In-situ carbon capture and conversion method based on three-way catalyst

Abstract

The present invention relates to the field of catalyst technology, and in particular to a method for in-situ carbon capture and conversion based on a three-way catalyst. The present invention proposes a design concept for in-situ carbon capture and conversion, achieved by designing a three-way catalyst comprising an active component A that catalyzes the steam reforming reaction of organic matter, an active component B that catalyzes the in-situ conversion of CO2, and a support with CO2 capture properties. The active component A is at least one of Ni, Co, Fe, Mn, Pt, Ru, Rh, and Pd; and the active component B is at least one of Ni, Fe, Co, Mo, Pt, Ru, Rh, Pd, Cu, Zn, and Al. This method has the multiple functions of catalyzing the steam reforming of organic matter to produce hydrogen, and achieving in-situ carbon dioxide capture and conversion to produce high-value organic fuels.

Description

Technical Field

[0001] The present invention relates to the field of catalyst technology, and in particular to an in-situ carbon capture and conversion method based on a three-way catalyst. Background Art

[0002] Steam reforming of organic matter is a process in which hydrocarbons (or hydrocarbon hydroxides) react with water vapor at high temperatures to produce CO2 and H2. The most typical reaction is the steam reforming of methane. Currently, over 80% of global hydrogen production comes from the reforming of compounds containing carbon and hydrogen. Optimizing and improving the energy efficiency of this reaction is of great significance.

[0003] By capturing CO2 in situ at the reaction equilibrium state, the reaction equilibrium can be shifted in the positive direction, the reaction conversion rate can be increased, the reaction temperature can be lowered, and the reaction heat loss can be reduced, thereby improving energy utilization efficiency and hydrogen production efficiency. After absorbing / adsorbing CO2, traditional CO2 capture materials usually require a regeneration process of the capture material, which is generally carried out by inert gas purging and vacuuming. Among them, the inert gas purge requires, on the one hand, raising the inert gas temperature to the reaction temperature, or lowering the capture material temperature to room temperature, both of which require a temperature rise and fall cycle, in which a large amount of heat is difficult to recover efficiently. In particular, the low efficiency of solid heat recovery restricts the improvement of carbon capture efficiency. By reducing the partial pressure by vacuuming, the mechanical efficiency of the vacuum pump decreases exponentially with the reduction of separation pressure. When the vacuum pressure drops below 0.01 bar, the mechanical efficiency will be less than 1%, so the separation energy consumption increases sharply, which also seriously limits the energy utilization efficiency of the carbon capture process.

[0004] In summary, low energy efficiency limits the large-scale application and promotion of carbon capture, but there is currently no technical solution to efficiently achieve carbon capture. Summary of the Invention

[0005] Based on the above, the present invention provides an in-situ carbon capture and conversion method based on a three-way catalyst. This method not only efficiently catalyzes the reforming reaction of organic compounds containing carbon and hydrogen with water vapor, but also efficiently captures the CO2 generated by the reaction and converts it under specific conditions, such as in-situ CO2 hydrogenation or methane reforming reactions. This allows the adsorbed / absorbed CO2 to be directly converted into high-value products, avoiding the energy-intensive regeneration process of the CO2 capture material and improving overall reaction efficiency.

[0006] To achieve the above object, the present invention provides the following solutions:

[0007] One of the technical solutions of the present invention is a three-way catalyst for in-situ carbon capture and conversion, comprising an active component A for catalyzing the steam reforming reaction of organic matter, an active component B for catalyzing the in-situ conversion reaction of CO2, and a carrier with CO2 capture performance;

[0008] The active component A is at least one of Ni, Co, Fe, Mn, Pt, Ru, Rh, and Pd;

[0009] The active component B is at least one of Ni, Fe, Co, Mo, Pt, Ru, Rh, Pd, Cu, Zn, and Al;

[0010] The carrier is at least one of CaO, MgO, Ca(OH)2, Mg(OH)2, Li2ZrO3, Li2SiO3, Li4SiO4, zeolite, hydrotalcite or molecular sieve.

[0011] The present invention considers adding a CO2 in-situ conversion reaction on the basis of the traditional organic steam reforming hydrogen production reaction, and combines the two reactions by creatively designing a three-way catalyst.

[0012] In some preferred embodiments of the present invention, the mass ratio of the active component A to the active component B is 1:(0.1-10), and the mass ratio of the active component A to the carrier is 1:(1-10000).

