Carbon dioxide capture and conversion integrated catalyst and preparation method thereof

Abstract

The invention discloses a carbon dioxide capture and conversion integrated catalyst and a preparation method thereof, the carbon dioxide capture and conversion integrated catalyst comprises: catalyst particles, the catalyst particles comprise a carrier and active components loaded on the carrier, the active components comprise a first active component, a second active component and a third active component, the first active component comprises one or two of Ni, Mn, Ce and Co, the second active component comprises one or two of K, Na and Mg, and the third active component comprises Ti; each catalyst particle comprises a first shell and a second shell, the outer surface of the carrier is coated with the first shell, and the outer surface of the first shell is coated with the second shell; wherein the first shell comprises a first active component and a second active component, and the second shell comprises a third active component. According to the carbon dioxide capture and conversion integrated catalyst provided by the embodiment of the invention, capture and conversion reactions of carbon dioxide can be realized at the same time, and the effect is more stable.

Description

Technical Field

[0001] The present invention relates to the field of catalysts, and in particular to a carbon dioxide capture and conversion integrated catalyst and a preparation method thereof. Background Art

[0002] Fossil fuels, as a primary energy source, emit carbon dioxide (CO2), a major greenhouse gas that contributes to global warming and climate change. Currently, the primary method is to capture CO2 emissions using absorbents to obtain high-concentration CO2, which is then converted into downstream products. However, this process is energy-intensive and complex to utilize. Therefore, a one-step method to directly capture CO2 from tail gas and convert it into fuels or chemicals can not only reduce the harmful effects of CO2, but also enable the production of fuels and chemicals, while also simplifying the process while reducing energy consumption.

[0003] Currently, metal-based catalysts suffer from sintering and carbon deposition during CO2 conversion, impacting their activity and stability. Molecular sieve catalysts also suffer from deactivation due to the migration of alkaline metal ions. To address these issues, the design and development of novel catalysts is crucial for achieving integrated CO2 capture and conversion. Precious metal catalysts can exhibit high activity, but their high cost and other drawbacks hinder their widespread application. Non-precious nickel-based catalysts are widely used in catalytic CO2 conversion reactions due to their low cost, good catalytic activity, and tunability. To achieve integrated capture and conversion, bifunctional catalysts that simultaneously perform CO2 adsorption and enrichment as well as hydrogenation conversion are also needed. Furthermore, granular catalysts offer high mass transfer efficiency and flexibility, allowing for flexible loading arrangements, such as fixed and fluidized beds, to accommodate diverse reaction conditions and process requirements, offering promising application prospects.

[0004] In recent years, Muller's team realized CO2 capture and conversion in a simulated flue gas atmosphere by mechanically mixing the Ni / MgO-Al2O3 catalyst prepared by co-precipitation method with limestone, and then carried out reforming to prepare syngas in CH4 atmosphere, but there was a problem of easy sintering of CaO (ACS Catal. 2018, 8, 4, 2815-2823). Veselovskaya's team realized direct capture and conversion of CO2 from air by means of reactor series, filled K2CO3 / Al2O3 adsorbent in the carbon capture reactor, after CO2 capture, H2 was introduced to realize CO2 desorption and carry into the catalytic reactor filled with 4% Ru / Al2O3 to carry out methanation reaction, and the CO2 conversion rate could reach 98% (Energy. 2018, 159, 15, 766-773). Although the existing catalyst or catalyst combination can realize the integration of CO2 capture and conversion, the catalyst is easy to deactivate, and the integration reaction needs to be completed by a combination of multiple catalysts, so it is urgent to realize the integration of CO2 capture and conversion on a single catalyst by optimizing the components and adding additives. SUMMARY

