A catalyst for the reforming of CO2 and CH4 to produce syngas under conditions containing CO gas components, its preparation method and application

Abstract

The application provides a catalyst for reforming CO2 and CH4 into synthesis gas in the presence of CO gas components as well as a preparation method and application thereof. The catalyst comprises a reforming active metal, a redox active metal and a carrier; the active metal has a grain size of less than or equal to 4.8 nm, and the catalyst has an oxygen storage capacity of 572-809 μmol / g. The preparation method comprises dissolving a carrier precursor salt in water, adding a flocculating agent and ammonia water to obtain a precipitate, filtering, washing, drying and then calcining under an inert atmosphere; dissolving a reforming active metal precursor salt, a redox active metal precursor salt and a dispersing agent in water to obtain an aqueous solution, then impregnating the aqueous solution into the calcination product in an equal volume, drying, heating, and then cooling to room temperature, and passivating. The catalyst is placed in a fixed bed reactor, and the reaction is carried out at a raw material space velocity of 1000-20000 h ‑1 , a pressure of 0.1-4.0 MPa and a heating rate of 0.5-2.0 ℃ / min to 650-950 ℃ to synthesize CO and H2. The catalyst can efficiently reform CO2 and CH4 into synthesis gas in the presence of CO, and meanwhile ensure the carbon deposition resistance and stability of the catalyst.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of catalysts, and particularly relates to a catalyst for reforming CO2 and CH4 into synthesis gas under the condition of a CO-containing gas component as well as a preparation method and application thereof. BACKGROUND

[0002] CO2 and CH4 are major greenhouse gases, and their massive emission has a significant impact on global climate warming. Direct reforming of CO2 and CH4 into synthesis gas (CO2+CH4→2CO+2H2), and then using the synthesis gas to synthesize chemicals such as methanol, fuel oil and olefins is one of the most effective ways for the comprehensive utilization of CO2 and CH4. The biggest technical problem currently faced by the reforming of CO2 and CH4 is catalyst coking, especially when the feed gas component contains other components such as CO (such as coke oven gas), coking is more likely to occur. The coking reaction mainly includes CH4 cracking coking (CH4→C+2H2) and CO disproportionation coking (2CO→C+CO2). After the catalyst cokes, its active sites are covered, and the surface pores are gradually blocked, thereby causing catalyst deactivation, until the reactor bed is blocked, causing the reaction to be forced to stop.

[0003] Under different temperatures and different reaction atmospheres, different types of coking reactions occur on the reforming catalyst, different carbon species are generated, the coking rate, carbon removal difficulty and the requirement for the anti-coking performance of the catalyst are different. For the reforming catalyst of CO2 and CH4, there are related patents reported, such as patents CN110652984B, CN113952956A, CN107790170B and CN108325566A, which disclose the preparation method and application conditions of the CO2 and CH4 dry reforming catalyst. However, the raw materials suitable for these catalysts are only CO2 and CH4, and do not contain CO and other components. These catalysts cannot adapt to the disproportionation reaction of CO, and the comprehensive anti-coking performance of the catalyst is not strong.

[0004] In view of this, the present application is proposed. SUMMARY

[0005] The present application aims to provide a catalyst for reforming CO2 and CH4 into synthesis gas under the condition of a CO-containing gas component as well as a preparation method and application thereof, so as to solve the above problems. The catalyst can efficiently reform CO2 and CH4 into synthesis gas in the presence of CO atmosphere, while ensuring the anti-coking performance and stability of the catalyst.

[0006] To achieve the above purpose, the present application adopts the following technical solutions:

[0007] A catalyst for reforming CO2 and CH4 into synthesis gas in the presence of CO-containing gas components, comprising a reforming active metal, a redox active metal and a carrier; the grain size of the reforming active metal and the redox active metal is less than or equal to 4.8 nm, and the oxygen storage capacity of the catalyst is 572-809 mu mol / g.

[0008] The CH4 cracking reaction and the CO disproportionation reaction are structure-sensitive reactions, and reducing the grain size of the active metal is conducive to reducing the rate of surface carbon species generation, thereby providing a time window for carbon elimination reactions, so that the catalyst has high reforming activity and carbon deposition resistance.

[0009] Optionally, the reforming active metal comprises one or a mixture of several of Mo, Co, Ni, Fe or Mn.

[0010] Optionally, the redox active metal comprises one or a mixture of several of Pt, Ru, La, Ce, Pd or Ag, and transition metals such as Mo and Co have the function of activating CH4.