[0013] Furthermore, the mass ratio of the active component A to the active component B is 1:(0.1-5), and the mass ratio of the active component A to the carrier is 1:(1-1000).

[0014] In some preferred embodiments of the present invention, the specific surface area of ​​the carrier is 1-500m 2 / g.

[0015] In some preferred embodiments of the present invention, the particle sizes of the active component A and the active component B are independently 10-10000 nm.

[0016] In some preferred embodiments of the present invention, the support is a CaO-MgO support or a Li2ZrO3-Al2O3 support;

[0017] The CaO-MgO carrier is prepared by mixing CaO powder and MgO powder in a mass ratio of 12:4.8, adding a small amount of deionized water, stirring evenly, and then drying at 100° C. for 12 hours.

[0018] The Li2ZrO3-Al2O3 carrier is prepared by mixing Li2ZrO3 powder and Al2O3 powder in a mass ratio of 3:1, adding a small amount of deionized water, stirring evenly to form a slurry, and then drying at 130°C for 18 hours.

[0019] Compared to single-component supports, composite supports can improve thermal stability and enhance redox capacity. Taking CaO-MgO and Li2ZrO3-Al2O3 as examples, supports prepared using the aforementioned raw material ratios, drying temperature, and time parameters exhibit a longer service life than supports prepared using other raw material ratios, drying temperature, and time parameters, while maintaining high CO2 absorption.

[0020] A second technical solution of the present invention is a method for preparing the above-mentioned three-way catalyst for in-situ carbon capture and conversion, which is prepared by compounding active component A and active component B with a carrier. The compounding method can adopt common preparation methods in the art, such as gas phase method, liquid phase method, solid phase method, plasma method, etc. The synthesis method of the three-way catalyst only needs to meet the following requirements, and the appropriate synthesis method can be selected according to the actual situation:

[0021] (1) Select the corresponding active component A, active component B and carrier components according to the reaction required for production;

[0022] (2) Rationally design the molar mass ratio of active component A, active component B, and support components in the three-way catalyst based on the catalytic effect;

[0023] (3) According to the designed ratio, select a suitable preparation method to achieve the working conditions required for synthesis, and combine the three different components (active component A, active component B and carrier component) into the desired target product.

[0024] For example, when a liquid phase method is used, the preparation method of the three-way catalyst for in-situ carbon capture and conversion comprises the following steps:

[0025] dissolving a salt containing active component A in water to obtain an active component A solution;

[0026] dissolving a salt containing active component B in water to obtain an active component B solution;

[0027] The active component A solution, the active component B solution and the carrier are uniformly mixed according to the mass ratio of active component A to active component B and the carrier, and then dried and calcined to obtain the three-way catalyst for in-situ carbon capture and conversion.

[0028] The drying temperature is 100-200° C. and the drying time is 2-18 hours.

[0029] The calcination temperature is 500-1000° C. and the calcination time is 4-12 hours.

[0030] In the present invention, the purpose of drying is to evaporate the water. If the drying step is omitted and calcination is performed directly, the catalyst structure will change due to excessive water, thereby affecting the catalytic performance.

[0031] The third technical solution of the present invention is the use of the above-mentioned three-way catalyst for in-situ carbon capture and conversion in catalyzing steam reforming reactions of organic matter and / or catalyzing in-situ conversion reactions of CO2.

[0032] A third technical solution of the present invention is an in-situ carbon capture and conversion method based on the above-mentioned three-way catalyst, wherein the three-way catalyst is used to catalyze the steam reforming reaction of organic matter. When the concentration of CO2 in the product remains unchanged, it indicates that the catalyst has absorbed CO2 and is close to saturation. The organic steam reforming reaction is basically completed, which means that CO2 has accumulated to be sufficient to support the next step of the CO2 in-situ conversion reaction. At this time, the organic steam reforming reaction is stopped, and the three-way catalyst is switched to catalyze the CO2 in-situ conversion reaction. During the catalytic CO2 in-situ conversion reaction, when the concentration of the target product (such as methane, ethane and / or ethylene gas) does not change, it indicates that the CO2 in-situ conversion reaction is basically completed. The three-way catalyst is switched to catalyze the steam reforming reaction of organic matter, and the above-mentioned catalytic organic steam reforming reaction and catalytic CO2 in-situ conversion reaction operations are repeated.