[0005] The present application aims to at least solve one of the technical problems existing in the prior art. To this end, one object of the present application is to propose a carbon dioxide capture and conversion integrated catalyst, the catalyst particle comprising a first shell and a second shell, by making the first shell comprise a first active component and a second active component, wherein the first active component comprises one or two of Ni, Mn, Ce and Co, the first active component can fix the captured carbon dioxide, and the second active component comprises one or two of K, Na and Mg, the second active component can capture carbon dioxide, so that the catalyst can realize the capture and conversion reaction of carbon dioxide at the same time, and does not contain noble metal, and the cost is lower; by making the second shell comprise a third active component, and the third active component comprises Ti, Ti can fully coat the first shell, realize the fixation of active center, so that the effect of the catalyst is more stable, and the risk of deactivation of the catalyst caused by the agglomeration of the first active component and the second active component is reduced.

[0006] The present application also proposes a preparation method of the above-mentioned carbon dioxide capture and conversion integrated catalyst.

[0007] According to an embodiment of the first aspect of the present invention, an integrated carbon dioxide capture and conversion catalyst includes: catalyst particles, the catalyst particles including a carrier and an active component loaded on the carrier, the active component including a first active component, a second active component and a third active component, the carrier including one or two of TiO2 and SiO2, the first active component including one or two of Ni, Mn, Ce and Co, the second active component including one or two of K, Na and Mg, and the third active component including Ti; the catalyst particles including a first shell and a second shell, the first shell being coated on the outer surface of the carrier, and the second shell being coated on the outer surface of the first shell; wherein, the first shell includes the first active component and the second active component, and the second shell includes the third active component.

[0008] According to the integrated carbon dioxide capture and conversion catalyst of an embodiment of the present invention, the catalyst particles include a first shell and a second shell. The first shell includes a first active component and a second active component, wherein the first active component includes one or two of Ni, Mn, Ce and Co, and the first active component can convert and fix the captured carbon dioxide, and the second active component includes one or two of K, Na, and Mg, and the second active component can capture carbon dioxide. In this way, the catalyst can simultaneously achieve carbon dioxide capture and conversion reactions, and does not include precious metals, so the cost is low. The second shell includes a third active component, and the third active component includes Ti, and Ti can fully cover the first shell to achieve fixation of the active center, so that the effect of the catalyst is more stable, and the risk of the first active component and the second active component agglomerating together to cause catalyst deactivation is reduced.

[0009] According to some embodiments of the present invention, in a single catalyst particle, the molar ratio of the carrier, the first active component, the second active component, and the third active component is 1:(0.01-0.2):(0.1-0.2):(0.01-0.05).

[0010] According to some embodiments of the present invention, a plurality of the catalyst particles form a catalyst ball, the catalyst ball is spherical, has holes inside, and has a diameter of 0.5-6 mm.

[0011] According to the second aspect of the present invention, the preparation method of the integrated carbon dioxide capture and conversion catalyst includes: preparing a first precursor solution containing the first active component and the second active component metal salt; adding the carrier to the first precursor solution, adding hexamethylenetetramine, and stirring at 40-90°C for 1-4 hours to obtain a first intermediate product; filtering and drying the first intermediate product, calcining it at 400-700°C in an air atmosphere for 1-6 hours, and then calcining it at 400-700°C in a hydrogen atmosphere for 1-6 hours to obtain a second intermediate product; preparing a second precursor solution containing a third active component metal salt; adding the second intermediate product to the second precursor solution, adding citric acid, stirring at 40-90°C for 1-4 hours, then filtering, drying at 80-120°C for 2-6 hours, and finally calcining it at 400-700°C in an air atmosphere for 1-6 hours to obtain a powdered integrated carbon dioxide capture and conversion catalyst.

[0012] According to the preparation method of the integrated carbon dioxide capture and conversion catalyst of an embodiment of the present invention, by adding a carrier to a first precursor solution including a first active component and a second active component metal salt, the catalyst can simultaneously achieve carbon dioxide capture and conversion reactions; by adding the second intermediate product to a second precursor solution including a third active component metal salt, the effect of the catalyst can be made more stable, and the risk of the first active component and the second active component agglomerating together to cause catalyst deactivation can be reduced.