[0011] The function of metals such as Pt and Ru is to form redox cycle active sites, thereby having the function of eliminating surface carbon species. The mechanism of action is that the redox metal (denoted as M) is oxidized by CO2 to MOx (see reaction formula 1), and MOx further oxidizes the carbon species formed on the surface of the catalyst, while MOx is reduced to M (see reaction formula 2), and in the process of completing the redox cycle, it plays a role in eliminating surface carbon species.

[0012] M + CO2 → CO + MOx (reaction formula 1)

[0013] MOx + C → CO + M (reaction formula 2)

[0014] Optionally, the carrier comprises a mixture of at least two of aluminum oxide, magnesium oxide, silicon oxide or titanium oxide. In the present catalyst, the carrier has abundant oxygen storage capacity.

[0015] By introducing abundant surface chemisorbed oxygen on the carrier, carbon species overflowing from the surface of the active metal to the carrier can be oxidized, thereby achieving the carbon elimination effect on the surface of the carrier (see reaction formula 3).

[0016] C + O 吸附 → CO (reaction formula 3)

[0017] Further, the reforming active metal, the redox active metal and the carrier are in a mass ratio of (3.9-18.5):(0.7-7.2):(74.3-95.4).

[0018] The present application also provides a preparation method of the catalyst, comprising the following steps:

[0019] S1: Dissolve the precursor salt of the support in water, add a flocculating agent and 15% ammonia water to obtain a precipitate, filter, wash, dry, and then calcine under an inert atmosphere to obtain sample one. Sample one comprises a solid organic polymer formed by the support metal oxide precipitate and the flocculating agent.

[0020] Optionally, the precursor salt of the support comprises a mixture of at least two of aluminum nitrate, magnesium nitrate, silica sol, or titanyl sulfate. The two support metals can mutually dope each other under high-temperature conditions to form oxygen defects, providing conditions for subsequent improvement of the support oxygen storage capacity.

[0021] Further, the flocculating agent comprises a high-molecular flocculating agent. Preferably, the flocculating agent comprises one or several of polyacrylic acid, polyacrylamide, or polyethyleneimine.

[0022] Further, the mass ratio of the precursor salt of the support to the flocculating agent is (1040.2-1335.6):(2.3-5.4). Only when the ratio of the precursor salt of the support to the flocculating agent meets the above range, the support precursor and the organic matter can be fully precipitated. Deviation from the ratio will cause insufficient precipitation of the support precursor and the organic matter, and the support cannot be effectively formed.

[0023] Further, the inert atmosphere is generally a nitrogen atmosphere, and the calcination temperature is 500-650°C. The organic matter introduced to the support surface by the flocculating agent reacts with the support metal oxide, causing part of the lattice oxygen of the metal oxide to be reduced by carbon, thereby forming oxygen defects on the surface of the support, providing conditions for subsequent improvement of the oxygen storage capacity. If the temperature is lower than 500°C, the reaction cannot proceed. However, if the temperature is higher than 650°C, the reaction rate of the precursor and the organic matter is too fast, causing the pore structure of the support to collapse.

[0024] S2: Dissolve the precursor salt of the reforming active metal, the precursor salt of the redox active metal, and a dispersant in water to obtain an aqueous solution, and then impregnate the aqueous solution in the sample one in an equal volume, and dry to obtain sample two.

[0025] Further, the mass ratio of the precursor salt of the reforming active metal, the precursor salt of the redox active metal, the dispersant, and water is (21.5-86.4):(4.8-36.9):(25.4-102.6):(90-120).

[0026] Optionally, the dispersant comprises one or several of urea, glycine, sucrose, or citric acid.

[0027] Further, the mass ratio of the aqueous solution to sample one is (8.6-10.4):(9.6-13.8).

[0028] S3: heating the sample two, so that the metal precursor salt and dispersant impregnated on the sample two can fully undergo redox reaction (see reaction formula 4), so that the metal precursor salt is decomposed into metal oxide, and after being lowered to room temperature, passivation is carried out in O2 and / or N2 atmosphere, thereby obtaining the catalyst.

