 7.1. Then, a holding step at 70° C. for 6 hours was carried out, followed by filtration, washing, drying at 100° C. for 24 hours, and then calcination at 500° C. for 4 hours to obtain spinel-type zinc-aluminum double oxide, which was denoted by the letter D. XPS showed that the molar ratio of Zn/Al in D is 1:4.5.

Example 5

7.7 g of Cr(NO ₃ ) ₃ 9H ₂ O was dissolved in 15 ml of deionized water, and then 20 g of catalyst B was impregnated with this solution at room temperature for 24 h, followed by drying at 100°C for 24 h and calcining at 500° C. for 4 hours to obtain a spinel-type zinc-aluminum double oxide containing 5 wt. % chromium, which was designated E.

Example 6

4.7 g of Zr(NO ₃ )4 5H ₂ O was dissolved in 15 ml of deionized water, and then 20 g of catalyst B was impregnated with this solution at room temperature for 24 h, after which drying was carried out at 100°C. for 24 hours and calcination at 500°C for 4 hours to obtain a 5 wt.% zirconium-containing double oxide of zinc and aluminum of the spinel type, which was designated by the letter F.

Catalyst Performance Evaluation

Example 7

Catalyst A was crushed and sieved to give particles ranging in size from 0.4 to 0.8 mm. 2 g of the resulting particles were loaded into a stainless steel reaction tube having an inner diameter of 8 mm and activated in a flow of 50 ml/min of hydrogen at 300° C. for 1 hour. The reaction was carried out under the following conditions: the reaction temperature (T) was 320° C, the reaction pressure (P) was 4.0 MPa, the molar ratio of hydrogen and carbon monoxide in the synthesis gas (H ₂ :CO) was 3:1, the space hourly space velocity of the synthesis gas under standard conditions (GHSV) was 6000 h ^-1 . After 500 hours of reaction, the product was analyzed by gas chromatography. The results of the reaction are presented in table. 1.

Examples 8-12.

The reaction conditions and the reaction results are presented in table. 1. Other procedures are the same as in example 7.

Example 13

Catalyst A was crushed and sieved to give particles ranging in size from 0.4 to 0.8 mm. 2 g of the resulting particles were loaded into a stainless steel reaction tube having an inner diameter of 8 mm and activated in a flow of 50 ml/min of hydrogen at 300° C. for 1 hour. The reaction was carried out under the following conditions: the reaction temperature (T) was 320° C, the reaction pressure (P) was 4.0 MPa, the molar ratio of hydrogen, carbon monoxide and carbon dioxide in the synthesis gas (H2:CO:CO2) was 3:1:0.04 (thus, the content of CO2 in the synthesis gas was 1%), the space hourly rate of supply of synthesis gas under standard conditions (GHSV) was 6000 h ^-1 . After reaction for 500 hours, the product was analyzed by gas chromatography. The results of the reaction are presented in table. 1.

Example 14

Catalyst A was crushed and sieved to give particles ranging in size from 0.4 to 0.8 mm. 2 g of the resulting particles were loaded into a stainless steel reaction tube having an inner diameter of 8 mm and activated in a flow of 50 ml/min of hydrogen at 300° C. for 1 hour. The reaction was carried out under the following conditions: the reaction temperature (T) was 320° C, the reaction pressure (P) was 4.0 MPa, the molar ratio of hydrogen, carbon monoxide and carbon dioxide in the synthesis gas (H2:CO:CO2) was 3:1:0.2 (thus, the content of CO2 in the synthesis gas was 4.8%), the space hourly velocity of the supply of synthesis gas under standard conditions (GHSV) was 6000 h ^-1 . After 500 hours of reaction, the product was analyzed by gas chromatography. The results of the reaction are presented in table. 1.

Example 15

Catalyst A was crushed and sieved to give particles ranging in size from 0.4 to 0.8 mm. 2 g of the resulting particles were loaded into a stainless steel reaction tube having an inner diameter of 8 mm and activated in a flow of 50 ml/min of hydrogen at 300° C. for 1 hour. The reaction was carried out under the following conditions: the reaction temperature (T) was 320° C, the reaction pressure (P) was 4.0 MPa, the molar ratio of hydrogen, carbon monoxide and carbon dioxide in the synthesis gas (H ₂ :CO:CO ₂ ) was 3:1:1 (thus, the content of CO2 in the synthesis gas was 20%), the space hourly rate of supply of synthesis gas under standard conditions (GHSV) was 6000 h ^-1 . After 500 hours of reaction, the product was analyzed by gas chromatography. The results of the reaction are presented in table. 1.