[0033] In some preferred embodiments of the present invention, in the organic matter steam reforming reaction, the molar ratio of steam to hydrocarbon is (1-10):1, and the space velocity is 1-360000m 3 h -1 , the reaction temperature is 100-1000℃, and the reaction pressure range is 1-30bar;

[0034] The temperature of the catalytic CO2 in-situ conversion reaction is 100-1000°C, and the reaction pressure ranges from 1-30 bar.

[0035] In some preferred embodiments of the present invention, the catalytic CO2 in-situ conversion reaction includes a CO2 hydrogenation reaction and a CO2 dry reforming reaction.

[0036] The present invention discloses the following technical effects:

[0037] Compared with traditional catalytic methods, the method proposed in this paper offers several advantages: 1) Improved energy efficiency of steam reforming of organic matter, lowering reaction temperature, reducing heat loss, and improving energy efficiency; 2) Reduced energy consumption for carbon capture material regeneration: By converting captured CO2 into high-value-added organic fuel in situ, the energy-intensive CO2 capture material regeneration process is avoided, saving energy in the carbon capture cycle. This conversion process can include hydrogenation and dry reforming reactions; 3) Highly integrated and compact system: The catalyst can realize steam reforming of organic matter, CO2 capture, and in-situ CO2 conversion reactions, integrating the three traditional system units into one, saving reaction space. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0039] Figure 1 Microscopic diagram of the three-way catalyst designed for the present invention.

[0040] Figure 2 The figure is a schematic diagram of the reaction flow for proposing the design idea of ​​the present invention.

[0041] In the figure, 1-active component A that catalyzes the hydrogen production reaction of low-value organic matter water vapor; 2-active component B that catalyzes the in-situ conversion reaction of CO2; 3-support with CO2 adsorption and desorption properties. DETAILED DESCRIPTION

[0042] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0043] It should be understood that the terms described herein are intended only to describe particular embodiments and are not intended to limit the present invention. In addition, for numerical ranges herein, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. The intermediate value within any stated value or stated range, and each smaller range between any other stated value or intermediate value within the stated range, is also encompassed within the present invention. The upper and lower limits of these smaller ranges may be independently included or excluded within the scope.

[0044] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0045] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0046] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0047] This invention provides a method for in-situ carbon capture and conversion using a three-way catalyst. This method incorporates a steam reforming reaction for organic matter, an in-situ CO2 capture reaction, and an in-situ CO2 conversion reaction (such as hydrogenation and dry reforming) to produce organic fuel. The three-way catalyst reduces process energy consumption and improves energy efficiency in both the reforming reaction and the carbon capture process.

[0048] The working process of the in-situ carbon capture and conversion method based on a three-way catalyst of the present invention includes three parts:

[0049] 1) Organic steam reforming reaction: Taking organic steam reforming as an example, most organic matter and water vapor undergo reforming reaction under high temperature conditions (100-1000℃) and the action of catalyst to produce CO, CO2 and H2. The chemical reaction formula of this process is:

[0050] C x H y O Z +H2O→CO+H2+CO2

[0051] 2) CO2 capture: organic steam reforming reaction (C x H y O Z +H2O→CO+H2+CO2), the gas components contain a certain amount of CO2. CO2 is adsorbed / absorbed by the capture material in the catalyst (such as CaO, MgO, etc.), which shifts the reforming reaction equilibrium in the positive direction, improves the reaction conversion rate and reduces the reaction temperature. As the CO2 concentration in the product (CO+H2+CO2) decreases, the CO and H2O in the product will further generate CO2 and H2 through the water gas shift reaction, and ultimately the product will be converted into H2 and captured CO2. Taking CaO as an example, the chemical reaction formula for this process is:

[0052] CO+H2O→CO2+H2

[0053] CO2+CaO→CaCO3

[0054] 3) In-situ CO2 conversion reaction: The catalyst after capturing CO2 is converted into high-value products in situ and the carbon capture material is regenerated. This can be achieved through in-situ hydrogenation and dry reforming reactions. Taking the hydrogenation reaction of CaO as the carbon capture material and methane as the product as an example, the chemical reaction formula of this process is:

[0055] CaCO3+4H2→CH4+2H2O+CaO

[0056] Taking the dry reforming reaction with CaO as the carbon capture material and methane as the reactant as an example, the chemical reaction formula of this process is:

[0057] CaCO3+CH4→2CO+2H2+CaO

[0058] Through the above process, the three-way catalyst of the present invention realizes efficient steam reforming of hydrocarbons, capture and in-situ conversion of CO2, thereby achieving the purpose of reducing energy consumption and improving carbon capture energy efficiency.