[0013] According to some embodiments of the present invention, the powdered integrated carbon dioxide capture and conversion catalyst is formed into raw balls through a rolling ball forming technology, and then the raw balls are calcined to obtain catalyst balls.

[0014] According to some embodiments of the present invention, the process further comprises: mixing the powdered carbon dioxide capture and conversion integrated catalyst by ball milling, wherein the ball milling speed is 200-500 r / min and the ball milling time is 10-30 min.

[0015] According to some embodiments of the present invention, the powdered carbon dioxide capture and conversion integrated catalyst is formed into raw balls through a rolling ball forming technology, comprising: adding the powdered carbon dioxide capture and conversion integrated catalyst into a ball forming machine, spraying in a binder, and finally forming the raw balls.

[0016] According to some embodiments of the present invention, the adhesive includes: a pore former, a binder, and a peptizing agent.

[0017] According to some embodiments of the present invention, the powdered carbon dioxide capture and conversion integrated catalyst and the binder are used in the following amounts, in parts by weight: The supported catalyst: 70-90 parts; The pore-forming agent: 3-10 parts; The binder: 5-15 parts; The peptizing agent: 2-5 parts.

[0018] According to some embodiments of the present invention, the raw pellets are calcined to obtain the integrated carbon dioxide capture and conversion catalyst, comprising: a calcination temperature of 300-600° C., and a calcination time of 2-8 h.

[0019] Additional aspects and advantages of the present invention will be set forth in part in the description which follows and, in part, will be obvious from the description which follows, or may be learned by practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] The above and / or additional aspects and advantages of the present invention will become apparent and readily understood from the description of the embodiments with reference to the following drawings, in which: Figure 1 The present invention provides a method for preparing an integrated catalyst for carbon dioxide capture and conversion according to some embodiments of the present invention. DETAILED DESCRIPTION

[0021] The following describes embodiments of the present invention in detail. Examples of the embodiments are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are intended only to explain the present invention and are not to be construed as limiting the present invention.

[0022] Reference below Figure 1 The integrated carbon dioxide capture and conversion catalyst according to an embodiment of the present invention is described.

[0023] An integrated carbon dioxide capture and conversion catalyst according to an embodiment of the first aspect of the present invention includes catalyst particles. The catalyst particles include a carrier and active components supported on the carrier, the active components including a first active component, a second active component, and a third active component. The carrier includes one or both of TiO2 and SiO2, the first active component includes one or both of Ni, Mn, Ce, and Co, the second active component includes one or both of K, Na, and Mg, and the third active component includes Ti.

[0024] The catalyst particles include a first shell and a second shell, wherein the first shell is coated on the outer surface of the carrier, and the second shell is coated on the outer surface of the first shell; wherein the first shell includes a first active component and a second active component, and the second shell includes a third active component.

[0025] By making the catalyst particle include a first shell, the first shell being coated on the outer surface of the carrier, and making the first shell include a first active component, wherein the first active component includes one or two of Ni, Mn, Ce and Co, the first active component can convert the captured carbon dioxide; by making the first shell include a second active component, wherein the second active component includes one or two of K, Na, and Mg, the second active component can capture carbon dioxide. In this way, the catalyst can simultaneously realize carbon dioxide capture and conversion reactions, and the catalyst does not include noble metals, and the cost of preparing the catalyst is lower.

[0026] By making the catalyst include a second shell, the second shell being coated on the outer surface of the first shell, and making the second shell include a third active component, and the third active component including Ti, Ti can sufficiently coat the first shell, realize the fixation of active centers, so that the effect of the catalyst is more stable, and the risk of the first active component and the second active component agglomerating together to cause the catalyst to be deactivated is reduced.