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Table 1

The results of the catalytic reaction in examples 7-15

Example Catalyst Reaction conditions CO conversion ratio (%) Selectivity towards dimethyl ether (%) Selectivity to methanol (%) Selectivity towards hydrocarbons (%) Selectivity towards CO ₂ (%) 7 A T = 320°C; P = 4.0 MPa; GHSV = 6000 h ¹ ; H ₂ : CO \u003d 3: 1 18.2 87.6 12.3 0.1 31.4 8 IN T = 360°C; P = 6.0 MPa; GHSV = 10000 h ¹ ; H ₂ : C0 \u003d 5: 1 25.7 90.3 9.5 0.2 28.7 9 WITH T = 370°C; P = 2.0 MPa; GHSV = 3000 h ¹ ; H ₂ : CO \u003d 6: 1 28.9 88.5 11.2 0.3 29.0 10 D T = 400°C; P = 8.0 MPa; GHSV = 15000 h ¹ ; H ₂ : CO \u003d 2: 1 17.5 82.4 17.2 0.4 35.7 AND E T = ZOO: P = 0.5 MPa; GHSV = 1000 h ¹ ; H ₂ : CO \u003d 9: 1 16.8 80.6 19.3 0.1 22.9 12 F T = 450°C; 2.1 82.4 17.3 0.3 20.0 P= 10.0 MPa; GHSV = 20000 h ¹ ; H ₂ : CO \u003d 1: 9 13 A T = 320°C; P = 4.0 MPa; GHSV = 6000 h'; H ₂ : CO: CO ₂ \u003d 3: 1: 0.04 17.2 86.5 13.4 0.1 23.1 14 A T = 320°C; P = 4.0 MPa; GHSV = 6000 h'; H ₂ : CO: CO ₂ \u003d 3: 1: 0.2 10.3 84.4 15.5 0.1 14.2 15 A T = 320°C; P = 4.0 MPa; GHSV = 6000 h'; H ₂ : CO: CO ₂ \u003d 3: 1: 1 8.8 83.5 16.4 0.1 3.2

Evaluation of performance characteristics of the regenerated catalyst

Example 16

The deactivated catalyst in example 7 was treated with a mixture containing 2 vol.% oxygen and 98 vol.% nitrogen at 550°C for 10 h to obtain a catalyst after one regeneration cycle and catalyze the reaction under the reaction conditions of example 7. Five regeneration cycles were carried out in the same way, and as a comparison, the catalytic activity data after the reaction for 500 hours in each cycle was chosen. The results are presented in table. 2.

table 2

The results of the catalytic reaction in example 16

Number of regeneration cycles CO conversion ratio (%) Selectivity to dimethyl ether (%) Selectivity to methanol (%) Selectivity to hydrocarbons (%) Selectivity towards CO ₂ (%) Service life per regeneration cycle (h) 1 17.9 88.6 11.3 0.1 31.0 8500 2 17.6 88.0 11.9 0.1 30.9 8700 3 17.7 87.3 12.6 0.1 30.0 8400 4 17.3 84.5 15.4 0.1 29.8 8500 5 16.9 83.8 16.1 0.1 29.7 8600

The above are just a few examples of the present invention, but it is not intended

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Claims (9)

to limit the present invention in any way. Although the present invention is disclosed in relatively preferred examples, they are not intended to limit the present invention. Without departing from the technical solutions of the present invention using the technical solutions described above, specialists in the art can make some variations or modifications, all of which are equivalent embodiments of the present invention and are within the scope of the technical solutions of the present invention. CLAIM 1. A method for the direct production of dimethyl ether from synthesis gas, in which: a) synthesis gas is passed through a reaction zone containing a catalyst and reacted under conditions sufficient to convert at least a portion of the synthesis gas feed and produce a reaction product containing dimethyl ether; And b) dimethyl ether is isolated from the reaction product; wherein the sole catalyst is a spinel zinc aluminum oxide, and wherein the Zn/Al molar ratio of the spinel zinc aluminum oxide is from 1:9 to 1:1. 2. The method according to claim 1, in which double oxide of zinc and aluminum, which is a spinel, is obtained by carrying out the stage in which the zinc salt and the aluminum salt are transferred into a mixed aqueous solution of metal salts; the mixed aqueous metal salt solution is brought into contact with the aqueous solution of the precipitating agent so as to co-precipitate the metal ions from the mixed aqueous metal salt solution, followed by aging; the resulting precipitate is washed, followed by drying, and then calcined to obtain double oxide of zinc and aluminum, which is a spinel. 3. The method of claim 2, wherein the method has at least one of the following characteristics: the zinc salt and the aluminum salt are selected from chloride, sulfate and nitrate; the precipitating agent is selected from sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, ammonium bicarbonate, aqueous ammonia, sodium hydroxide, potassium hydroxide and mixtures thereof; coprecipitation is carried out at a temperature in the range from 20 to 95°C; the pH value during co-precipitation is in the range from 7.0 to 9.0; the duration of exposure is at least 1 hour; and calcination is carried out at a temperature in the range from 450 to 800°C. 4. The method of claim 1 wherein at least one additional element selected from chromium, zirconium, copper, magnesium, indium, gallium and silicon is added to the spinel zinc alumina double oxide by impregnation and/or co-precipitation using a salt solution of at least one additional element, and the mass fraction of at least one additional element in the double oxide of zinc and aluminum, which is spinel, is less than or equal to 10%. 5. The method of claim 4 wherein the salt of at least one additional element is selected from chloride, sulfate and nitrate. 6. The method of claim 1, wherein the reaction zone comprises one fixed bed reactor or a plurality of fixed bed reactors connected in series and/or in parallel. 7. The method according to claim 1, in which the following reaction conditions are used: reaction temperature in the range from 300 to 450°C, reaction pressure in the range from 0.5 to 10.0 MPa, molar ratio of hydrogen and carbon monoxide in synthesis gas in the range from 1:9 to 9:1 and the volumetric rate of supply of synthesis gas under standard conditions in the range from 1000 to 20000 h ^-1 . 8. The method according to claim 7, in which the following reaction conditions are used: reaction temperature in the range from 310 to 360 ° C, reaction pressure in the range from 1.0 to 4.0 MPa, the molar ratio of hydrogen and carbon monoxide in synthesis gas in the range from 3:1 to 6:1 and the volumetric rate of supply of synthesis gas under standard conditions in the range from 3000 to 8000 h ^-1 . 9. The method of claim 1, wherein the synthesis gas contains carbon dioxide and the molar concentration of carbon dioxide in the synthesis gas is in the range of 1.0 to 20.0%. -