Supported metal oxide catalytic material, preparation method and application thereof, and method for preparing methanol through carbon dioxide hydrogenation

Abstract

The invention relates to the technical field of methanol preparation through carbon dioxide hydrogenation, and discloses a supported metal oxide catalytic material, a preparation method and application thereof, and a method for preparing methanol through carbon dioxide hydrogenation. The invention relates to a supported metal oxide catalytic material, the supported metal oxide catalytic material comprises a magnesium oxide carrier and active components supported on the magnesium oxide carrier, the active components comprise a first active component copper and a second active component, and the second active component is selected from at least one of iron, cobalt and nickel; the average particle size of the magnesium oxide carrier is 100-500 nm; the average particle size of the active component is less than 10nm. According to the supported metal oxide catalytic material, magnesium oxide is used as a carrier to cooperate with an active component, the dispersity of the active component is improved, the production cost is reduced, and meanwhile the conversion rate of reaction raw materials for preparing methanol through carbon dioxide hydrogenation and the selectivity of target product methanol are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of carbon dioxide hydrogenation to methanol, in particular to a supported metal oxide catalytic material and a preparation method and application thereof, and a method for carbon dioxide hydrogenation to methanol. BACKGROUND

[0002] Carbon reduction chemical processes can reduce the amount of carbon dioxide emissions in industrial production. However, for some reactions, carbon dioxide as a product or byproduct is difficult to avoid. Therefore, the resource utilization of carbon is an indispensable part of achieving the goal of carbon neutrality. From another perspective, carbon dioxide as a cheap and readily available, environmentally friendly renewable carbon resource, its resource utilization not only reduces carbon dioxide emissions, but also provides a green preparation technology route, which is of great significance to green and sustainable development. Methanol is a basic organic chemical raw material and has a wide range of uses.

[0003] Methanol can be used to synthesize fibers, formaldehyde, plastics, medicines, pesticides, dyes, synthetic proteins and other chemical products. Methanol can also be used as a liquid fuel for direct methanol fuel cells (DMFC) and improved diesel engines. Methanol can also release hydrogen by cracking, thus becoming a carrier for hydrogen storage. Methanol has a simple molecular structure, and the process of preparing methanol from carbon dioxide is relatively easy to implement, so methanol is one of the ideal products obtained from CO2 reduction. By preparing methanol from carbon dioxide, green manufacturing of chemical products can be achieved based on the existing C1 chemical system, so methanol is expected to become an important direction for CO2 resource utilization. SUMMARY

[0004] The purpose of the present application is to overcome the problems existing in the prior art, provide a supported metal oxide catalytic material and a preparation method and application thereof, and a method for carbon dioxide hydrogenation to methanol. The supported metal oxide catalytic material uses magnesium oxide as a carrier to cooperate with active components, improves the dispersion of active components, reduces production costs, and improves the conversion rate of raw materials and the selectivity of target product methanol in the reaction of carbon dioxide hydrogenation to methanol.

[0005] To achieve the above-mentioned purpose, the first aspect of the present application provides a supported metal oxide catalytic material, wherein the supported metal oxide catalytic material comprises a magnesium oxide carrier and an active component supported on the magnesium oxide carrier, the active component comprises a first active component copper and a second active component, and the second active component is selected from at least one of iron, cobalt and nickel; the average particle size of the magnesium oxide carrier is 100-500 nm; and the average particle size of the active component is less than 10 nm.

[0006] Preferably, the average particle size of the magnesium oxide carrier is 100-200 nm.

[0007] Preferably, the CO2-TPD desorption temperature of the supported metal oxide catalytic material is 50-500℃, and further preferably 200-300℃.

[0008] The second aspect of the present application provides a preparation method of a supported metal oxide catalytic material, wherein the method comprises the following steps:

[0009] (1) performing a hydrothermal reaction on dispersion liquid A containing a first active component copper precursor and a magnesium oxide carrier in the presence of an alkaline compound;

[0010] (2) performing a co-precipitation reaction on dispersion liquid B containing the hydrothermal reaction product and a second active component precursor in the presence of a precipitant, and then performing drying and calcination;

[0011] The second active component is selected from at least one of iron, cobalt and nickel, and is preferably cobalt;

[0012] The average particle size of the magnesium oxide carrier is 100-500 nm.

[0013] The third aspect of the present application provides an application of the supported metal oxide catalytic material of the first aspect or the supported metal oxide catalytic material prepared by the preparation method of the second aspect in a carbon dioxide hydrogenation reaction for preparing methanol.