[0029] Further, the heating temperature is 500-700℃. Firstly, at this temperature, the metal precursor salt and the dispersant can undergo redox reaction, and a large amount of gas is released. The pore-forming effect of the gas makes the metal precursor salt decomposed into metal oxide with ultra-fine particle size. The active site with ultra-fine particle size can reduce the carbon deposition rate, thereby providing sufficient time for the surface carbon elimination reaction. Secondly, CO2 is generated in the process of surface redox reaction, and the surface oxygen defects of the carrier introduced in step S1 can activate CO2 to generate CO and surface chemisorbed oxygen (see reaction formula 5), thereby improving the oxygen storage capacity of the carrier.

[0030] M x (NO3) y +C a H b O c N d →MO e +N2+CO2+H2O (reaction formula 4)

[0031] CO2→CO+O 吸附 (Reaction formula 5)

[0032] If the heating temperature is lower than 500℃, the calcination of the active metal precursor salt and the organic matter cannot be fully reacted and decomposed; and if it is higher than 700℃, the calcination reaction is violent, which causes the particle size of the active metal of the catalyst to increase.

[0033] The application further provides an application of the catalyst: the catalyst is placed in a fixed bed reactor, the molar ratio of CO:CO2:CH4 in the reaction atmosphere can be any ratio, and the reaction is carried out at a raw material space velocity of 1000-20000h-1 and a pressure of 0.1-4.0MPa, and the temperature is increased to 650-950℃ at a rate of 0.5-2.0℃ / min, thereby synthesizing CO and H2. -1

[0034] In the application, there are at least three key factors for controlling the carbon deposition of the CO2 and CH4 reforming catalyst: firstly, the carbon deposition reaction is a structure-sensitive reaction, and the particle size of the active component of the catalyst can be controlled to effectively slow down the carbon deposition of the catalyst; secondly, a double-center active site is constructed, one of which is used for the activation and conversion of CH4, and the other of which is used for the redox cycle of the surface carbon species; thirdly, the surface active oxygen of the carrier is constructed, which is used for the oxidation and elimination of the carbon species overflowing on the carrier.

[0035] ​Compared with the prior art, the application creatively introduces a redox active site, surface chemisorption oxygen, and control of active metal particle size, so that the catalyst has excellent CO2 and CH4 reforming activity and carbon deposition resistance, and can be particularly applied to a raw material gas containing CO in a reaction atmosphere.

[0036] The preparation method has simple operation, controllable conditions, and potential for large-scale industrial application. DETAILED DESCRIPTION

[0037] To make the purposes, technical solutions and advantages of the embodiments of the application clearer, the technical solutions in the embodiments of the application will be clearly and completely described below. Obviously, the described embodiments are only some of the embodiments of the application, rather than all the embodiments of the application. Based on the embodiments in the application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the application. The unexplained material proportion relationships can be any proportion mixture.

[0038] Embodiment 1

[0039] A preparation method of the catalyst:

[0040] Aluminum nitrate 258.2 g and magnesium nitrate 930.4 g were weighed and dissolved in water to form an aqueous solution, 3.6 g of polyacrylic acid and 1000 ml of 15% ammonia water were weighed and added to the above aqueous solution to form a precipitate; the precipitate was filtered, washed, and left to stand at room temperature for 2 h, and then dried at 100 ℃ for 4 h, followed by calcination at 550 ℃ under nitrogen for 2 h to obtain sample one.

[0041] Cobalt nitrate 50.4 g, cerium nitrate 26.3 g and urea 72.6 g were weighed and added to 100 ml of deionized water to obtain a solution, and an equal volume of the solution was impregnated on sample one, left to stand at room temperature for 2 h, and then dried at 100 ℃ for 2 h to obtain sample two.

[0042] Sample two was heated to 600 ℃ and calcined for 3 h, and then cooled to room temperature, and then passivated under N2 atmosphere for 4 h to obtain the catalyst.

[0043] The obtained catalyst comprises reforming active metal cobalt, redox active metal cerium, an alumina carrier and a magnesium oxide carrier, and the mass ratio of the three is 10.2:4.9:84.9, the cobalt metal crystal grain is 4.0 nm, the cerium metal crystal grain is 4.7 nm, and the oxygen storage capacity of the catalyst is 653 μmol / g.

[0044] The catalyst was placed in a fixed bed reactor, and the molar ratio of H2:CO:CO2:CH4 in the reaction atmosphere was 0:76:15:9, the raw material space velocity was 5000 h -1, and the synthesis of CO and H2 was carried out by raising the temperature to 750℃ at a rate of 1.0℃ / min under a pressure of 1.0 MPa. The reaction results are listed in Table 1.

