Catalyst for catalyzing carbon dioxide reverse water-gas shift and its preparation method and application

Abstract

The present invention provides a catalyst for catalyzing the reverse water-gas shift of carbon dioxide and a preparation method and application thereof. The catalyst has the following chemical composition: Cu a Ni b Ce c Zr m O d , wherein 1≤a≤2, 1≤b≤2, 1≤c≤2, 4≤d≤8, 0.01≤m≤0.02. The catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the present invention uses copper, nickel, cerium and zirconium as active metals, and their synergistic effect can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the reverse water-gas reaction of carbon dioxide to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved.

Description

Technical Field

[0001] The present invention belongs to the field of material technology, and in particular relates to a catalyst for catalyzing carbon dioxide reverse water-gas shift, and a preparation method and application thereof. Background Art

[0002] As the use of fossil energy gradually increases, a large amount of carbon dioxide is emitted into the atmosphere, causing the greenhouse effect to become increasingly obvious. As human society's demand for energy is increasing, it is difficult to find an energy source that can completely replace fossil fuels in the short term. Therefore, carbon dioxide capture and conversion technology is one of the most feasible ways to solve the greenhouse effect. In particular, carbon dioxide conversion technology can convert captured carbon dioxide into cheap C1 resources to prepare high-value chemicals.

[0003] At present, the reverse water gas reaction is considered to be one of the most promising and promising ways to convert carbon dioxide. It produces carbon monoxide and water through the reaction of carbon dioxide and hydrogen. Among them, carbon monoxide is an important intermediate raw material for coal chemical industry and natural gas chemical industry. By mixing carbon monoxide and hydrogen to prepare synthesis gas, a series of chemical products and oil products can be synthesized, such as Fischer-Tropsch synthesis of oil products, as well as low-carbon alcohols, olefins, aromatics and other downstream chemical products with high added value. However, in the prior art, the reverse water gas reaction still has the problems of low carbon dioxide conversion rate and low carbon monoxide selectivity. Summary of the invention

[0004] The main purpose of the present invention is to provide a catalyst for catalyzing the reverse water-gas shift of carbon dioxide. When the catalyst is used in the reverse water-gas reaction, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved.

[0005] The present invention also provides a method for preparing a catalyst, which can prepare the above catalyst with simple process and low cost.

[0006] The present invention also provides a method for preparing carbon monoxide, which is obtained by using the above catalyst to catalyze carbon dioxide to undergo a reverse water gas reaction, thereby improving the conversion rate of carbon dioxide and the selectivity of carbon monoxide.

[0007] In a first aspect, the present invention provides a catalyst for catalyzing the reverse water-gas shift of carbon dioxide, having a chemical composition as shown in Formula 1,

[0008] Cu a Ni b Ce c Zr m O d , Formula 1,

[0009] Among them, 1≤a≤2, 1≤b≤2, 1≤c≤2, 4≤d≤8, 0.01≤m≤0.02.

[0010] In the catalyst as described above, a is 2, b is 2, c is 2, d is 8, and m is 0.01.

[0011] The catalyst as described above is prepared by a method comprising the following process:

[0012] The mixed solution including the copper source, the nickel source, the cerium source and the zirconium source is sequentially subjected to standing, filtering, washing, drying and calcining treatments to obtain the catalyst.

[0013] In a second aspect, the present invention provides a method for preparing the catalyst as described above, comprising the following steps:

[0014] 1) adjusting the pH value of the solution including the copper source, the nickel source, the cerium source and the zirconium source to 8-9 to obtain a mixed solution;

[0015] 2) The mixed solution is sequentially subjected to a standing treatment, a filtering treatment, a washing treatment, a drying treatment, and a calcining treatment to obtain the catalyst.

[0016] In the method for preparing the catalyst as described above, the molar ratio of copper element, nickel element, cerium element and zirconium element in the copper source, nickel source, cerium source and zirconium source is (1-2): (1-2): (1-2): (4-8).

[0017] In the above-mentioned method for preparing the catalyst, the temperature of the calcination treatment is 500-550° C. and the time is 3-5 hours.

[0018] The method for preparing the catalyst as described above, wherein the temperature of the drying treatment is 100-120°C;

[0019] And / or, the static treatment time is 36-48h.

