A low-temperature catalytic oxidation of CH4 by CO2 to produce C 2+ Preparation method of catalyst for oxygen-containing compounds

Abstract

The present invention belongs to the field of carbon resource utilization technology C1 chemistry. 2+ The invention discloses a method for preparing a catalyst for oxygen-containing compounds, comprising the following steps: co-precipitating any two or three nitrates of Ce, La, Ga, and Ir with an alkaline solution in a suspension of zirconium hydroxide, zinc hydroxide, and calcium hydroxide, and then sequentially aging, washing, filtering, drying, and roasting, and then grinding to form a powder; placing one of SiO2 molecular sieve, titanium silicon molecular sieve, and mordenite treated with 30-50% by weight nitric acid or 50-70% by weight hydrogen peroxide in a mixed solution of any three nitrates of Co, Ni, W, Sr, Cs, Cu, and Fe, and performing the process of placing, stirring, and heating the mixture into a paste; and sequentially washing, drying, and roasting the mixture, and then grinding the mixture into a powder; and mixing the mixture by ball milling at a mass ratio of 1-4.

Description

Technical Field

[0001] The present invention belongs to the field of carbon resource utilization technology C1 chemistry. Specifically, it relates to a method for producing C by coupling CO2 low temperature catalytic oxidation of CH4. 2+ Preparation and application of catalysts for oxygen-containing compounds. Background Art

[0002] CO2 and CH4 are major greenhouse gases and are the main culprits of global warming. How to effectively reduce the concentration of greenhouse gases and convert them into high-value chemicals is a research hotspot that has attracted worldwide attention. Using CO2 and CH4 as raw materials and carbon sources for other carbon-rich chemicals to replace coal, oil, and natural gas may be one of the most promising methods to achieve this goal. Low-temperature catalytic oxidation of CO2 and CH4 into high-value C 2+ Oxygen-containing compounds are of great significance for the efficient utilization of C1 resources, the reduction of greenhouse gas emissions, the reduction of the impact of the "greenhouse effect" on the atmospheric environment, the resolution of increasingly serious environmental problems, and the realization of sustainable development. At the same time, the process of reforming CO2 and CH4 to produce synthesis gas (DRM) is currently the most widely studied technical route for the comprehensive utilization of CO2 and CH4. However, this process requires breaking all the original chemical bonds of CO2 and CH4, resulting in high energy consumption. In addition, synthesis gas is not a product that can be used directly, and usually needs to be indirectly converted into liquid high-value products through the Fischer-Tropsch synthesis reaction. Under the "dual carbon" goal, the development of conversion technologies based on the structural characteristics of raw materials and the full realization of the intrinsic value of raw materials are the approaches that chemical process research and development should adopt. It is one of the future development directions of chemical processes under the "dual carbon" goal.

[0003] In traditional C1 chemical industry, the conversion of CO2 and CH4 into liquid chemicals requires first being subjected to high-temperature conditions to convert them into synthesis gas (CO and H2), and then indirectly achieving the final conversion through Fischer-Tropsch synthesis under high-pressure conditions. This process is complex, the conditions are harsh, and the cost is extremely high.

[0004] CN201711325666.4 provides a catalyst for producing synthesis gas by reforming methane with carbon dioxide and a preparation method thereof. The catalyst has the advantages of good dispersion of active components, high activity, and low carbon deposition, but the reaction temperature is 800°C and the process energy consumption is high.

[0005] CN202111543168 provides a method for preparing liquid products by low-temperature plasma catalysis of CO2 and CH4 mixed gas. The reaction process introduces plasma catalysis to synthesize C 2+ Liquid products are produced, but the intervention of plasma limits the subsequent catalytic reaction engineering scale-up and the reaction conditions are relatively harsh.

[0006] Coupling of CO2 to CH4 and CO2 to C at Low Temperature2+ Oxygenated compounds do not need to be converted into synthesis gas but can be directly synthesized into high-quality C 2+ The present invention adopts a new method of bifunctional synergistic catalytic synthesis of chemicals by using low-temperature chemical adsorption of CO2 to catalyze the activation of CO bonds and CH bonds in CH4, thereby achieving the selective conversion of CO2 and CH4 into high-value C 2+ Target chemicals containing oxygenates. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for producing C by coupling CO2 with CH4 at low temperature with high selectivity under low temperature reaction conditions. 2+ Preparation and application of catalysts for oxygen-containing compounds.