[0027] According to the carbon dioxide capture and conversion integrated catalyst provided by the embodiment of the present application, the catalyst particle includes a first shell and a second shell, by making the first shell include a first active component and a second active component, wherein the first active component includes one or two of Ni, Mn, Ce and Co, the first active component can convert and fix the captured carbon dioxide, and the second active component includes one or two of K, Na, and Mg, the second active component can capture carbon dioxide, in this way, the catalyst can simultaneously realize carbon dioxide capture and conversion reactions, and does not include noble metals, and the cost is lower; by making the second shell include a third active component, and the third active component including Ti, Ti can sufficiently coat the first shell, realize the fixation of active centers, so that the effect of the catalyst is more stable, and the risk of the first active component and the second active component agglomerating together to cause the catalyst to be deactivated is reduced.

[0028] According to some embodiments of the present application, in a single catalyst particle, the molar ratio between the carrier, the first active component, the second active component, and the third active component is 1:(0.01-0.2):(0.1-0.2):(0.01-0.05). By making the ratio between the carrier, the first active component, the second active component, and the third active component be 1:(0.01-0.2):(0.1-0.2):(0.01-0.05), the content of the first active component and the second active component can be more sufficient, carbon dioxide can be more sufficiently captured and converted, and the third active component can more sufficiently fix the coating of the first active component and the second active component, so that the effect of the catalyst is more stable.

[0029] According to some embodiments of the present invention, a plurality of catalyst particles are formed into catalyst spheres, the catalyst spheres are spherical, have pores inside, and have a diameter of 0.5-6 mm. By making the catalyst spheres spherical and having pores inside, the contact area between the catalyst and the environment is increased, the number of active sites of the catalyst is increased, and the catalytic efficiency of the catalyst is improved.

[0030] Reference Figure 1 , according to the second embodiment of the present invention, the preparation method of the integrated carbon dioxide capture and conversion catalyst comprises: preparing a first precursor solution containing a first active component and a second active component metal salt; Adding the carrier to the first precursor solution, adding hexamethylenetetramine, and stirring at 40-90° C. for 1-4 hours to obtain a first intermediate product; The first intermediate product is filtered and dried, and then calcined at 400-700°C in an air atmosphere for 1-6 hours, and then calcined at 400-700°C in a hydrogen atmosphere for 1-6 hours to obtain a second intermediate product; preparing a second precursor solution containing a third active component metal salt; The second intermediate product is added to the second precursor solution, citric acid is added, and the mixture is stirred at 40-90°C for 1-4 hours, then filtered, dried at 80-120°C for 2-6 hours, and finally calcined at 400-700°C in an air atmosphere for 1-6 hours to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0031] For example, the metal salt containing the first active component can be nitrate, carbonate, acetate and citrate of Ni, Mn, Ce and Co; the metal salt containing the second active component can be nitrate, carbonate and acetate of K, Na and Mg; the metal salt containing the third active component can be nitrate, carbonate, acetate, citrate or organic titanium of Ti.

[0032] By first preparing a first precursor solution containing a first active component and a second active component metal salt, and then adding a carrier to the first precursor solution, a first shell including the first active component and the second active component can be coated on the surface of the carrier, so that the catalyst has the integrated function of capturing and converting carbon dioxide.

[0033] By adding hexamethylenetetramine to the first precursor solution, the hexamethylenetetramine can more evenly disperse and coat the first active component and the second active component on the carrier surface, reduce the agglomeration of the first active component and the second active component, and improve the catalytic performance of the catalyst.

[0034] The first intermediate product is filtered and dried, and then calcined in an air atmosphere and then in a hydrogen atmosphere. The calcination in the air atmosphere can more firmly fix the first active component and the second active component on the surface of the carrier to form a first shell, thereby preventing the first shell from falling off from the carrier and causing a decrease in the catalyst effect. By calcining the first intermediate product in a hydrogen atmosphere, the oxides of the first active component and the second active component can be reduced.

[0035] By preparing a second precursor solution containing a third active component and then adding the second intermediate product to the second precursor solution, a second shell containing the third active component can be coated on the outer surface of the first shell, which can make the effect of the catalyst more stable and reduce the risk of the first active component and the second active component agglomerating together to cause catalyst deactivation.