[0059] The microscopic schematic diagram of the three-way catalyst of the present invention is as follows Figure 1 As shown; the reaction flow diagram of the three-way catalyst of the present invention is as shown Figure 2 In the figure, 1 is the active component A that catalyzes the steam reforming reaction of organic matter; 2 is the active component B that catalyzes the in-situ conversion reaction of CO2; 3 is the carrier with CO2 capture performance.

[0060] Unless otherwise specified, the technical solutions described in the present invention are all conventional solutions in the field, and the reagents or raw materials used, unless otherwise specified, are purchased from commercial channels or have been disclosed.

[0061] The technical solutions provided by the present invention are described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0062] Example 1: Preparation of a three-way catalyst (Ni-Cu CaMgO2) with Ni and Cu as active components

[0063] Prepare active component A solution: weigh 5 g of Ni(NO3)2·6H2O and dissolve it in 100 mL of deionized water to obtain Ni(NO3)2 solution.

[0064] Prepare active component B solution: weigh 5 g of Cu(NO3)2·3H2O and dissolve it in 100 mL of deionized water to obtain a Cu(NO3)2 solution.

[0065] Preparation of carrier C material: 25 g of CaO powder and 25 g of MgO powder were weighed and mixed, a small amount of deionized water was added and stirred evenly to form a slurry, and dried at 100° C. for 12 hours to obtain a CaO-MgO carrier material.

[0066] Preparation of a three-way catalyst: Active component A solution, active component B solution, and carrier C material were uniformly mixed in a Ni:Cu:CaO-MgO carrier material mass ratio of 1:1:10, dried at 100°C for 12 hours, and then calcined at 500°C for 4 hours to obtain a three-way catalyst (the Ni particle size in the three-way catalyst was 10-100 nm, and the Cu particle size was 5-50 nm).

[0067] The mechanism of action of the three-way catalyst prepared in this embodiment is as follows:

[0068] In the catalytic methane steam reforming reaction, the Ni active component catalyzes the reaction of methane and steam at high temperature to produce synthesis gas. The Ni surface provides reactive sites, promoting the decomposition of CH4 and its reaction with H2O. The reaction that occurs at this time is:

[0069] CH4+2H2O→CO2+4H2

[0070] The CO2 generated by the reforming reaction is adsorbed by the CaO-MgO support material at the reaction temperature. Due to the high specific surface area and adsorption properties of CaO-MgO, CO2 can be effectively captured. Under the catalytic action of the Ni active component, the captured CO2 is methanated with H2 to produce high-value products. The mechanism is that the Ni surface provides active sites, and Cu acts as a co-catalyst, jointly promoting the reaction of CO2 and H2:

[0071] CO2+4H2→CH4+2H2O

[0072] Example 2: Preparation of a three-way catalyst (Ni / CuO-ZnO-Al2O3 / CaO-Al2O3) with CuZnAl as the active component

[0073] Prepare active component A solution: weigh 0.05 mol Cu(NO3)2 and dissolve it in 50 mL of deionized water to obtain a Cu(NO3)2 solution.

[0074] Prepare active component B solution: weigh 0.05 mol Zn(NO3)2 and dissolve it in 50 mL deionized water to obtain Zn(NO3)2 solution.

[0075] Prepare active component C solution: weigh 0.05 mol Al(NO3)3 and dissolve it in 50 mL deionized water to obtain Al(NO3)3 solution.

[0076] Prepare active component D solution: weigh 0.01 mol Ni(NO3)2 and dissolve it in 50 mL deionized water to obtain Ni(NO3)2 solution.

[0077] Preparation of carrier E material: 10 g of CaO powder was weighed and mixed with 2 g of porous Al2O3 powder. A small amount of deionized water was added and stirred evenly to form a slurry. The slurry was dried at 130°C for 18 hours to obtain a CaO-Al2O3 carrier material.

[0078] Preparation of a three-way catalyst: The above solution A, solution B, solution C, solution D, and material E were uniformly mixed, citric acid was added to adjust the pH of the reaction system to 5, the mixture was dried at 100° C. for 12 hours, and then calcined at 500° C. for 6 hours to obtain a three-way catalyst (the particle size of the CuZnAl metal oxide in the three-way catalyst was approximately 10-100 nm, and the particle size of the Ni oxide was approximately 5-50 nm).

[0079] The mechanism of action of the three-way catalyst prepared in this embodiment is as follows:

[0080] Catalytic methane steam reforming reaction: The nickel active component catalyzes the reaction of methane and water vapor at high temperatures. The mechanism is that the nickel surface provides reactive sites, promoting the decomposition of CH4 and its reaction with H2O.