[0008] The technical solution adopted by the present invention is: a method for producing C by coupling CO2 low temperature catalytic oxidation of CH4 2+ The preparation method of the catalyst of oxygen-containing compound is carried out according to the following steps:

[0009] Step 1: Prepare the first catalytic component by co-precipitating any two or three nitrates of Ce, La, Ga, and Ir with an alkaline solution in a suspension of zirconium hydroxide, zinc hydroxide, and calcium hydroxide. The mixture is then aged, washed, filtered, dried, and calcined in sequence, and then ground into a powder, which is referred to as the first catalytic component and used in the co-precipitation method.

[0010] Step 2: preparing a second catalytic component by placing one of SiO2 molecular sieve, titanium silicon molecular sieve, and mordenite treated with 30-50% by weight nitric acid or 50-70% by weight hydrogen peroxide in a mixed solution of any three nitrates of Co, Ni, W, Sr, Cs, Cu, and Fe, placing, stirring, and heating to form a paste, and then sequentially washing, drying, and calcining, and grinding into a powder, which is recorded as the second catalytic component;

[0011] Step 3: Synthesize the catalyst: mix the first catalytic component and the second catalytic component in a mass ratio of 1-4 by ball milling, press the mixture into tablets, and crush the tablets into 40-60 mesh particles to obtain the catalyst.

[0012] In step 1, the ratio of the total molar number of Ce, La, Ga, and Ir to the total molar number of zirconium hydroxide, zinc hydroxide, and calcium hydroxide is 1-3.

[0013] In step 1, during the co-current co-precipitation, the temperature is 30-70° C. and the pH value is 7-9.

[0014] In step 1, the drying temperature is 80-120°C, and the roasting temperature is 350-500°C.

[0015] In step 2, the ratio of the total molar number of Co, Ni, W, Sr, Cs, Cu, and Fe to the total molar number of SiO2 molecular sieve, titanium silicalite molecular sieve, and mordenite is 2-3.

[0016] In step 2, the particle size of the SiO2 particles in the SiO2 molecular sieve is 50-100 nanometers, and the microstructure is a spherical or mesh configuration; in step 2, the TS-1 particle size range in the titanium silicalite molecular sieve is 20-100 nanometers, the titanium-silicon atomic ratio is 20-50, and the skeleton is composed of a two-dimensional pore structure of silicon oxide tetrahedrons and titanium oxide tetrahedrons; the particle size of the MOR particles in the mordenite zeolite is 30-100 nanometers, the titanium-silicon atomic ratio is 10-30, and the skeleton is a topological structure, which is an elliptical twelve-membered ring main channel with an eight-membered ring channel configuration between the main channels.

[0017] In step 2, the placement time is 24-48 hours, the heating temperature is 80-90°C, the drying temperature is 80-120°C, and the roasting temperature is 300-450°C.

[0018] Application of a catalyst prepared by a catalyst preparation method for the low-temperature catalytic oxidation of CH4 by CO2 to produce C2+ oxygen-containing compounds, wherein the reducing atmosphere is H2, the temperature is 260-400℃, the pressure is 0.2-1.5Mp, and the space velocity is 1000h -1 ; Reaction temperature is 200-350℃, pressure is 3-12.0MPa, and space velocity is 1000-10000h -1 , H2 / CO=0.5-2.0, suitable for fixed bed and fluidized bed reactors.

[0019] C 2+ Oxygen-containing compounds mainly include C 2+ Mixed oxygen-containing compounds such as alcohols, aldehydes, carboxylic acids, esters, etc.

[0020] The beneficial effects of the present invention are: using the catalyst of the present invention to catalyze the oxidation of CH4 to produce C2 at low temperature 2+ Oxygenated compounds, CO2 conversion rate 15~40%, CH4 conversion rate 20~40%, C 2+ The selectivity of oxygenated compounds is 65~90%, C 2+ Hydrocarbon selectivity 5~20%, total C 2+ The space-time yield of oxygen-containing compounds is 0.20~0.30g / h.mL.cat.

[0021] The present invention directly catalytically oxidizes and couples greenhouse gases CO2 and CH4 to generate high value-added C 2+ The reducing compound has the advantages of low energy consumption, mild reaction process conditions, high raw material conversion rate, high product selectivity, high yield and high stability.

[0022] The components of the catalyst of the present invention are not precious metals, and the preparation cost is low, which greatly reduces the production cost of the catalyst.