[0036] By adding citric acid to the second precursor solution, the citric acid can make the third active component more fully dispersed on the surface of the first shell.

[0037] According to the preparation method of the integrated carbon dioxide capture and conversion catalyst of an embodiment of the present invention, by adding a carrier to a first precursor solution including a first active component and a second active component metal salt, the catalyst can simultaneously achieve carbon dioxide capture and conversion reactions; by adding the second intermediate product to a second precursor solution including a third active component metal salt, the effect of the catalyst can be made more stable, and the risk of the first active component and the second active component agglomerating together to cause catalyst deactivation can be reduced.

[0038] Reference Figure 1 According to some embodiments of the present invention, a powdered carbon dioxide capture and conversion integrated catalyst is formed into raw balls through a rolling ball forming technology, and then the raw balls are roasted to obtain catalyst balls. By forming a powdered carbon dioxide capture and conversion integrated catalyst into raw balls through a rolling ball forming technology, and then roasting the raw balls to obtain catalyst balls, the catalyst can be formed into spherical catalyst balls, which increases the contact area between the catalyst and the gas, increases the active sites of the catalyst, and enhances the effect of the catalyst. Molding the catalyst material into catalyst balls through the rolling ball forming technology can ensure the uniform distribution of active components, thereby improving the catalytic performance and stability of the catalyst; at the same time, this molding method makes the integral catalyst exhibit extremely high stability, which can not only remain stable under high-speed airflow blowing, but also resist external force impact and is not easily broken.

[0039] According to some embodiments of the present invention, the method for preparing an integrated carbon dioxide capture and conversion catalyst further includes: mixing the powdered integrated carbon dioxide capture and conversion catalyst by ball milling, wherein the ball milling speed is 200-500 r / min and the ball milling time is 10-30 min. By mixing the powdered integrated carbon dioxide capture and conversion catalyst by ball milling, the powdered integrated carbon dioxide capture and conversion catalyst can be more fully mixed and the powdered integrated carbon dioxide capture and conversion catalyst can be more easily prepared into raw pellets.

[0040] Reference Figure 1 According to some embodiments of the present invention, a powdered integrated carbon dioxide capture and conversion catalyst is formed into green pellets using a rolling ball forming technique, including: adding the powdered integrated carbon dioxide capture and conversion catalyst to a pelletizer, spraying a binder, and ultimately forming green pellets. By adding the powdered integrated carbon dioxide capture and conversion catalyst to a pelletizer, spraying a binder, and ultimately forming green pellets, the contact area between the catalyst and the gas is increased, the number of active sites of the catalyst is increased, and the catalyst's effectiveness is enhanced.

[0041] According to some embodiments of the present invention, the adhesive includes: a pore-forming agent, a binder, and a peptizing agent. For example, the pore-forming agent may include one or more of polyvinyl alcohol, polyethylene glycol, polyacrylamide, carboxymethyl cellulose, and starch; the binder may include one or more of sesbania powder, boric acid, water glass, silica sol, and alumina sol; and the peptizing agent may include one or more of oxalic acid, citric acid, acetic acid, and ammonia water.

[0042] Among them, the pore-forming agent can make the final catalyst ball have more pores, which can increase the contact area between the catalyst ball and carbon dioxide and improve the catalytic speed of the catalyst ball; the binder can make the powdered carbon dioxide capture and conversion integrated catalyst bonded to form a sphere; the peptizing agent can be used to adjust the pH of the powdered carbon dioxide capture and conversion integrated catalyst to improve the effect of the catalyst.

[0043] According to some embodiments of the present invention, the powdered carbon dioxide capture and conversion integrated catalyst and binder are calculated in parts by weight, and the amounts of each raw material used are as follows: supported catalyst: 70-90 parts; pore former: 3-10 parts; binder: 5-15 parts; peptizer: 2-5 parts.