[0020] In a third aspect, the present invention provides a method for preparing carbon monoxide, comprising the following steps: using the catalyst as described above or a catalyst prepared by the method for preparing the catalyst as described above to catalyze a reverse water gas reaction of carbon dioxide to obtain carbon monoxide.

[0021] The method for preparing carbon monoxide as described above comprises the following steps:

[0022] 1) activating the catalyst using hydrogen to obtain an activated catalyst;

[0023] 2) At a temperature of 400-600° C. and a pressure of 0.15-0.25 MPa, hydrogen and carbon dioxide are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the reverse water gas reaction to obtain the carbon monoxide.

[0024] In the method for preparing carbon monoxide as described above, the volume ratio of hydrogen to carbon dioxide is 3-3.5:1.

[0025] The catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the present invention uses copper, nickel, cerium and zirconium as active metals, and their synergistic effect can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the reverse water-gas reaction of carbon dioxide to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0027] In a first aspect, the present invention provides a catalyst for catalyzing the reverse water-gas shift of carbon dioxide, having a chemical composition as shown in Formula 1,

[0028] Cu a Ni b Ce c Zr m O d , Formula 1,

[0029] Among them, 1≤a≤2, 1≤b≤2, 1≤c≤2, 4≤d≤8, 0.01≤m≤0.02.

[0030] Exemplarily, the value of a can be 1, 1.5, 2, 2.5, 3 or a range consisting of any two of them; the value of b can be 1, 1.5, 2, 2.5, 3 or a range consisting of any two of them; the value of c can be 1, 1.5, 2, 2.5, 3 or a range consisting of any two of them; the value of d can be 4, 5, 6, 7, 8 or a range consisting of any two of them; the value of m can be 0.01, 0.011, 0.012, 0.013, 0.014, 0.015, 0.016, 0.017, 0.018, 0.019, 0.02 or a range consisting of any two of them.

[0031] The catalyst provided by the present invention can be used to catalyze carbon dioxide to undergo a reverse water gas reaction to obtain carbon monoxide. The chemical composition of the catalyst is: Cu a Ni b Ce c Zr m O d, where 1≤a≤2, 1≤b≤2, 1≤c≤2, 4≤d≤8, 0.01≤m≤0.02. When catalyzing carbon dioxide to undergo a reverse water gas reaction to obtain carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved. It is speculated that this may be because: the presence of copper, nickel, cerium, and zirconium elements provide more active sites on the catalyst surface. These active sites can more effectively adsorb carbon dioxide molecules and promote the conversion of carbon dioxide molecules into carbon monoxide on the catalyst surface, thereby improving the catalytic efficiency. Therefore, when the catalyst has Cu a Ni b Ce c Zr m O d The catalyst has a chemical composition of 1≤a≤2, 1≤b≤2, 1≤c≤2, 4≤d≤8, and 0.01≤m≤0.02, and has a high catalytic activity, can improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide, and is helpful to reduce energy consumption and production costs, and improve economic benefits. When the number of copper atoms in the catalyst is not within 1-2, and / or the number of nickel atoms is not within 1-2, and / or the number of cerium atoms is not within 1-2, and / or the number of zirconium atoms is not within 0.01-0.02, and / or the number of oxygen atoms is not within 4-8, the catalyst does not play such a role, and thus cannot catalyze carbon dioxide to generate carbon monoxide by reverse water gas reaction or carbon dioxide to generate carbon monoxide by reverse water gas reaction, the conversion rate of carbon dioxide is low, and the selectivity of carbon monoxide is low.

[0032] The catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the present invention uses copper, nickel, cerium and zirconium as active metals, and their synergistic effect can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the reverse water-gas reaction of carbon dioxide to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved.

[0033] In some embodiments of the present invention, a is 2, b is 2, c is 2, d is 8, and m is 0.01. When carbon dioxide is catalyzed to undergo a reverse water gas reaction to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be further improved.

[0034] In some embodiments of the present invention, the catalyst is prepared by a method comprising the following process:

[0035] The mixed solution including the copper source, the nickel source, the cerium source and the zirconium source is sequentially subjected to standing, filtering, washing, drying and calcining treatments to obtain the catalyst.