[0023] The catalyst preparation method of the present invention is simple and easy to operate. It can be directly formed after ball milling, or it can be formed into tablets or extruded strips by adding a binder. The catalyst has relatively high mechanical strength and is easy to scale up for production. DETAILED DESCRIPTION

[0024] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not intended to limit the present invention.

[0025] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention. Example 1

[0026] First, 10g of zirconium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of Ce:La=1:1 was prepared into a 50% wt nitrate mixed solution. At 30°C, it was co-precipitated with ammonia water in the zirconium hydroxide suspension solution until the molar ratio of Ce:La:Zr=1:1:1 was reached. The pH of the mixed solution was maintained at 7-8. The solution was aged for 3h and then washed with distilled water until neutral. After filtration, it was dried at 120°C and calcined in air at 400°C for 6h. The first catalytic component was obtained by pulverizing. 10g of SiO treated with 50% nitric acid was weighed and mixed with water. 2， Then, a 50% wt. nitrate-SiO2 impregnation solution was prepared using a molar ratio of Co:Ni:W:SiO2 = 1:1:1:2. After 24 hours of continuous stirring, the solution was heated to 80°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 300°C, and pulverized to obtain the second catalytic component. Finally, the powdered catalyst (1#) and the second catalytic component were ball-milled at a ratio of 2:1 for 1 hour and crushed into tablets with a 40-60 mesh size.

[0027] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 260℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 200 ° C, P = 12.0 MPa, GHSV = 1000 h -1 The reaction results are shown in Table 1. Example 2

[0028] First, 10g of zinc hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of Ga: Ir = 1:1 was prepared into a 50% wt nitrate mixed solution. At 40°C, it was co-precipitated with a 50wt% potassium carbonate solution in the zinc hydroxide suspension solution until the molar ratio of Ga: Ir: Zn = 1:1:1 was reached. The pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 400°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of TS-1 treated with 50% nitric acid was weighed and ， A 50% nitrate TS-1 impregnation solution was then prepared using a molar ratio of Sr:Cu:Fe:TS-1 of 1:1:1:2. After 24 hours of continuous stirring, the solution was heated to 80°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 350°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic component were ball-milled at a ratio of 3:1 for 1 hour and pressed into tablets to form a 40-60 mesh finished catalyst.

[0029] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 280℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 220 ° C, P = 11.0 MPa, GHSV = 2000 h -1 The reaction results are shown in Table 1. Example 3

[0030] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga = 1:1 was prepared into a 50% wt nitrate mixed solution. At 50°C, it was co-precipitated with a 50wt% potassium carbonate solution in the calcium hydroxide suspension solution until the molar ratio of La: Ga: Ca = 1:1:1 was reached, and the pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 450°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% hydrogen peroxide was weighed. ， A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Sr:Cu:Fe:MOR = 1:1:1:2. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 400°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 4:1 for 2 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0031] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 300℃, and the reducing space velocity is 1000h -1Reaction conditions: T = 230 ° C, P = 10.0 MPa, GHSV = 3000 h -1 The reaction results are shown in Table 1. Example 4

[0032] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga: Ir = 1:1:1 was prepared into a 50% wt nitrate mixed solution. At 60°C, it was co-precipitated with a 50wt% potassium carbonate solution in a zirconium hydroxide suspension solution until the molar ratio of La: Ga: Ir: Zr was 1:1:1:2, and the pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 450°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% hydrogen peroxide was weighed. ， A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Co:Cu:Fe:MOR of 1:1:1:3. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 450°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 2:1 for 1 hour and pressed into tablets to form a 40-60 mesh finished catalyst.

[0033] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 320℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 240 ° C, P = 9.0 MPa, GHSV = 4000 h -1 The reaction results are shown in Table 1. Example 5

[0034] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of Ce: La: Ga = 1:1:1 was prepared into a 50% wt nitrate mixed solution. At 70°C, it was co-precipitated with a 50wt% sodium carbonate solution in the calcium hydroxide suspension solution until the molar ratio of La: Ga: Ca = 1:1:2 was reached, and the pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 500°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% nitric acid was weighed. ，A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Co:Ni:Fe:MOR of 1:1:1:3. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 300°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 3:1 for 1.5 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0035] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 350℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 260 ° C, P = 5.0 MPa, GHSV = 5000 h -1 The reaction results are shown in Table 1. Example 6