[0044] According to some embodiments of the present invention, calcining raw pellets to obtain an integrated carbon dioxide capture and conversion catalyst includes calcining at a temperature of 300-600°C for 2-8 hours. By calcining the raw pellets at a temperature of 300-600°C for 2-8 hours, the raw pellets can be more fully calcined.

[0045] For example, the catalyst can be loaded into a fluidized bed reactor and applied to the integrated carbon dioxide capture and conversion reaction. Refer to the following Figure 1 The preparation method of the integrated carbon dioxide capture and conversion catalyst according to the embodiment of the present invention is further described in conjunction with some embodiments and comparative examples of the present invention.

[0046] Example 1 (1) The carrier titanium dioxide is added to an aqueous solution of nickel nitrate and sodium nitrate, hexamethylenetetramine is added and the mixture is stirred at 80°C for 2 h, filtered and dried, calcined at 600°C in an air atmosphere for 2 h, and then calcined at 600°C in a hydrogen atmosphere for 2 h to obtain a second intermediate product. The second intermediate product is added to an aqueous solution of titanium nitrate, citric acid is added to adjust the pH, the mixture is stirred at 80°C for 2 h, filtered and dried, and finally calcined at 600°C in an air atmosphere for 2 h to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0047] (2) 90 parts of powdered carbon dioxide capture and conversion integrated catalyst were selected and placed in a pelletizer. A binder consisting of 3 parts of polyethylene glycol, 5 parts of boric acid, and 2 parts of ammonia water was sprayed into the pelletizer. The pellets were rolled to prepare raw material pellets with a particle size of 5 mm. The raw material pellets were then calcined at 600°C for 2 h to obtain the carbon dioxide capture and conversion integrated catalyst.

[0048] (3) The carbon dioxide capture and conversion integrated catalyst is loaded into a multi-circulating fluidized bed reactor and applied to the carbon dioxide capture and conversion integrated reaction.

[0049] Example 2 (1) The carrier titanium dioxide is added to an aqueous solution of nickel nitrate, cerium nitrate and sodium nitrate, hexamethylenetetramine is added and the mixture is stirred at 80°C for 3 h, filtered and dried, calcined at 700°C in an air atmosphere for 2 h, and then calcined at 650°C in a hydrogen atmosphere for 2 h to obtain a second intermediate product. The second intermediate product is added to an aqueous solution of titanium nitrate, citric acid is added to adjust the pH, the mixture is stirred at 80°C for 2 h, filtered and dried, and finally calcined at 600°C in an air atmosphere for 2 h to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0050] (2) 80 parts of powdered carbon dioxide capture and conversion integrated catalyst were selected and placed in a pelletizer. A binder consisting of 5 parts of polyethylene glycol, 12 parts of boric acid, and 3 parts of ammonia water was sprayed into the pelletizer. The pellets were rolled to prepare raw material balls with a particle size of 2 mm. The raw material balls were then calcined at 600°C for 2 h to obtain the carbon dioxide capture and conversion integrated catalyst.

[0051] (3) The carbon dioxide capture and conversion integrated catalyst is loaded into a multi-circulating fluidized bed reactor and applied to the carbon dioxide capture and conversion integrated reaction.

[0052] Example 3 (1) The carrier titanium dioxide is added to an aqueous solution of nickel nitrate, manganese nitrate and potassium nitrate, hexamethylenetetramine is added and the mixture is stirred at 70°C for 3 h, filtered and dried, calcined at 600°C in an air atmosphere for 2 h, and then calcined at 600°C in a hydrogen atmosphere for 2 h to obtain a second intermediate product. The second intermediate product is added to an aqueous solution of titanium nitrate, citric acid is added to adjust the pH, and the mixture is stirred at 80°C for 2 h, filtered and dried, and finally calcined at 600°C in an air atmosphere for 2 h to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0053] (2) 85 parts of powdered carbon dioxide capture and conversion integrated catalyst were selected and placed in a pelletizer. A binder consisting of 4 parts of polyethylene glycol, 9 parts of boric acid, and 2 parts of ammonia water was sprayed into the pelletizer. The pellets were rolled to prepare raw material pellets with a particle size of 5 mm. The raw material pellets were then calcined at 700°C for 2 h to obtain the carbon dioxide capture and conversion integrated catalyst.