[0036] In one embodiment, a copper source, a nickel source, a cerium source, and a zirconium source can be dissolved in an appropriate amount of water and completely dissolved under stirring to form a mixed solution. Then, an alkaline solution is added dropwise to the mixed solution under stirring to adjust the pH of the system to be alkaline, for example, 8-9, so that the mixed solution forms a precipitate. The mixed solution is then allowed to stand, filtered, washed, dried, and calcined to obtain a catalyst containing active components of copper, nickel, cerium, and zirconium.

[0037] The catalyst preparation method of the present invention can prepare the above catalyst, the synthesis method is simple, the process conditions are easy to control, the catalyst has a long service life, and is convenient for industrial scale-up production.

[0038] In a second aspect, the present invention provides a method for preparing the catalyst as described above, comprising the following steps:

[0039] 1) adjusting the pH value of the solution including the copper source, the nickel source, the cerium source and the zirconium source to 8-9 to obtain a mixed solution;

[0040] 2) The mixed solution is sequentially subjected to a standing treatment, a filtering treatment, a washing treatment, a drying treatment, and a calcining treatment to obtain the catalyst.

[0041] In step 1) of the present invention, optionally, the copper source can be a copper salt, for example, copper nitrate trihydrate; the nickel source can be a nickel salt, for example, nickel nitrate hexahydrate; the cerium source can be a cerium salt, for example, cerium nitrate hexahydrate; the zirconium source can be a zirconium salt, for example, zirconium chloride. The copper source, nickel source, cerium source, and zirconium source are dissolved in water and completely dissolved under stirring to form an aqueous solution; an alkaline substance, for example, ammonium carbonate and ammonium hydroxide are dissolved in water to form an alkaline solution; and then the alkaline solution is added dropwise to the aqueous solution to adjust the pH value of the system to 8-9, for example, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9 or any two thereof, so that a precipitate is formed in the aqueous solution to obtain a mixed solution.

[0042] In step 2), the obtained mixed solution is post-treated to obtain a catalyst containing active components of copper, nickel, cerium and zirconium. The post-treatment includes standing treatment, filtering treatment, washing treatment, drying treatment and roasting treatment. Standing treatment is used to make the active components evenly distributed. Filtration treatment is used to filter out excess alkaline solution. Washing treatment is used to remove impurities in the catalyst. Drying treatment is used to remove moisture from the surface of the catalyst. The roasting treatment can be carried out in a muffle furnace to remove volatile components in the catalyst, form a stable structure, and enable the catalyst to obtain a certain crystal form, grain size, pore structure and specific surface area, and obtain a catalyst containing active components of copper, nickel, cerium and zirconium, wherein the number of copper atoms is within 1-2, the number of nickel atoms is within 1-2, the number of cerium atoms is within 1-2, the number of zirconium atoms is within 0.01-0.02, and the number of oxygen atoms is within 4-8.

[0043] The preparation method of the catalyst of the present invention can prepare the catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the first aspect of the present invention. When the catalyst catalyzes the reverse water-gas reaction of carbon dioxide to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved. The preparation method is simple and easy, convenient for industrial scale-up production, does not use precious metals, has low production cost, long service life, and has good application prospects.

[0044] In some embodiments of the present invention, the molar ratio of copper element, nickel element, cerium element and zirconium element in the copper source, nickel source, cerium source and zirconium source is (1-2): (1-2): (1-2): (0.01-0.02).

[0045] Illustratively, the molar ratio of copper element, nickel element, cerium element and zirconium element in the copper source, nickel source, cerium source and zirconium source can be 1:1:1:0.01, 1:1:1:0.02, 1:2:2:0.01, 1:2:2:0.02, 2:2:2:0.01, 2:2:2:0.02 or a range consisting of any two of them.

[0046] In the present invention, controlling the molar ratio of copper, nickel, cerium and zirconium in the copper source, nickel source, cerium source and zirconium source within the above-mentioned range is conducive to obtaining the catalyst for catalyzing the reverse water-gas shift of carbon dioxide according to the first aspect of the present invention, that is, by controlling the atomic numbers of copper, nickel, cerium and zirconium in the catalyst within the above-mentioned range, the catalyst can improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide when catalyzing the reverse water-gas reaction of carbon dioxide to generate carbon monoxide.