[0014] The fourth aspect of the present application provides a method for preparing methanol by carbon dioxide hydrogenation, wherein the method comprises: performing a hydrogenation reaction on reaction raw materials carbon dioxide and hydrogen in the presence of a catalytic material, and the catalytic material is the supported metal oxide catalytic material of the first aspect or the supported metal oxide catalytic material prepared by the preparation method of the second aspect.

[0015] The supported metal oxide catalytic material provided by the present application can improve the selectivity of the target product of the carbon dioxide hydrogenation reaction for preparing methanol and the conversion rate of carbon dioxide on the one hand, and can reduce the production cost on the other hand, thereby providing a new catalytic material for the carbon dioxide hydrogenation reaction for preparing methanol, and the selectivity of the target product methanol can reach more than 95%.

[0016] The supported metal oxide catalytic material provided by the present application uses magnesium oxide with a specific average particle size as a carrier to cooperate with the active component, promotes the dispersion of the active component, improves the dispersion degree of the active component, makes the active component have good dispersion degree, improves the selectivity of the target product of the carbon dioxide hydrogenation reaction for preparing methanol and the conversion rate of the raw material carbon dioxide.

[0017] The supported metal oxide catalytic material provided by the application has preferably high carbon dioxide adsorption capacity, the active component has stronger interaction with carbon dioxide molecules, and the selectivity of the target product of the carbon dioxide hydrogenation to methanol reaction and the conversion rate of the raw material carbon dioxide are improved.

[0018] The preparation method provided by the application has the advantages that the active component is grown in situ on the magnesium oxide carrier with a specific average particle size, and is converted into the active component oxide with high carbon dioxide hydrogenation to methanol catalytic activity by calcination, which is beneficial to improving the activity; and the magnesium oxide is used as the carrier, and the production cost can be reduced.

[0019] The preparation method provided by the application has the advantage that by controlling the addition sequence of the active components, the first active component copper is first loaded on the magnesium oxide carrier, and then the second active component is loaded, so that the first active component copper is more uniformly dispersed on the magnesium oxide carrier, and the dispersion degree of the active component is improved.

[0020] The preparation method provided by the application has the advantage that preferably, the in-situ deposition and subsequent calcination treatment conditions can effectively adjust the active component-carrier interaction, form a bimetallic active center, and be beneficial to improving the conversion rate of carbon dioxide in the carbon dioxide hydrogenation to methanol reaction. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 FIG. 1 is a particle size distribution diagram of the active component of the supported metal oxide catalytic material of Example 1;

[0022] Figure 2 FIG. 2 is a CO2-TPD curve diagram of the supported metal oxide catalytic material of Example 1. DETAILED DESCRIPTION

[0023] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The ranges or values should be construed to be roughly about the ranges or values. For values comprising a range, the endpoints of the ranges are not included between the individual values, the endpoints of the ranges and the individual values, and the individual values are not included between themselves. New ranges or values can be formed by combining the endpoints of the ranges or values with each other, and these new ranges or values should be considered to be specifically disclosed herein.

[0024] The first aspect of the application provides a supported metal oxide catalytic material, wherein the supported metal oxide catalytic material comprises a magnesium oxide carrier and an active component loaded on the magnesium oxide carrier, the active component comprises a first active component copper and a second active component, the second active component is selected from at least one of iron, cobalt and nickel; the average particle size of the magnesium oxide carrier is 100-500 nm; and the average particle size of the active component is less than 10 nm.

[0025] The supported metal oxide catalytic material provided by the application can improve the selectivity of the target product of the carbon dioxide hydrogenation reaction and the conversion rate of carbon dioxide.

[0026] The supported metal oxide catalytic material provided by the application has good dispersion of the active component, and can improve the selectivity of the target product of the carbon dioxide hydrogenation reaction and the conversion rate of carbon dioxide.

[0027] In the application, the average particle size of the magnesium oxide carrier is measured by high-resolution transmission electron microscopy, and the test conditions are as follows: 50-100 magnesium oxide nanoparticles are randomly taken, the length of the longest side of the particle is measured, and then the average value is calculated as the average particle size of the magnesium oxide carrier.

[0028] In the application, the average particle size of the active component refers to the average particle size of the first active component copper and the second active component, and the average particle size of the active component is measured by high-resolution transmission electron microscopy, and the specific test conditions are as follows: 50-100 active component nanoparticles are randomly taken, the length of the longest side of the particle is measured, and then the average value is calculated as the average particle size of the active component.