[0054] (3) The carbon dioxide capture and conversion integrated catalyst is loaded into a multi-circulating fluidized bed reactor and applied to the carbon dioxide capture and conversion integrated reaction.

[0055] Example 4 (1) A mixture of carrier titanium dioxide and silicon dioxide is added to an aqueous solution of nickel nitrate, manganese nitrate and sodium nitrate, hexamethylenetetramine is added and the mixture is stirred at 80°C for 3 h, filtered and dried, calcined at 650°C in an air atmosphere for 2 h, and then calcined at 650°C in a hydrogen atmosphere for 4 h to obtain a second intermediate product. The second intermediate product is added to an aqueous solution of titanium nitrate, citric acid is added to adjust the pH, stirred at 80°C for 2 h, filtered and dried, and finally calcined at 600°C in an air atmosphere for 3 h to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0056] (2) 80 parts of powdered carbon dioxide capture and conversion integrated catalyst were selected and placed in a pelletizer. A binder consisting of 5 parts of polyethylene glycol, 12 parts of boric acid, and 3 parts of ammonia water was sprayed into the pelletizer. The pellets were rolled to prepare raw balls with a particle size of 3 mm. The raw balls were then calcined at 600°C for 2 h to obtain the carbon dioxide capture and conversion integrated catalyst.

[0057] (3) The carbon dioxide capture and conversion integrated catalyst is loaded into a multi-circulating fluidized bed reactor and applied to the carbon dioxide capture and conversion integrated reaction.

[0058] Example 5 (1) The carrier silica is added to an aqueous solution of nickel nitrate, cerium nitrate and magnesium nitrate, hexamethylenetetramine is added and the mixture is stirred at 80°C for 2 h, filtered and dried, calcined at 600°C in an air atmosphere for 2 h, and then calcined at 600°C in a hydrogen atmosphere for 2 h to obtain a second intermediate product. The second intermediate product is added to an aqueous solution of titanium nitrate, citric acid is added to adjust the pH, the mixture is stirred at 80°C for 2 h, filtered and dried, and finally calcined at 600°C in an air atmosphere for 2 h to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

[0059] (2) 83 parts of powdered carbon dioxide capture and conversion integrated catalyst were selected and placed in a pelletizer. A binder consisting of 4 parts of polyethylene glycol, 11 parts of boric acid, and 2 parts of ammonia water was sprayed into the pelletizer. The pellets were rolled to prepare raw material balls with a particle size of 3 mm. The raw material balls were then calcined at 600°C for 2 h to obtain the carbon dioxide capture and conversion integrated catalyst.

[0060] (3) The carbon dioxide capture and conversion integrated catalyst is loaded into a multi-circulating fluidized bed reactor and applied to the carbon dioxide capture and conversion integrated reaction.

[0061] In the description of the present invention, it should be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "up", "down", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inside", "outside", "clockwise", "counterclockwise", "axial", "radial", "circumferential" and the like to indicate orientations or positional relationships based on the orientations or positional relationships shown in the accompanying drawings, and are only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be understood as limiting the present invention.

[0062] In the description of the present invention, "first feature" or "second feature" may include one or more of the features.

[0063] In the description of the present invention, "plurality" means two or more.

[0064] In the description of the present invention, a first feature being “on” or “under” a second feature may include the first and second features being in direct contact with each other, or the first and second features not being in direct contact with each other but being in contact with each other via another feature therebetween.

[0065] In the description of the present invention, “on”, “above” and “above” a first feature of a second feature include the first feature being directly above and obliquely above the second feature, or simply means that the first feature is horizontally higher than the second feature.