[0047] In some embodiments of the present invention, the calcination treatment is carried out at a temperature of 500-550° C. and for a time of 3-5 hours.

[0048] For example, the calcination temperature may be 500° C., 510° C., 520° C., 530° C., 540° C., 550° C., or any two thereof. The calcination time may be 3 h, 3.5 h, 4 h, 4.5 h, 5 h, or any two thereof.

[0049] The temperature and time of the calcination treatment in the present invention are within the above ranges, which can ensure that volatile components such as organic matter in the catalyst are completely removed, stabilize the crystal structure of the catalyst, and improve the thermal stability and catalytic activity of the catalyst.

[0050] In some embodiments of the present invention, the drying temperature is 100-120°C;

[0051] In some embodiments, the static treatment time is 36-48 hours.

[0052] For example, the drying temperature may be 100° C., 105° C., 110° C., 115° C., 120° C., or any two thereof. The standing time may be 36 h, 38 h, 40 h, 42 h, 45 h, 48 h, or any two thereof.

[0053] The drying temperature of the present invention is within the above range, which can effectively remove most of the water in the catalyst, and at the same time avoid the destruction of the catalyst structure or the loss of active components caused by excessively high temperature; it is also beneficial to maintain the appropriate pore structure and specific surface area of ​​the catalyst, improve the stability of the catalyst, and extend the service life of the catalyst. The static treatment time is within the above range, which can cause a slow chemical reaction or structural adjustment inside the catalyst, optimize the microstructure and performance of the catalyst, and is beneficial to the uniform distribution of active components, thereby improving the catalytic activity of the catalyst, so that when it catalyzes carbon dioxide to generate carbon monoxide by the reverse water gas reaction, it can improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide.

[0054] In a third aspect, the present invention provides a method for preparing carbon monoxide, comprising the following steps: using the catalyst as described above or a catalyst prepared by the method for preparing the catalyst as described above to catalyze a reverse water gas reaction of carbon dioxide to obtain carbon monoxide.

[0055] The present invention utilizes the catalyst provided in the first aspect or the catalyst prepared by the preparation method provided in the second aspect to catalyze carbon dioxide to undergo a reverse water gas reaction to obtain carbon monoxide, thereby improving the conversion rate of carbon dioxide and the selectivity of carbon monoxide.

[0056] In some embodiments, the temperature of the reverse water gas reaction can be 400-600°C, and the pressure of the reverse water gas reaction can be 0.15-0.25MPa. Exemplarily, the temperature of the reverse water gas reaction can be 400°C, 420°C, 450°C, 470°C, 500°C, 520°C, 550°C, 570°C, 600°C, or a range consisting of any two of them. The pressure of the reverse water gas reaction can be 0.15MPa, 0.16MPa, 0.17MPa, 0.18MPa, 0.19MPa, 0.2MPa, 0.21MPa, 0.22MPa, 0.23MPa, 0.24MPa, 0.25MPa, or a range consisting of any two of them. The reaction temperature and time allow the catalyst to catalyze carbon dioxide to react with reverse water gas to obtain carbon monoxide, which can improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide.

[0057] In some embodiments of the present invention, the preparation method comprises the following steps:

[0058] 1) activating the catalyst using hydrogen to obtain an activated catalyst;

[0059] 2) At a temperature of 400-600° C. and a pressure of 0.15-0.25 MPa, hydrogen and carbon dioxide are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the reverse water gas reaction to obtain the carbon monoxide.

[0060] In the present invention, hydrogen is first used to activate the catalyst to obtain an activated catalyst, and then the activated catalyst is used to perform a reverse water gas reaction on carbon dioxide to obtain carbon monoxide.

[0061] In some embodiments, the temperature of the activation treatment may be 300-400° C., and the time of the activation treatment may be 0.5-1.5 h. For example, the temperature of the activation treatment may be 300° C., 350° C., 400° C., or a range consisting of any two thereof. The time of the activation treatment may be 0.5 h, 1 h, 1.5 h, or a range consisting of any two thereof.