[0036] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga = 1:1 was prepared into a 50% wt nitrate mixed solution. At 30°C, it was co-precipitated with a 50wt% potassium carbonate solution in the calcium hydroxide suspension solution until the molar ratio of La: Ga: Ca = 1:1:2 was reached, and the pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 350°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% hydrogen peroxide was weighed. ， A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Sr:Cu:Fe:MOR = 1:1:1:3. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 350°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 4:1 for 2 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0037] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 300℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 250 ° C, P = 8.0 MPa, GHSV = 6000 h -1 The reaction results are shown in Table 1. Example 7

[0038] First, 10g of zirconium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of Ce:La=1:1 was prepared into a 50% wt nitrate mixed solution. At 50°C, it was co-precipitated with a 50wt% sodium carbonate solution in the zirconium hydroxide suspension solution until the molar ratio of Ce:La:Zr=1:1:3 was reached. The pH of the mixed solution was maintained at 7-8. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 400°C in air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of SiO treated with 50% nitric acid was weighed and 2， Then, a 50% nitrate-SiO2 impregnation solution was prepared using a molar ratio of Co:Ni:W:SiO2 = 1:1:1:2. After 24 hours of continuous stirring, the solution was heated to 80°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 400°C, and pulverized to obtain the second catalytic component. Finally, the powdered catalyst (1#) and the second catalytic component were ball-milled at a ratio of 2:1 for 1 hour and crushed into tablets with a mesh size of 40-60.

[0039] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 380℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 260 ° C, P = 7.0 MPa, GHSV = 7000 h -1 The reaction results are shown in Table 1. Example 8

[0040] First, 10g of zinc hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of Ga: Ir = 1:1 was prepared into a 50% wt nitrate mixed solution. At 60°C, it was co-precipitated with ammonia water in the zinc hydroxide suspension solution until the molar ratio of Ga: Ir: Zn = 1:1:3 was reached. The pH of the mixed solution was maintained at 8-9. After aging for 3 hours, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined in an air atmosphere at 450°C for 6 hours, and crushed to obtain the first catalytic component. 10g of TS-1 treated with 50% hydrogen peroxide was weighed. ， A 50% nitrate TS-1 impregnation solution was then prepared using a molar ratio of Sr:Cu:Fe:TS-1 of 1:1:1:2. After 24 hours of continuous stirring, the solution was heated to 80°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 450°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 3:1 for 1.5 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0041] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 300℃, and the reducing space velocity is 1000h -1Reaction conditions: T = 270 ° C, P = 6.0 MPa, GHSV = 8000 h -1 The reaction results are shown in Table 1. Example 9

[0042] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga = 1:1 was prepared into a 50% wt nitrate mixed solution. At 70°C, it was co-precipitated with a 50wt% sodium carbonate solution in the calcium hydroxide suspension solution until the molar ratio of La: Ga: Ca = 1:1:3 was reached, and the pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 450°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% hydrogen peroxide was weighed. ， A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Sr:Cu:Fe:MOR = 1:1:1:2. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 350°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 4:1 for 2 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0043] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 400℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 280 ° C, P = 5.0 MPa, GHSV = 9000 h -1 The reaction results are shown in Table 1. Example 10

[0044] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga: Ir = 1:1:1 was prepared into a 50% wt nitrate mixed solution. At 50°C, it was co-precipitated with a 50wt% potassium carbonate solution in a zirconium hydroxide suspension solution until the molar ratio of La: Ga: Ir: Zr was 1:1:1:3. The pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 500°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% nitric acid was weighed. ，A 50% wt. nitrate-MOR impregnation solution was then prepared using a molar ratio of Ni:Cu:Fe:MOR = 1:1:1:3. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 400°C, and pulverized to obtain the second catalytic component. Finally, the powdered catalysts 1# and 2# were ball-milled at a ratio of 1:1 for 1.5 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0045] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 300℃, and the reducing space velocity is 1000h -1 Reaction conditions: T = 290 ° C, P = 4.0 MPa, GHSV = 10000 h -1 The reaction results are shown in Table 1. Example 11