[0081] CH4+2H2O→CO2+4H2

[0082] The CO2 generated by the reforming reaction is adsorbed by the CaO support material at the reaction temperature. Due to the high specific surface area and adsorption properties of porous Al2O3, CO2 can be effectively captured.

[0083] The captured CO2 reacts with H2 to produce methanol under the catalytic action of the surface active sites of the CuZnAl active component.

[0084] CO2+3H2→CH3OH+H2O

[0085] Effect Example 1

[0086] 20 g of the catalyst prepared in the above example and the carrier CaO-Al2O3 without active components were taken as benchmarks for comparison, and the performance of the catalyst was tested using the following method.

[0087] The test process was conducted in two fixed-bed reactors, using 10 g of catalyst. The steam reforming reaction temperature for organic matter (methane) was 550°C, with a steam-to-methane molar ratio of 3:1 and a gas flow rate of 200 mL / min. The reaction occurred as CH₄ + 2H₂O → CO₂ + 4H₂. The in-situ catalytic CO₂ conversion reaction was conducted in a hydrogenation reactor at 300°C and a pressure of 10 bar, with the reaction occurring as CO₂ + 3H₂ → CH₃OH + H₂O. The catalyst circulated repeatedly between the two reactors, with a residence time of 10 hours in the steam reforming reactor and 30 minutes in the hydrogenation reactor. After 1 and 10 hours of steam reforming, the reaction products were analyzed by gas chromatography-mass spectrometry, monitoring the real-time concentrations of gases such as H₂, CO₂, and CH₄. The results are summarized in Table 1. After the hydrogenation reactor reacted for 30 minutes, the reaction products were analyzed by gas mass spectrometry, and the statistical results are shown in Table 2.

[0088] Table 1. Results of steam methane reforming reactions catalyzed by three-way catalysts

[0089]

[0090] Note: “-” in the table means that the target product was not detected in this group of experiments, that is, no target product was generated or the concentration of the target product was lower than the lower limit of instrument detection accuracy (0.01%).

[0091] Effect Example 2

[0092] The only difference from Example 1 is that the catalytic CO2 in-situ conversion reaction is carried out in a hydrogenation reactor at a temperature of 400°C and a pressure of 1 bar. The reaction is CO2 + 4H2 → CH4 + 2H2O. The results are summarized in Table 2.

[0093] Effect Example 3

[0094] The only difference from Example 1 is that the catalytic CO2 in-situ conversion reaction was carried out in a hydrogenation reactor at a reaction temperature of 800°C and a pressure of 10 bar. The reactions that occurred were 2CO2 + 7H2 → C2H6 + 4H2O, 2CO2 + 6H2 → C2H4 + 4H2O, and 3CO2 + 10H2 → C3H8 + 6H2O. The results are summarized in Table 2.

[0095] Effect Example 4

[0096] The only difference from Example 1 is that the catalytic CO2 in-situ conversion reaction was carried out in a hydrogenation reactor at a temperature of 250°C and a pressure of 1 bar, and the reaction occurred as CO2 + H2 → CO + H2O. The results are summarized in Table 2.

[0097] Table 2. Gas data of the three-way catalyst after saturation with CO2 and hydrogenation at 650℃ for 2h

[0098]

[0099] As shown in Table 1, the three-way catalysts prepared according to the preparation method of the three-way catalyst provided by the present invention exhibited higher methane conversion, hydrogen yield, and carbon dioxide absorption rates than the benchmark catalyst CaO-Al2O3 at different time periods in the steam methane reforming reaction. This indicates that the three-way catalyst of the present invention can effectively generate hydrogen and increase methane yield in the steam methane reforming reaction. Compared with conventional industrial steam methane reforming catalysts, the three-way catalyst of the present invention not only has higher activity and stability, but also promotes the reaction and improves reaction selectivity.

[0100] Analysis of Table 2 shows that the three-way catalyst of the present invention can convert carbon dioxide in situ to increase the yield of organic matter, avoid the high energy consumption of CO2 capture material regeneration process, convert carbon dioxide into high-value products, improve energy utilization, and reduce energy consumption in the reaction.