[0062] Specifically, in step 1), the catalyst of 20-40 mesh is screened and activated by hydrogen at 300-400°C for 0.5-1.5h to obtain an activated catalyst. It can be understood that after the catalyst is prepared, it is often necessary to activate the passive catalyst to convert it into an activated catalyst. The purpose of activation is to form active sites required for the catalytic reaction on the catalyst, especially on the catalyst surface.

[0063] In step 2), a certain amount of activated catalyst, for example 1 g, is loaded into a fixed bed reaction tube, wherein the reaction tube of the fixed bed reaction device has an inner diameter of 10 mm and a length of 40 cm, and then the temperature of the fixed bed is adjusted to within the range of 400-600°C, and the reaction raw materials hydrogen and carbon dioxide are introduced for gas-solid contact to carry out a reverse water gas reaction, and the pressure is controlled within the range of 0.15-0.25 MPa. Under the action of the catalyst, carbon dioxide reacts with hydrogen to generate carbon monoxide and water.

[0064] The present invention uses the above-mentioned catalyst containing metal copper, nickel, cerium and zirconium to catalyze carbon dioxide to undergo a reverse water gas reaction to obtain carbon monoxide. The catalyst has high activity, so the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved.

[0065] In some embodiments of the present invention, the volume ratio of hydrogen to carbon dioxide is 3-3.5:1.

[0066] In the present invention, the volume ratio of hydrogen to carbon dioxide is within the above range, so that carbon dioxide and hydrogen can fully react to finally generate carbon monoxide, which can further improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide.

[0067] The technical solution of the present invention is further described below in conjunction with specific embodiments.

[0068] Example 1

[0069] The preparation method of this embodiment comprises the following steps:

[0070] 1) Dissolve 24.2g Cu(NO3)2·3H2O, 43.6g Ni(NO3)2·6H2O, 86.8g Ce(NO3)3·6H2O and 0.47g ZrCl4 in 150mL water and stir to dissolve them completely to obtain a first solution. Dissolve 47g ammonium carbonate in 150mL water to form a second solution. Add the second solution dropwise to the first solution under stirring, adjust the pH to 8.5, let stand for 48h, filter, wash, dry at 120℃ for 8h, and calcine at 500℃ for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr. The chemical composition of the catalyst is CuNi 1.5 Ce2Zr 0.02 O 6.5 .

[0071] 2) The above catalyst was activated in H2 atmosphere at 300°C for 1h to obtain an activated catalyst. The reaction tube of the fixed bed reaction device has an inner diameter of 10mm and a length of 40cm. 1g of the above activated catalyst was loaded into the reaction tube, the temperature was adjusted to 500°C, and the reaction raw materials carbon dioxide and hydrogen were introduced for gas-solid contact to perform a reverse water gas reaction, wherein the volume ratio of hydrogen to carbon dioxide was 3:1, the reaction pressure was controlled at 0.2MPa, and the reaction product carbon monoxide was connected to an online gas chromatograph through a pipeline for analysis. The results are shown in Table 1.

[0072] Example 2

[0073] The preparation method of Example 2 is basically the same as that of Example 1, except that in step 1), 48.3g Cu(NO3)2·3H2O, 58.2g Ni(NO3)2·6H2O, 43.4g Ce(NO3)3·6H2O and 0.23g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is Cu2Ni2CeZr 0.01 O6.

[0074] Example 3

[0075] The preparation method of Example 3 is basically the same as that of Example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O, 58.2g Ni(NO3)2·6H2O, 43.4g Ce(NO3)3·6H2O and 0.23g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is CuNi2CeZr 0.01 O5.

[0076] Example 4

[0077] The preparation method of Example 4 is basically the same as that of Example 1, except that in step 1), 336.2g Cu(NO3)2·3H2O, 58.2g Ni(NO3)2·6H2O, 43.4g Ce(NO3)3·6H2O and 0.47g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is Cu 1.5 Ni2CeZr 0.02 O 5.5 .

[0078] Example 5

[0079] The preparation method of Example 5 is basically the same as that of Example 1, except that in step 1), 48.3g Cu(NO3)2·3H2O, 29.1g Ni(NO3)2·6H2O, 86.8g Ce(NO3)3·6H2O and 0.23g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is Cu2NiCe2Zr 0.01 O7.