[0029] In the application, preferably, the total loading amount of the active component in the supported metal oxide catalytic material is 5-15% in terms of elements based on the mass of the magnesium oxide carrier, and is further preferably 7.5-12%. The advantage of this preferred embodiment is that the active component-carrier interaction is optimal, and the catalytic activity is highest.

[0030] In the application, the loading amount of the active component is measured by inductively coupled plasma emission spectrometry.

[0031] In the application, preferably, the active component includes the first active component copper and the second active component cobalt. The advantage of this preferred embodiment is that the interaction strength between the active component and the reactants and reaction intermediates is optimized by compounding the active component, and the activity of the bimetallic oxide and the selectivity of the target product are improved.

[0032] In the present application, preferably, the ratio of the loadings of the first active component copper and the second active component cobalt is 4.5-10:1, further preferably 4.5-7.5:1, in terms of elements. The advantage of using this preferred embodiment is that the ratio of the loadings of the active components is optimal for the interaction of the active sites with the reactants and reaction intermediates, thereby improving the selectivity of the target product.

[0033] In the present application, preferably, the average particle size of the magnesium oxide carrier is 100-200 nm. The advantage of using this preferred embodiment is that the dispersion of the active components is promoted while ensuring that the bimetallic oxide has a suitable specific surface area, thereby improving the dispersion of the active components.

[0034] In the present application, preferably, the average particle size of the active components is 2-8 nm.

[0035] In the present application, preferably, the specific surface area of the supported metal oxide catalytic material is 500-800 cm 2 / g, further preferably 700-800 cm 2 / g. The advantage of using this preferred embodiment is that it is beneficial for the active components to be in full contact with the molecules of the reactants, thereby improving the conversion rate of the reaction raw materials and the selectivity of the target product.

[0036] In the present application, the specific surface area of the supported metal oxide catalytic material is measured by the nitrogen isothermal adsorption-desorption curve method.

[0037] In the present application, preferably, the CO2-TPD desorption temperature of the supported metal oxide catalytic material is 50-500℃, further preferably 200-300℃. The advantage of using this preferred embodiment is that the interaction between the metal active sites and the carbon dioxide molecules is moderate, when the carbon dioxide desorption temperature is too high, the carbon dioxide molecules are too strongly adsorbed, making it difficult to deoxidize and hydrogenate; when the temperature is too low, the active sites are difficult to adsorb and activate the carbon dioxide molecules.

[0038] In the present application, the TPD carbon dioxide desorption temperature of the bimetallic oxide refers to the temperature at which carbon dioxide begins to desorb from the surface of the catalytic material during the testing process, which is used to evaluate the adsorption properties of the catalytic material for carbon dioxide. The TPD carbon dioxide desorption temperature is used to indicate the strength of the interaction between the catalytic material and the molecules of the reactants.

[0039] In the present application, the TPD carbon dioxide desorption temperature of the bimetallic oxide is measured by the CO2-TPD method, specifically: the CO2-TPD test is carried out by heating the catalytic material, desorbing the adsorbed CO2 from the surface of the catalytic material, and then detecting and recording the temperature at which CO2 starts to desorb from the surface of the catalytic material during the desorption process. The specific test conditions are as follows: the CO2-TPD experiment uses helium as the carrier gas and carbon dioxide as the treatment gas. First, the inert gas is blown for 10-20 minutes at room temperature, the helium is blown at a temperature increasing rate of 10 degrees per minute, and then the temperature is kept constant for 1 hour before being reduced to 100 DEG C. Carbon dioxide is introduced, and the temperature is kept constant for 20-30 minutes. Helium is blown, and the temperature is reduced to room temperature. After the baseline is flat, the desorption is carried out under the programmed temperature conditions.

[0040] The second aspect of the present application provides a preparation method of a supported metal oxide catalytic material, wherein the method comprises the following steps:

[0041] (1) hydrothermal reaction of dispersion liquid A containing a first active component copper precursor and a magnesium oxide carrier in the presence of an alkaline compound;

[0042] (2) co-precipitation reaction of dispersion liquid B containing the hydrothermal reaction product and a second active component precursor in the presence of a precipitant, followed by drying and calcination;

[0043] The second active component is selected from at least one of iron, cobalt and nickel, and is preferably cobalt;

[0044] The average particle size of the magnesium oxide carrier is 100-500 nm.

[0045] The preparation method provided by the present application ensures the specific surface area of the supported metal oxide catalytic material while improving the dispersion of the active component by growing the active component in situ on the magnesium oxide carrier with a specific average particle size, and can prepare a supported metal oxide catalytic material with an average particle size of the active component less than 10 nm; further, the active component is converted into an active metal oxide with high carbon dioxide hydrogenation to methanol catalytic activity by calcination, which is beneficial to improve the activity; at the same time, using magnesium oxide as the carrier, the cost is low, which can reduce the production cost of the supported metal oxide catalytic material.