[0046] First, 10g of calcium hydroxide was dispersed in water and stirred continuously to form a suspension solution. Then, a nitrate with a molar ratio of La: Ga: Ir = 1:1:1 was prepared into a 50% wt nitrate mixed solution. At 60°C, it was co-precipitated with a 50wt% sodium carbonate solution in a zirconium hydroxide suspension solution until the molar ratio of La: Ga: Ir: Zr was 1:1:1:3. The pH of the mixed solution was maintained at 8-9. After aging for 3h, it was washed with distilled water until neutral, filtered, dried at 120°C, calcined at 450°C in an air atmosphere for 6h, and crushed to obtain the first catalytic component. 10g of MOR treated with 50% nitric acid was weighed. ， A 50% nitrate-MOR impregnation solution was then prepared using a molar ratio of Sr:W:Co:MOR = 1:1:1:3. After 48 hours of continuous stirring, the solution was heated to 90°C to form a paste. The paste was then washed with distilled water until neutral, dried at 120°C, calcined at 450°C, and pulverized to obtain the second catalytic component. Finally, the powdered 1# and second catalytic components were ball-milled at a ratio of 2:1 for 2 hours and pressed into tablets to form a 40-60 mesh finished catalyst.

[0047] H2 is used as reducing atmosphere under normal pressure, the reducing temperature is 400℃, and the reducing space velocity is 1000h -1 Reaction conditions: T=300℃, P=3.0MPa, GHSV=6000h -1 The reaction results are shown in Table 1.

[0048] Table 1 Example catalyst reaction results

[0049]

[0050] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

Claims

1. A low-temperature catalytic oxidation of CH4 by CO2 to produce C 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: Proceed as follows: Step 1: Prepare the first catalytic component by co-precipitating any two or three nitrates of Ce, La, Ga, and Ir with an alkaline solution in a suspension of zirconium hydroxide, zinc hydroxide, and calcium hydroxide. The mixture is then aged, washed, filtered, dried, and calcined in sequence, and then ground into a powder, which is referred to as the first catalytic component and used in the co-precipitation method. Step 2: preparing a second catalytic component by placing one of SiO2 molecular sieve, titanium silicon molecular sieve, and mordenite treated with 30-50wt% nitric acid or 50-70wt% hydrogen peroxide in a mixed solution of any three nitrates of Co, Ni, W, Sr, Cs, Cu, and Fe, placing, stirring, and heating to form a paste, and then sequentially washing, drying, and calcining, and grinding into a powder, which is recorded as the second catalytic component; Step 3: Synthesize the catalyst: mix the first catalytic component and the second catalytic component in a mass ratio of 1-4 by ball milling, press the mixture into tablets, and crush the tablets into 40-60 mesh particles to obtain the catalyst.

2. A method for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 according to claim 1 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: In step 1, the ratio of the total molar number of Ce, La, Ga, and Ir to the total molar number of zirconium hydroxide, zinc hydroxide, and calcium hydroxide is 1-3.

3. A method for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 according to claim 1 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: In step 1, during the co-current co-precipitation, the temperature is 30-70° C. and the pH value is 7-9.

4. A method for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 according to claim 1 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: In step 1, the drying temperature is 80-120°C, and the roasting temperature is 350-500°C.

5. A method for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 according to claim 1 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: In step 2, the ratio of the total molar number of Co, Ni, W, Sr, Cs, Cu, and Fe to the total molar number of SiO2 molecular sieve, titanium silicalite molecular sieve, and mordenite is 2-3.

6. A method for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 according to claim 1 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized by: In step 2, the particle size of the SiO2 particles in the SiO2 molecular sieve is 50-100 nanometers, and the microstructure is a spherical or mesh configuration; in step 2, the TS-1 particle size range in the titanium silicalite molecular sieve is 20-100 nanometers, the titanium-silicon atomic ratio is 20-50, and the skeleton is composed of a two-dimensional pore structure of silicon oxide tetrahedrons and titanium oxide tetrahedrons; the particle size of the MOR particles in the mordenite zeolite is 30-100 nanometers, the titanium-silicon atomic ratio is 10-30, and the skeleton is a topological structure, which is an elliptical twelve-membered ring main channel with an eight-membered ring channel configuration between the main channels.

7. The method of claim 1 for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: In step 2, the placement time is 24-48 hours, the heating temperature is 80-90°C, the drying temperature is 80-120°C, and the roasting temperature is 300-450°C.

8. The method of claim 1 for producing C by coupling CO2 low-temperature catalytic oxidation of CH4 2+ A method for preparing a catalyst for an oxygen-containing compound, characterized in that: The reducing atmosphere is H2, the temperature is 260-400℃, the pressure is 0.2-1.5 MPa, and the volume space velocity is 1000h -1 The reaction temperature is 200-350℃, the pressure is 3-12.0MPa, and the volume space velocity is 1000-10000h -1 , H2 / CO=0.5-2.0, suitable for fixed bed and fluidized bed reactors.

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