[0045] Example 2

[0046] A method for preparing the catalyst comprises the following steps:

[0047] A solution was prepared by dissolving 645.9 g of titanyl sulfate and 394.3 g of magnesium nitrate in water. 4.9 g of polyacrylamide and 1000 ml of 15% ammonia water were added to the solution to form a precipitate. The precipitate was filtered and washed, and then was allowed to stand at room temperature for 2 h and was dried at 100℃ for 3 h. Subsequently, the precipitate was calcined at 600℃ under a nitrogen atmosphere for 2 h to obtain sample one.

[0048] A solution was prepared by dissolving 86.4 g of molybdenum nitrate, 36.9 g of silver nitrate and 102.6 g of citric acid in 90 ml of deionized water. The solution was impregnated on sample one in an equal volume, and then was allowed to stand at room temperature for 2 h and was dried at 100℃ for 2 h to obtain sample two.

[0049] Sample two was heated to 550℃ and was calcined for 5 h. Subsequently, the temperature was lowered to room temperature, and sample two was passivated under an O2 atmosphere for 4 h to obtain the catalyst.

[0050] The catalyst comprises reforming active metal molybdenum, redox active metal silver, a carrier composed of titanium oxide and magnesium oxide, and the mass ratio of the three is 18.5:7.2:74.3. The grain size of molybdenum is 4.8 nm, and the grain size of silver is 3.8 nm. The oxygen storage capacity of the catalyst is 572 μmol / g.

[0051] The catalyst was placed in a fixed bed reactor, and the synthesis of CO and H2 was carried out by raising the temperature to 650℃ at a rate of 2.0℃ / min under a pressure of 0.1 MPa. The reaction results are listed in Table 1. -1

[0052] Example 3

[0053] A method for preparing the catalyst comprises the following steps:

[0054] A solution was prepared by dissolving 824.0 g of aluminum nitrate and 511.6 g of magnesium nitrate in water. 2.3 g of polyethyleneimine and 1000 ml of 15% ammonia water were added to the solution to form a precipitate. The precipitate was filtered and washed, and then was allowed to stand at room temperature for 2 h and was dried at 100℃ for 4 h. Subsequently, the precipitate was calcined at 650℃ under a nitrogen atmosphere for 2 h to obtain sample one.

[0055] ​Take 21.5 g of manganese nitrate, 4.8 g of platinum nitrate and 25.4 g of sucrose into 110 ml of deionized water to obtain a solution, and impregnate the solution into sample one in an equal volume, stand at room temperature for 2 h, dry at 100 °C for 2 h, and obtain sample two.

[0056] Heat sample two to 650 °C, calcine for 3 h, then reduce to room temperature, and passivate in N2 atmosphere for 4 h to obtain the catalyst.

[0057] The obtained catalyst comprises reforming active metal manganese, redox active metal platinum, alumina and magnesia carrier, and the mass ratio of the three is 3.9:0.7:95.4, the grain size of manganese is 4.2 nm, the metal grain size of platinum is 4.5 nm, and the oxygen storage capacity of the catalyst is 809 μmol / g.

[0058] Place the catalyst in a fixed bed reactor, and react under the reaction atmosphere of H2:CO:CO2:CH4 molar ratio of 8:15:37:40, at raw material space velocity of 20000 h-1, pressure of 2.0 MPa, and temperature rising rate of 0.5 °C / min to 850 °C to synthesize CO and H2. The reaction results are shown in Table 1. -1

[0059] Example 4

[0060] A preparation method of the catalyst comprises the following steps:

[0061] Take 904.3 g of aluminum nitrate and 376.7 g of magnesium nitrate into water to form an aqueous solution, take 5.4 g of polyacrylic acid and 1000 ml of 15% ammonia water together into the aqueous solution to form a precipitate, filter and wash the precipitate, stand at room temperature for 2 h, dry at 100 °C for 4 h, then calcine at 550 °C under nitrogen atmosphere for 2 h to obtain sample one.

[0062] Take 35.1 g of molybdenum nitrate, 12.4 g of silver nitrate and 40.2 g of citric acid into 120 ml of deionized water to obtain a solution, and impregnate the solution into sample one in an equal volume, stand at room temperature for 2 h, and dry at 100 °C for 2 h to obtain sample two.

[0063] Heat sample two to 550 °C, calcine for 5 h, then reduce to room temperature, and passivate in O2 atmosphere for 4 h to obtain the catalyst.