[0046] The preparation method provided by the present application controls the addition sequence of the active component, loads the first active component copper on the magnesium oxide carrier first, and then loads the second active component, so that the first active component copper is more uniformly dispersed on the magnesium oxide carrier, and the dispersion of the active component is improved.

[0047] The preparation method provided by the present application, preferably, the adjustment of in-situ deposition and subsequent calcination treatment conditions can effectively adjust the active component-carrier interaction, form a bimetallic active center, and is beneficial to improving the carbon dioxide conversion rate in the carbon dioxide hydrogenation to methanol reaction.

[0048] In the present application, the average particle size of the magnesium oxide carrier has the same meaning as that of the magnesium oxide carrier of the first aspect, and will not be repeated here.

[0049] In the present application, the type of basic compound is not particularly limited, and substances that are conventionally defined as basic in the art can all be suitable for the present application. Preferably, in step (1), the basic compound is selected from at least one of sodium hydroxide, potassium hydroxide, aqueous ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, and ammonium bicarbonate.

[0050] In the present application, the order of addition of the basic compound is not particularly limited, and preferably, the step (1) comprises: adding a basic compound to the dispersion liquid A containing the first active component copper precursor and the magnesium oxide carrier, mixing, and then performing a hydrothermal reaction. The present application has a wide range of choices for the conditions of mixing, and preferably, the mixing time is 10-100 min.

[0051] In the present application, the amount of the basic compound is not particularly limited. Preferably, in step (1), the mass ratio of the basic compound to the first active component copper precursor in terms of elements is 0.3-2:1.

[0052] In the present application, the type of the first active component copper precursor is not particularly limited, as long as it can provide copper elements. Preferably, in step (1), the first active component copper precursor is selected from soluble compounds of copper, and is further preferably selected from at least one of copper nitrate, copper chloride, and copper sulfate, and is more preferably copper nitrate. In the present application, the copper nitrate can be copper nitrate containing crystal water or copper nitrate not containing crystal water, and preferably it is copper nitrate containing crystal water, for example, it can be copper nitrate trihydrate, copper nitrate pentahydrate, etc.

[0053] In the present application, preferably, the dispersion liquid A containing the first active component copper precursor and the magnesium oxide carrier is prepared by dispersing the first active component copper precursor and the magnesium oxide carrier in solvent A. The type of solvent in the present application is not particularly limited, as long as it can achieve the dispersion of each substance, and preferably, the solvent A can be water. The amount of solvent in the present application is also not particularly limited, and preferably, the amount of solvent is 100-1000 mL compared to 100 g of the magnesium oxide carrier.

[0054] In the present application, preferably, in step (1), the average particle size of the magnesium oxide carrier is 100-200 nm.

[0055] In the present application, the conditions of the hydrothermal reaction are not particularly limited. Preferably, in step (1), the conditions of the hydrothermal reaction include a temperature of 80-180℃ and a time of 6-24h; further preferably, in step (1), the conditions of the hydrothermal reaction include a temperature of 120-150℃ and a time of 12-18h.

[0056] In the present application, the second active component precursor can be selected from a wide range of compounds. Preferably, in step (2), the second active component precursor is selected from at least one of iron nitrate, iron chloride, nickel nitrate, basic nickel carbonate, nickel chloride, cobalt nitrate and cobalt carbonate, more preferably cobalt nitrate.

[0057] In the present application, preferably, the dispersion B containing the hydrothermal reaction product is prepared by dispersing the hydrothermal reaction product in solvent B. In the present application, the type of solvent B is not particularly limited and can be the same as or different from solvent A, preferably the same. In the present application, the amount of solvent B is also not particularly limited and can be adjusted by those skilled in the art according to actual needs.

[0058] In the present application, the type of precipitant is not particularly limited and any precipitant capable of achieving co-precipitation in the art can be used in the present application. Preferably, in step (2), the precipitant is an alkaline compound, further preferably at least one of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate.

[0059] In the present application, the amount of precipitant is not particularly limited. Preferably, in step (2), the mass ratio of the precipitant to the second active component precursor in terms of elements is 2-15:1.

[0060] In the present application, the conditions of the co-precipitation reaction are not particularly limited. Preferably, in step (2), the conditions of the co-precipitation reaction include a time of 0.5-12h, further preferably 2-6h.