[0066] Throughout this specification, reference to terms such as "one embodiment," "some embodiments," "illustrative embodiments," "examples," "specific examples," or "some examples" means that a specific feature, structure, material, or characteristic described in conjunction with that embodiment or example is included in at least one embodiment or example of the present invention. In this specification, illustrative uses of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0067] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to the embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the claims and their equivalents.

Claims

1. A carbon dioxide capture and conversion integrated catalyst, characterized in that: include: Catalyst particles, the catalyst particles comprising a carrier and active components supported on the carrier, the active components comprising a first active component, a second active component, and a third active component, the carrier comprising one or both of TiO2 and SiO2, the first active component comprising one or both of Ni, Mn, Ce, and Co, the second active component comprising one or both of K, Na, and Mg, and the third active component comprising Ti; The catalyst particles include a first shell and a second shell, wherein the first shell is coated on the outer surface of the carrier, and the second shell is coated on the outer surface of the first shell; The first shell includes a first active component and a second active component, and the second shell includes a third active component.

2. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 1, characterized in that: In a single catalyst particle, the molar ratio of the carrier, the first active component, the second active component, and the third active component is 1:(0.01-0.2):(0.1-0.2):(0.01-0.05).

3. The integrated carbon dioxide capture and conversion catalyst according to claim 1, characterized in that include: A plurality of the catalyst particles form a catalyst ball. The catalyst ball is spherical and has holes inside. The diameter of the catalyst ball is 0.5-6 mm.

4. A method for preparing an integrated carbon dioxide capture and conversion catalyst according to any one of claims 1 to 3, characterized in that: include: preparing a first precursor solution containing the first active component and the second active component metal salt; adding the carrier to the first precursor solution, adding hexamethylenetetramine, and stirring at 40-90° C. for 1-4 hours to obtain a first intermediate product; The first intermediate product is filtered and dried, and then calcined at 400-700° C. in an air atmosphere for 1-6 hours, and then calcined at 400-700° C. in a hydrogen atmosphere for 1-6 hours to obtain a second intermediate product; preparing a second precursor solution containing a third active component metal salt; The second intermediate product is added to the second precursor solution, citric acid is added, and the mixture is stirred at 40-90°C for 1-4 hours, then filtered, dried at 80-120°C for 2-6 hours, and finally calcined at 400-700°C in an air atmosphere for 1-6 hours to obtain a powdered carbon dioxide capture and conversion integrated catalyst.

5. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 4, characterized in that: The powdered carbon dioxide capture and conversion integrated catalyst is formed into raw balls through a rolling ball forming technology, and then the raw balls are calcined to obtain catalyst balls.

6. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 4, characterized in that: Also includes: The powdered carbon dioxide capture and conversion integrated catalyst is mixed by ball milling, wherein the ball milling speed is 200-500 r / min and the ball milling time is 10-30 min.

7. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 6, characterized in that: The step of forming the powdered carbon dioxide capture and conversion integrated catalyst into raw balls through a rolling ball forming technology comprises: adding the powdered carbon dioxide capture and conversion integrated catalyst into a ball forming machine, spraying a binder, and finally forming the raw balls.

8. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 7, characterized in that: The adhesive comprises a pore-forming agent, a binder and a peptizing agent.

9. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 8, characterized in that: The powdered carbon dioxide capture and conversion integrated catalyst and the binder are calculated in parts by weight, and the amounts of each raw material used are as follows: The supported catalyst: 70-90 parts; The pore-forming agent: 3-10 parts; The binder: 5-15 parts; The peptizing agent: 2-5 parts.

10. The method for preparing the integrated carbon dioxide capture and conversion catalyst according to claim 4, wherein: The raw material pellets are roasted to obtain the carbon dioxide capture and conversion integrated catalyst, comprising: a roasting temperature of 300-600° C. and a roasting time of 2-8 h.

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