[0101] The present invention prepares a method for in-situ carbon capture and conversion based on a three-way catalyst by combining an active component that catalyzes the steam reforming reaction of organic matter with an active component that catalyzes the in-situ conversion reaction of CO2 and a carrier with CO2 capture performance. The method can avoid the high-energy consumption CO2 capture material regeneration process, convert carbon dioxide into high-value products, reduce the reaction temperature and reaction heat loss, improve energy utilization efficiency and hydrogen production efficiency, and achieve the technical effect of 1+1+1 greater than 3.

[0102] It should be noted that the catalytic CO2 in-situ conversion reaction in the present invention does not require desorption of the CO2 in the catalyst. In the catalytic CO2 in-situ conversion reaction, the CO2 in the catalyst is allowed to participate in the reaction by hydrogenation or the introduction of methane. As the carbon dioxide hydrogenation reaction or the methane dry reforming reaction proceeds, the carbon dioxide captured in the catalyst is consumed, that is, the catalytic CO2 in-situ conversion reaction process is the regeneration process of the carbon dioxide capture material (such as adsorbent, absorbent).

[0103] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. An in-situ carbon capture and conversion method, characterized in that: Using a three-way catalyst to catalyze an organic steam reforming reaction, when the concentration of CO2 in the product remains unchanged, stopping the organic steam reforming reaction, and switching the three-way catalyst to catalyze an in-situ CO2 conversion reaction; during the catalytic CO2 in-situ conversion reaction, when the concentration of the target product does not change, switching the three-way catalyst to catalyze an organic steam reforming reaction, and repeating the above-mentioned catalytic organic steam reforming reaction and catalytic CO2 in-situ conversion reaction operations; The three-way catalyst is a three-way catalyst Ni-Cu CaMgO2 with Ni and Cu as active components, or a three-way catalyst Ni / CuO-ZnO-Al2O3 / CaO-Al2O3 with CuZnAlNi as active components; The preparation method of the Ni-Cu CaMgO2 comprises the following steps: Prepare active component A solution: weigh 5 g Ni(NO3)2·6H2O and dissolve it in 100 mL deionized water to obtain Ni(NO3)2 solution; Prepare active component B solution: weigh 5 g of Cu(NO3)2·3H2O and dissolve it in 100 mL of deionized water to obtain Cu(NO3)2 solution; Prepare the support C material: Weigh 25 g of CaO powder and 25 g of MgO powder, mix them, add a small amount of deionized water and stir evenly to make a slurry, and dry it at 100°C for 12 hours to obtain the CaO-MgO support material; Preparation of three-way catalyst: Active component A solution, active component B solution and carrier C material were mixed evenly in a Ni:Cu:CaO-MgO carrier material mass ratio of 1:1:10, dried at 100°C for 12 hours, and then calcined at 500°C for 4 hours to obtain Ni-Cu CaMgO2; The preparation method of Ni / CuO-ZnO-Al2O3 / CaO-Al2O3 comprises the following steps: Prepare active component A solution: weigh 0.05 mol Cu(NO3)2 and dissolve it in 50 mL deionized water to obtain Cu(NO3)2 solution; Prepare active component B solution: weigh 0.05 mol Zn(NO3)2 and dissolve it in 50 mL deionized water to obtain Zn(NO3)2 solution; Prepare active component C solution: weigh 0.05 mol Al(NO3)3 and dissolve it in 50 mL deionized water to obtain Al(NO3)3 solution; Prepare active component D solution: weigh 0.01 mol Ni(NO3)2 and dissolve it in 50 mL deionized water to obtain Ni(NO3)2 solution; Preparation of carrier E material: 10 g of CaO powder was weighed and mixed with 2 g of porous Al2O3 powder. A small amount of deionized water was added and stirred to form a slurry. The mixture was dried at 130°C for 18 hours to obtain a CaO-Al2O3 carrier material. Preparation of a three-way catalyst: Mix solution A, solution B, solution C, solution D, and material E above, add citric acid to adjust the pH of the reaction system to 5, dry at 100°C for 12 hours, and then calcine at 500°C for 6 hours to obtain Ni / CuO-ZnO-Al2O3 / CaO-Al2O3; In the organic matter steam reforming reaction, the molar ratio of steam to hydrocarbon is (1-10):1, and the space velocity is 1-360000m 3 h -1 , the reaction temperature is 100-1000℃, and the reaction pressure range is 1-30bar; The temperature of the catalytic CO2 in-situ conversion reaction is 100-1000°C, and the reaction pressure ranges from 1-30 bar; The catalytic CO2 in-situ conversion reaction includes a CO2 hydrogenation reaction and a CO2 dry reforming reaction.

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