[0061] In the present application, preferably, step (2) further includes solid-liquid separation of the co-precipitation reaction product. In the present application, the specific method of solid-liquid separation is not particularly limited and can be selected by those skilled in the art according to actual needs.

[0062] In the present application, the conditions for drying are selected in a wide range, and those skilled in the art can select according to actual needs.

[0063] In the present application, the conditions for calcination are selected in a wide range. Preferably, in step (2), the conditions for calcination include: temperature of 200-600℃, time of 2-8h, and heating rate of 2-10℃ / min; further preferably, in step (2), the conditions for calcination include: temperature of 400-500℃, time of 4-6h, and heating rate of 2-5℃ / min.

[0064] In the present application, preferably, the calcination is carried out in a protective atmosphere, preferably the protective atmosphere is selected from at least one of nitrogen or inert gas. In the present application, the type of inert gas is not particularly limited, for example, it can be helium, argon, neon, etc. In the present application, the flow rate of the protective atmosphere is not particularly limited, preferably, the flow rate of the protective atmosphere is 10-80mL / min compared with 1g of coprecipitation product.

[0065] In the present application, preferably, the amounts of the first active component copper precursor, the magnesium oxide carrier and the second active component precursor are such that the total loading amount of the first active component and the second active component in the prepared supported metal oxide catalytic material is 4.5-15% in terms of element based on the mass of the magnesium oxide carrier, and further preferably 7.5-12%.

[0066] In the present application, preferably, the amounts of the first active component copper precursor and the second active component precursor are such that the loading amount ratio of the first active component copper and the second active component cobalt in the prepared supported metal oxide catalytic material is 4.5-10:1 in terms of element, and further preferably 4.5-7.5:1.

[0067] The third aspect of the present application provides an application of the supported metal oxide catalytic material of the first aspect or the supported metal oxide catalytic material prepared by the preparation method of the second aspect in a carbon dioxide hydrogenation reaction for preparing methanol.

[0068] The fourth aspect of the present application provides a method for preparing methanol by carbon dioxide hydrogenation, wherein the method comprises: carrying out a hydrogenation reaction of reaction raw materials carbon dioxide and hydrogen in the presence of a catalytic material, and the catalytic material is the supported metal oxide catalytic material of the first aspect or the supported metal oxide catalytic material prepared by the preparation method of the second aspect.

[0069] In the present application, the conditions for the hydrogenation reaction are selected in a wide range. Preferably, the conditions for the hydrogenation reaction include: volume ratio of carbon dioxide to hydrogen of 2-4:1, and volume space velocity of carbon dioxide and hydrogen mixed gas of 5000-40000mL·g-1·h-1.-1 ·min -1 , the temperature is 180-300℃, the time is 2-24h, and the pressure is 1-10MPa; further preferably, the conditions of the hydrogenation reaction include: the volume ratio of carbon dioxide and hydrogen is 3-4:1, the volume space velocity of the mixed gas is 5000-10000mL·g -1 ·min -1 , the temperature is 200-240℃, the time is 4-6h, and the pressure is 3-6MPa.

[0070] The supported metal oxide catalytic material provided by the application is used as a catalytic material for the reaction of carbon dioxide hydrogenation to methanol, which can improve the raw material conversion rate and the selectivity of the target product methanol, and the selectivity of the target product methanol reaches more than 95%.

[0071] The application will be described in detail below through examples.

[0072] In the following examples, the raw materials used are all from commercially available products unless otherwise specified.

[0073] Example 1

[0074] (1) 26.6g of copper nitrate trihydrate and 100g of magnesium oxide (average particle size is 150nm) were weighed and uniformly dispersed in 500mL of water, 10g of sodium hydroxide was added and stirred for 30min, then transferred to a polytetrafluoroethylene-lined crystallization kettle, and hydrothermal reaction was carried out at 150℃ for 15h, and the obtained solid was recovered.

[0075] (2) The above solid was uniformly dispersed in 200mL of water, 4.9g of cobalt nitrate hexahydrate was added, and after stirring, 10g of potassium hydroxide was added, and the stirring reaction was continued for 3h, then the obtained solid was recovered by centrifugation, dried, and then calcined at 450℃ under argon atmosphere for 5h, the heating rate was 5℃ / min, compared with 1g of the solid product of step (2), the argon flow rate was 50mL / min, and after cooling, the supported metal oxide catalytic material was obtained.

[0076] Figure 1 is the particle size distribution diagram of the active component of the supported metal oxide catalytic material of Example 1, and the average particle size of the active component is calculated to be 2.5nm.