[0080] Example 6

[0081] The preparation method of Example 6 is basically the same as that of Example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O, 58.2g Ni(NO3)2·6H2O, 86.8g Ce(NO3)3·6H2O and 0.23g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is CuNi2Ce2Zr 0.01 O7.

[0082] Example 7

[0083] The preparation method of Example 7 is basically the same as that of Example 1, except that in step 1), 48.3g Cu(NO3)2·3H2O, 5832g Ni(NO3)2·6H2O, 86.8g Ce(NO3)3·6H2O and 0.23g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, Ce and Zr, the chemical composition of which is Cu2Ni2Ce2Zr 0.01 O8.

[0084] Example 8

[0085] The preparation method of Example 8 is basically the same as that of Example 1, except that in step 1), the pH is adjusted to 8.

[0086] Example 9

[0087] The preparation method of Example 9 is basically the same as that of Example 1, except that in step 1), the pH is adjusted to 9.

[0088] Example 10

[0089] The preparation method of Example 10 is basically the same as that of Example 1, except that in step 1), the calcination temperature is 550°C.

[0090] Embodiment 11

[0091] The preparation method of Example 11 is basically the same as that of Example 1, except that in step 1), the calcination time is 3 hours.

[0092] Example 12

[0093] The preparation method of Example 12 is basically the same as that of Example 1, except that in step 1), the calcination time is 5 hours.

[0094] Embodiment 13

[0095] The preparation method of Example 13 is basically the same as that of Example 1, except that in step 1), the drying temperature is 100°C.

[0096] Embodiment 14

[0097] The preparation method of Example 14 is basically the same as that of Example 1, except that in step 1), the static treatment time is 36 hours.

[0098] Embodiment 15

[0099] The preparation method of Example 15 is basically the same as that of Example 1, except that in step 2), the temperature of the reverse water gas reaction is 400°C.

[0100] Example 16

[0101] The preparation method of Example 16 is basically the same as that of Example 1, except that in step 2), the temperature of the reverse water gas reaction is 600°C.

[0102] Embodiment 17

[0103] The preparation method of Example 17 is basically the same as that of Example 1, except that in step 2), the pressure of the reverse water gas reaction is 0.15 MPa.

[0104] Embodiment 18

[0105] The preparation method of Example 18 is basically the same as that of Example 1, except that in step 2), the pressure of the reverse water gas reaction is 0.25 MPa.

[0106] Embodiment 19

[0107] The preparation method of Example 19 is basically the same as that of Example 1, except that in step 2), the volume ratio of hydrogen to carbon dioxide is 3.5:1.

[0108] Comparative Example 1

[0109] The preparation method of Comparative Example 1 is basically the same as that of Example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O, 86.8g Ce(NO3)3·6H2O and 0.47g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution. Under stirring, the second solution is added dropwise to the first solution, the pH is adjusted to 8.5, and the solution is allowed to stand for 48h, filtered, washed, dried at 120℃ for 8h, and calcined at 500℃ for 4h to obtain a catalyst containing active components Cu, Ce, and Zr. The chemical composition of the catalyst is CuCe2Zr 0.02 O5.

[0110] Comparative Example 2

[0111] The preparation method of Comparative Example 2 is basically the same as that of Example 1, except that in step 1), 43.6g Ni(NO3)2·6H2O, 86.8g Ce(NO3)3·6H2O and 0.47g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution. Under stirring, the second solution is added dropwise to the first solution, the pH is adjusted to 8.5, and the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Ni, Ce, and Zr. The chemical composition of the catalyst is Ni 1.5 Ce2Zr 0.02 O 5.5 .

[0112] Comparative Example 3

[0113] The preparation method of Comparative Example 3 is basically the same as that of Example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O and 86.8g Ce(NO3)3·6H2O are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, and the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu and Ce, the chemical composition of which is CuCe2O5.

[0114] Comparative Example 4

[0115] The preparation method of Comparative Example 4 is basically the same as that of Example 1, except that in step 1), 43.6 g Ni(NO3)2·6H2O and 86.8 g Ce(NO3)3·6H2O are dissolved in 150 mL of water and completely dissolved under stirring to obtain a first solution. 47 g ammonium carbonate is dissolved in 150 mL of water to form a second solution. Under stirring, the second solution is added dropwise to the first solution, the pH is adjusted to 8.5, and the solution is allowed to stand for 48 hours, filtered, washed, dried at 120°C for 8 hours, and calcined at 500°C for 4 hours to obtain a catalyst containing active components Ni and Ce. The chemical composition of the catalyst is Ni 1.5 Ce2O 5.5 .