[0064] The obtained catalyst comprises reforming active metal molybdenum, redox active metal silver, alumina and magnesia carrier, and the mass ratio of the three is 6.4:2.1:91.5, the grain size of molybdenum is 3.9 nm, the metal grain size of silver is 4.3 nm, and the oxygen storage capacity of the catalyst is 724 μmol / g.

[0065] ​The catalyst was placed in a fixed bed reactor, and reacted at a raw material space velocity of 10000 h -1 under a reaction atmosphere of H2:CO:CO2:CH4 at a molar ratio of 50:23:18:9, and a pressure of 4.0 MPa, and was heated to 950℃ at a rate of 1.0℃ / min to synthesize CO and H2. The reaction results are shown in Table 1.

[0066] Comparative Example 1

[0067] A preparation method of the catalyst, which is different from that of Example 3, is that the carrier is a single metal oxide carrier, aluminum oxide.

[0068] Aluminum nitrate 1525.3 g was dissolved in water to form an aqueous solution, 2.3 g of polyethyleneimine and 1000 ml of 15% ammonia water were added to the aqueous solution to form a precipitate; the precipitate was filtered, washed, and left to stand at room temperature for 2 h, dried at 100℃ for 4 h, and then calcined at 650℃ under nitrogen for 2 h to obtain sample one. The subsequent preparation method was the same as that of Example 3.

[0069] The obtained catalyst comprises reforming active metal manganese, redox active metal platinum, and an aluminum oxide carrier, and the mass ratio of the three is 3.9:0.7:95.4, the crystal grain size of manganese is 4.3 nm, and the metal crystal grain size of platinum is 4.4 nm. The oxygen storage capacity of the catalyst is 426 μmol / g.

[0070] The catalyst evaluation conditions were the same as those of Example 3, and the reaction results are shown in Table 1.

[0071] Comparative Example 2

[0072] A preparation method of the catalyst, which is different from that of Example 3, is that no flocculating agent is added when preparing the carrier.

[0073] Aluminum nitrate 824.0 g and magnesium nitrate 511.6 g were dissolved in water to form an aqueous solution, and 1000 ml of 15% ammonia water was added to the aqueous solution to form a precipitate; the precipitate was filtered, washed, and left to stand at room temperature for 2 h, dried at 100℃ for 4 h, and then calcined at 650℃ under nitrogen for 2 h to obtain sample one. The subsequent preparation method was the same as that of Example 3.

[0074] The obtained catalyst comprises reforming active metal manganese, redox active metal platinum, and a carrier composed of aluminum oxide and magnesium oxide, and the mass ratio of the three is 3.9:0.7:95.4, the crystal grain size of manganese is 4.1 nm, and the metal crystal grain size of platinum is 4.6 nm. The oxygen storage capacity of the catalyst is 342 μmol / g.

[0075] The catalyst evaluation conditions were the same as those of Example 3, and the reaction results are shown in Table 1.

[0076] Comparative Example 3

[0077] A preparation method of the catalyst was as described in Example 3, except that no dispersant was added when preparing sample two.

[0078] The obtained catalyst included reforming active metal manganese, redox active metal platinum, a carrier composed of alumina and magnesia, the mass ratio of the three being 3.9:0.7:95.4, the crystal grain size of manganese being 4.1 nm, the metal crystal grain size of platinum being 4.3 nm, and the oxygen storage capacity of the catalyst being 305 μmol / g.

[0079] The catalyst evaluation conditions were the same as in Example 3, and the reaction results are listed in Table 1.

[0080] Comparative Example 4

[0081] A preparation method of the catalyst was as described in Example 3, except that the carrier was calcined in an air atmosphere.

[0082] The obtained catalyst included reforming active metal manganese, redox active metal platinum, a carrier composed of alumina and magnesia, the mass ratio of the three being 3.9:0.7:95.4, the crystal grain size of manganese being 4.1 nm, the metal crystal grain size of platinum being 4.3 nm, and the oxygen storage capacity of the catalyst being 305 μmol / g.

[0083] The catalyst evaluation conditions were the same as in Example 3, and the reaction results are listed in Table 1.