[0077] Figure 2 is the CO2-TPD curve diagram of the supported metal oxide catalytic material of Example 1, from which it can be seen that the desorption temperature of the supported metal oxide catalytic material is 250℃, and the catalytic material has moderate carbon dioxide adsorption capacity, which is conducive to improving the conversion rate of raw material carbon dioxide and the selectivity of the target product methanol.

[0078] Example 2

[0079] (1) 38.0 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 11 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 155°C for 14.5 h. The obtained solid was recovered.

[0080] (2) The above solid was uniformly dispersed in 200 mL of water, 9.9 g of cobalt nitrate hexahydrate was added, and after stirring, 10 g of potassium hydroxide was added. After stirring for 3.5 h, the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 445°C for 5 h at a heating rate of 4.5°C / min. The flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, a supported metal oxide catalyst material was obtained.

[0081] Example 3

[0082] (1) 51.3 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 8 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 150°C for 15 h. The obtained solid was recovered.

[0083] (2) The above solid was uniformly dispersed in 200 mL of water, 7.4 g of cobalt nitrate hexahydrate was added, and after stirring, 10 g of potassium hydroxide was added. After stirring for 3 h, the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 450°C for 5 h at a heating rate of 5°C / min. The flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, a supported metal oxide catalyst material was obtained.

[0084] Example 4

[0085] (1) 26.6 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 150°C for 15 h. The obtained solid was recovered.

[0086] (2) The above solid was uniformly dispersed in 200 mL of water, 5.0 g of nickel nitrate hexahydrate was added, and after stirring, 10 g of potassium hydroxide was added. After stirring for 3 h, the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 450°C for 5 h at a heating rate of 5°C / min. The flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, a supported metal oxide catalyst material was obtained.

[0087] Example 5

[0088] (1) 26.6 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 150°C for 15 h, and the obtained solid was recovered.

[0089] (2) The above solid was uniformly dispersed in 200 mL of water, 7.2 g of iron nitrate nonahydrate was added, and after stirring, 10 g of potassium hydroxide was added, and the stirring reaction was continued for 3 h, then the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 450°C for 5 h, the heating rate was 5°C / min, and the flow rate of argon was 50 mL / min compared with 1 g of the solid product of step (2), and after cooling, a supported metal oxide catalytic material was obtained.

[0090] Example 6

[0091] (1) 26.6 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 150°C for 15 h, and the obtained solid was recovered.

[0092] (2) The above solid was uniformly dispersed in 200 mL of water, 7.2 g of iron nitrate nonahydrate was added, and after stirring, 10 g of potassium hydroxide was added, and the stirring reaction was continued for 3 h, then the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 450°C for 5 h, the heating rate was 5°C / min, and the flow rate of argon was 50 mL / min compared with 1 g of the solid product of step (2), and after cooling, a supported metal oxide catalytic material was obtained.

[0093] Example 7

[0094] (1) 26.6 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was carried out at 150°C for 15 h, and the obtained solid was recovered.

[0095] (2) The above solid was uniformly dispersed in 200 mL of water, 7.2 g of iron nitrate nonahydrate was added, and after stirring, 10 g of potassium hydroxide was added, and the stirring reaction was continued for 3 h, then the obtained solid was recovered by centrifugation, dried, and then calcined in an argon atmosphere at 450°C for 5 h, the heating rate was 5°C / min, and the flow rate of argon was 50 mL / min compared with 1 g of the solid product of step (2), and after cooling, a supported metal oxide catalytic material was obtained.

[0096] Comparative Example 1

[0097] (1) 87.5 g of copper nitrate trihydrate was weighed and uniformly dispersed in 500 mL of water, 50 g of sodium hydroxide was added and stirred for 30 min, and then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was performed at 150°C for 15 h. The obtained solid was recovered.

[0098] (2) The above solid was uniformly dispersed in 200 mL of water, 12.5 g of cobalt nitrate hexahydrate was added, and after stirring, 10 g of potassium hydroxide was added, and the stirring was continued for 3 h. The obtained solid was recovered by centrifugation, dried, and then calcined at 450°C for 5 h in an argon atmosphere, and the flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, the catalytic material was obtained.

[0099] Comparative Example 2

[0100] (1) 30.4 g of copper nitrate trihydrate and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, and then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was performed at 150°C for 15 h. The obtained solid was recovered.

[0101] (2) The above solid was uniformly dispersed in 200 mL of water, and after stirring, 10 g of potassium hydroxide was added, and the stirring was continued for 3 h. The obtained solid was recovered by centrifugation, dried, and then calcined at 450°C for 5 h in an argon atmosphere, and the flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, the catalytic material was obtained.