[0116] Comparative Example 5

[0117] The preparation method of comparative example 5 is basically the same as that of example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O, 43.6g Ni(NO3)2·6H2O, and 86.8g Ce(NO3)3·6H2O are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution, which is added dropwise to the first solution under stirring, the pH is adjusted to 8.5, and the solution is allowed to stand for 48h, filtered, washed, dried at 120°C for 8h, and calcined at 500°C for 4h to obtain a catalyst containing active components Cu, Ni, and Ce. The chemical composition of the catalyst is CuNi 1.5 Ce2O 6.5 .

[0118] Comparative Example 6

[0119] The preparation method of Comparative Example 6 is basically the same as that of Example 1, except that in step 1), 24.2g Cu(NO3)2·3H2O, 43.6g Ni(NO3)2·6H2O and 0.47g ZrCl4 are dissolved in 150mL water and completely dissolved under stirring to obtain a first solution. 47g ammonium carbonate is dissolved in 150mL water to form a second solution. Under stirring, the second solution is added dropwise to the first solution, the pH is adjusted to 8.5, and the solution is allowed to stand for 48h, filtered, washed, dried at 120℃ for 8h, and calcined at 500℃ for 4h to obtain a catalyst containing active components Cu, Ni and Zr. The chemical composition of the catalyst is CuNi 1.5 Zr 0.02 O 2.5 .

[0120] Table 1 Carbon dioxide conversion and carbon monoxide selectivity of Examples 1-19 and Comparative Examples 1-6

[0121]

[0122] As can be seen from Table 1, compared with the comparative example, the catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the present invention has copper, nickel, cerium and zirconium as active metals, and their synergistic effect can improve the catalytic activity of the catalyst, so that when the catalyst catalyzes the reverse water-gas reaction of carbon dioxide to generate carbon monoxide, the conversion rate of carbon dioxide and the selectivity of carbon monoxide can be improved.

[0123] From the comparison between Example 1 and Comparative Examples 1-6, it can be seen that the catalyst for catalyzing the reverse water-gas shift of carbon dioxide provided by the present invention can improve the conversion rate of carbon dioxide and the selectivity of carbon monoxide when catalyzing the reverse water-gas reaction of carbon dioxide to generate carbon monoxide.

[0124] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or replace some or all of the technical features therein with equivalents. However, these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing carbon monoxide, characterized in that: The following steps are involved: Using a catalyst to catalyze carbon dioxide to undergo a reverse water gas reaction to obtain carbon monoxide; The method for preparing the catalyst comprises the following steps: 1) adjusting the pH value of the solution including the copper source, the nickel source, the cerium source and the zirconium source to 8-9 to obtain a mixed solution; 2) subjecting the mixed solution to a standing treatment, a filtering treatment, a washing treatment, a drying treatment, and a calcining treatment in sequence to obtain the catalyst; The molar ratio of copper element, nickel element, cerium element and zirconium element in the copper source, nickel source, cerium source and zirconium source is (1-2): (1-2): (1-2): (0.01-0.02).

2. The method for preparing carbon monoxide according to claim 1, characterized in that: The calcination treatment is carried out at a temperature of 500-550° C. and for a time of 3-5 hours.

3. The method for preparing carbon monoxide according to claim 1, characterized in that: The temperature of the drying process is 100-120°C; And / or, the static treatment time is 36-48h.

4. The method for preparing carbon monoxide according to claim 1, characterized in that: The preparation method comprises the following steps: 1) activating the catalyst using hydrogen to obtain an activated catalyst; 2) At a temperature of 400-600° C. and a pressure of 0.15-0.25 MPa, hydrogen and carbon dioxide are introduced into a fixed bed containing the activated catalyst for gas-solid contact to carry out the reverse water gas reaction to obtain the carbon monoxide.

5. The method for preparing carbon monoxide according to claim 4, characterized in that: The volume ratio of hydrogen to carbon dioxide is 3-3.5:1.

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