[0084] Table 1 Performance evaluation comparison of the catalysts obtained in Examples 1-4 and Comparative Examples 1-4

[0085]

[0086] From Table 1, it can be seen that the CO2 or CH4 conversion rate of the catalysts of Examples 1-4 is >90%, especially that of Example 3, both of which have high conversion rates; while from Comparative Example 1, it can be seen that if a single metal oxide carrier is used, oxygen defects cannot be formed by mutual doping, and the oxygen storage capacity of the catalyst is reduced, and the conversion rates are significantly lower than that of Example 3; from Comparative Example 2, it can be seen that if no flocculating agent is added when the carrier is prepared, and no oxygen defects are formed by reduction of the metal oxide by the surface carbon species during calcination, the oxygen storage capacity of the catalyst is reduced, and the conversion rates are significantly lower than that of Example 3; from Comparative Example 3, it can be seen that if no dispersing agent is added when loading the active metal precursor and the redox metal precursor, the metal particle size cannot be controlled, and the conversion rates are significantly lower than that of Example 3. From Comparative Example 4, it can be seen that if air calcination is used when the carrier is prepared, the surface carbon species is oxidized by oxygen in the air, and the carbon species cannot reduce the metal oxide to form oxygen defects, the oxygen storage capacity of the catalyst is reduced, and the conversion rates are significantly decreased.

[0087] Please note that any combination of the technical features of the above embodiments can be made, and in order to make the description simple, all possible combinations of the technical features in the above embodiments are not described, however, as long as the combination of the technical features does not exist, it should be considered as the scope of the description. The above embodiments only express several implementation manners of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be pointed out that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are all within the scope of the present application. Therefore, the scope of the patent of the present application should be subject to the appended claims.

Claims

1. A method for preparing a catalyst for the reforming of CO2 and CH4 to syngas under conditions containing CO gas components, characterized in that, Includes the following steps: S1: Dissolve the precursor salt of the carrier in water, add flocculant and ammonia to obtain a precipitate, filter, wash, dry, and then calcine under an inert atmosphere to obtain sample one. S2: Dissolve the precursor salt of the reforming active metal, the precursor salt of the redox active metal, and the dispersant in water to obtain an aqueous solution, then impregnate the sample one with an equal volume, and dry to obtain sample two; S3: Heat the second sample, cool it to room temperature, and then passivate it under an O2 and / or N2 atmosphere to obtain the final product; The flocculant includes one or more of polyacrylic acid, polyacrylamide, or polyethyleneimine. The dispersant includes one or more of urea, glycine, sucrose, or citric acid; The reforming active metal includes one or a mixture of several of Mo, Co, Ni, Fe or Mn; The redox active metal includes one or a mixture of several of Pt, Ru, La, Ce, Pd, or Ag.

2. The preparation method according to claim 1, characterized in that, In step S1, the precursor salt of the carrier includes a mixture of at least two of aluminum nitrate, magnesium nitrate, silica sol, or titanium oxysulfate.

3. The preparation method according to claim 2, characterized in that, In step S1, the mass ratio of the precursor salt of the carrier to the flocculant is (1040.2-1335.6):(2.3-5.4).

4. The preparation method according to claim 1, characterized in that, In step S1, the roasting temperature is 500-650℃.

5. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of the precursor salt of the reforming active metal, the precursor salt of the redox active metal, the dispersant and water is (21.5-86.4):(4.8-36.9):(25.4-102.6):(90-120).

6. The preparation method according to claim 1, characterized in that, In step S2, the mass ratio of the aqueous solution to sample one is (8.6-10.4):(9.6-13.8).

7. The preparation method according to claim 1, characterized in that, In step S3, the heating temperature is 500-700℃.

8. A catalyst prepared by the method according to any one of claims 1-7, characterized in that, It includes a reforming active metal, a redox active metal, and a support; the crystal size of the reforming active metal and the redox active metal is ≤4.8nm, and the oxygen storage capacity of the catalyst is 572-809 μmol / g.

9. The catalyst according to claim 8, characterized in that, The carrier comprises a mixture of at least two of aluminum oxide, magnesium oxide, silicon oxide, or titanium oxide.

10. The catalyst according to claim 8, characterized in that, The reforming active metal, redox active metal, and support are in a mass ratio of (3.9-18.5): (0.7-7.2): (74.3-95.4).

11. The application of a catalyst prepared by the method according to any one of claims 1 to 7, characterized in that, The catalyst was placed in a fixed-bed reactor, with an arbitrary molar ratio of CO:CO2:CH4 in the reaction atmosphere, and a feed space velocity of 1000-20000 h⁻¹. -1 The reaction is carried out under a pressure of 0.1-4.0 MPa, with the temperature increased to 650-950℃ at a rate of 0.5-2.0℃ / min, to synthesize CO and H2.

Images