[0102] Comparative Example 3

[0103] (1) 26.6 g of copper nitrate trihydrate, 4.9 g of cobalt nitrate hexahydrate, and 100 g of magnesium oxide (average particle size of 150 nm) were weighed and uniformly dispersed in 500 mL of water, 10 g of sodium hydroxide was added and stirred for 30 min, and then transferred to a polytetrafluoroethylene-lined autoclave, and hydrothermal reaction was performed at 150°C for 15 h. The obtained solid was recovered.

[0104] (2) The above solid was uniformly dispersed in 200 mL of water, and after stirring, 10 g of potassium hydroxide was added, and the stirring was continued for 3 h. The obtained solid was recovered by centrifugation, dried, and then calcined at 450°C for 5 h in an argon atmosphere, and the flow rate of argon was 50 mL / min compared to 1 g of the solid product of step (2). After cooling, the catalytic material was obtained.

[0105] Comparative Example 4

[0106] The method of Example 1 was followed except that the average particle size of the magnesium oxide was 900 nm.

[0107] The compositions of the catalytic materials of the above examples and comparative examples are shown in Table 1, and the property parameters are shown in Table 2.

[0108] Table 1

[0109]

[0110] Note: In Table 1, the loading of the active component is calculated in terms of elements, wherein the loading of the active component in Examples 1-7 and Comparative Examples 2-4 is calculated based on the mass of the magnesium oxide carrier, and the loading of the active component in Comparative Example 1 is calculated based on the total mass of the catalytic material.

[0111] Table 2

[0112] Average particle size (nm) Specific surface area (cm 2 / g) Desorption temperature (°C) Example 1 2.5 795.5 250.0 Example 2 7.5 750.6 300.0 Example 3 9.5 620.1 495.0 Example 4 6.5 550.6 180.0 Example 5 2.5 642.5 450.0 Example 6 8.5 701.4 320.0 Example 7 14.3 522.6 182.0 Comparative Example 1 100.0 94.5 45.0 Comparative Example 2 15.0 450.6 510.0 Comparative Example 3 32.5 357.8 600.0 Comparative Example 4 50.2 154.6 172.1

[0113] Test Example

[0114] The catalytic materials of the above examples and comparative examples were subjected to activity tests for the hydrogenation of carbon dioxide to methanol using a fixed bed microreactor, the feed gas was CO2 and H2 (volume ratio of 3:1), the space velocity of the mixed gas was 8000 mL.g -1 ·min -1 The catalyst loading was 1.0 g, the ratio of quartz sand was 4.0 g, the reaction temperature was 220°C, the reaction pressure was 3 MPa, the time was 6 h, and a chromatograph equipped with a hydrogen flame ion detector and a thermal conductivity cell detector was used for analysis, and the test results are shown in Table 3.

[0115] The conversion of the raw material and the selectivity of each product were calculated by the following formula:

[0116] Carbon dioxide conversion = (moles of carbon dioxide in raw material - moles of carbon dioxide in product) / moles of carbon dioxide in raw material x 100%;

[0117] Methanol = methanol generation rate / (methanol generation rate + carbon monoxide generation rate + methane generation rate) x 100%;

[0118] Carbon monoxide = carbon monoxide generation rate / (methanol generation rate + carbon monoxide generation rate + methane generation rate) x 100%;

[0119] Methane = methane generation rate / (methanol generation rate + carbon monoxide generation rate + methane generation rate) x 100%.

[0120] Table 3

[0121]

[0122] It can be seen from the results in the above table that the load type metal oxide catalytic material in the embodiment of the present application is used in the reaction of carbon dioxide hydrogenation to prepare methanol, which can improve the conversion rate of raw material carbon dioxide and the selectivity of target product methanol, wherein the selectivity of methanol can reach more than 95%; in addition, the selection of magnesium oxide as the carrier can also reduce the production cost.

[0123] The preferred embodiments of the present application are described in detail above, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as the disclosed content of the present application, and all belong to the protection scope of the present application.

Claims

1. A supported metal oxide catalytic material, wherein, The supported metal oxide catalytic material includes a magnesium oxide support and an active component supported on the magnesium oxide support. The active component includes a first active component, copper, and a second active component. The second active component is selected from at least one of iron, cobalt, and nickel. The average particle size of the magnesium oxide support is 100-500 nm. The average particle size of the active component is less than 10 nm.

2. The supported metal oxide catalytic material according to claim 1, wherein, Based on the mass of the magnesium oxide support, the total loading of the active components in the supported metal oxide catalytic material, calculated by element, is 5-15%, preferably 7.5-12%. Preferably, the active component includes a first active component, copper, and a second active component, cobalt; Preferably, the loading ratio of the first active component copper and the second active component cobalt is 4.5-10:1, more preferably 4.5-7.5:1; Preferably, the average particle size of the magnesium oxide support is 100-200 nm.

3. The supported metal oxide catalytic material according to claim 1 or 2, wherein, The average particle size of the active component is 2-8 nm; And / or, the specific surface area of ​​the supported metal oxide catalyst is 500-800 cm². 2 / g, preferably 700-800cm 2 / g; And / or, the CO2-TPD desorption temperature of the supported metal oxide catalyst is 50-500℃, preferably 200-300℃.

4. A method for preparing a supported metal oxide catalytic material, wherein, The method includes the following steps: (1) In the presence of an alkaline compound, a dispersion A containing the first active component, a copper precursor, and a magnesium oxide carrier undergoes a hydrothermal reaction. (2) In the presence of a precipitant, the dispersion B containing the hydrothermal reaction product and the second active component precursor are mixed for co-precipitation reaction, and then dried and calcined. The second active component is selected from one of iron, cobalt, and nickel, preferably cobalt; The average particle size of the magnesium oxide support is 100-500 nm.

5. The method according to claim 4, wherein, In step (1), the alkaline compound is selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate, and ammonium bicarbonate. Preferably, in step (1), the mass ratio of the alkaline compound to the first active component copper precursor, calculated by element, is 0.3-2:1; Preferably, in step (1), the first active component copper precursor is selected from copper-soluble compounds, and more preferably from at least one of copper nitrate, copper chloride and copper sulfate; Preferably, in step (1), the average particle size of the magnesium oxide support is 100-200 nm; Preferably, in step (1), the conditions for the hydrothermal reaction include: a temperature of 80-180℃ and a time of 6-24h.

6. The method according to claim 4 or 5, wherein, In step (2), the second active component precursor is selected from compounds containing each second active component, and more preferably selected from at least one of ferric nitrate, ferric chloride, nickel nitrate, basic nickel carbonate, nickel chloride, cobalt nitrate and basic cobalt carbonate; Preferably, in step (2), the precipitant is an alkaline compound, and more preferably selected from at least one of sodium hydroxide, potassium hydroxide, ammonia, sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate; Preferably, in step (2), the mass ratio of the precipitant to the second active component precursor (based on elemental composition) is 2-15:1; Preferably, in step (2), the conditions for the coprecipitation reaction include: a time of 0.5-12 hours; Preferably, in step (2), the calcination conditions include: a temperature of 200-600℃, a time of 2-8h, and a heating rate of 2-10℃ / min.

7. The method according to any one of claims 4-6, wherein, The amounts of the first active component copper precursor, the magnesium oxide support, and the second active component precursor are such that, based on the mass of the magnesium oxide support, the total loading of the first and second active components in the prepared supported metal oxide catalytic material is 4.5-15% by element, more preferably 7.5-12%. Preferably, the amounts of the first active component copper precursor and the second active component precursor are such that, in terms of elemental composition, the loading ratio of the first active component copper to the second active component cobalt in the prepared supported metal oxide catalyst is 4.5-10:1, more preferably 4.5-7.5:

1.

8. The application of the supported metal oxide catalyst material according to any one of claims 1-3 or the supported metal oxide catalyst material prepared by the preparation method according to any one of claims 4-7 in the reaction of carbon dioxide hydrogenation to methanol.

9. A method for producing methanol by hydrogenation of carbon dioxide, wherein, The method includes: in the presence of a catalytic material, reactants carbon dioxide and hydrogen undergo a hydrogenation reaction, wherein the catalytic material is a supported metal oxide catalytic material as described in any one of claims 1-3 or a supported metal oxide catalytic material prepared by any one of claims 4-7.

10. The method according to claim 9, wherein, The conditions for the hydrogenation reaction include: a volume ratio of carbon dioxide to hydrogen of 2-4:1, and a volume hourly space velocity (VHSV) of 5000-40000 mL·g for the carbon dioxide and hydrogen mixture. -1 ·min -1 The temperature is 180-300℃, the time is 2-24h, and the pressure is 1-10MPa. Preferably, the conditions for the hydrogenation reaction include: a volume ratio of carbon dioxide to hydrogen of 3-4:1, and a volume hourly space velocity (VHSV) of 5000-10000 mL·g for the carbon dioxide and hydrogen mixture. -1 ·min -1 The temperature is 200-240℃, the time is 4-6h, and the pressure is 3-6MPa.

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