CN115970742A - Low-temperature oxidation of CH 4 Coupling of CO 2 Catalyst for directly preparing oxide and preparation method and application thereof - Google Patents

Low-temperature oxidation of CH 4 Coupling of CO 2 Catalyst for directly preparing oxide and preparation method and application thereof Download PDF

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CN115970742A
CN115970742A CN202211635986.0A CN202211635986A CN115970742A CN 115970742 A CN115970742 A CN 115970742A CN 202211635986 A CN202211635986 A CN 202211635986A CN 115970742 A CN115970742 A CN 115970742A
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刘勇军
张超宇
昝雪玉
陶诗琪
吴怡枭
王柯静
李智雯
黄伟
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Taiyuan University of Technology
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Abstract

Low-temperature oxidation of CH 4 Coupling of CO 2 A catalyst for directly preparing oxide, a preparation method and application thereof, belonging to the technical field of chemical industry, wherein the form of the catalyst is X-Cu-ZSM-5, wherein ZSM-5 is a carrier, cu and X are active components, and X is at least one of Zn, ce, in, co, fe, pd, rh or an alkali metal. The catalyst is prepared by adopting an ion exchange method, the mass fractions of Cu and X are less than or equal to 5 percent and the Si/Al ratio of the molecular sieve is 15 to 100 according to the mass percent, the X-Cu-ZSM-5 catalyst prepared by the invention has simple preparation process and good repeatability, and is applied to trickle bed continuous reaction at low temperature (less than 100 ℃) and H 2 O 2 Under the condition, the oxygen-containing compound can be directly obtained with high yield and high selectivity, and high energy consumption of CH is avoided 4 And CO 2 Reforming to produce synthetic gas, and hydrogenating the synthetic gas.

Description

Low-temperature oxidation of CH 4 Coupling of CO 2 Catalyst for directly preparing oxide and preparation method and application thereof
Technical Field
The invention belongs to the technical field of chemical industry, and particularly relates to low-temperature oxidation of CH 4 Coupling of CO 2 A catalyst for directly preparing oxide and a preparation method and application thereof.
Background
Since the industrial revolution, fossil energy has largely used discharged CO 2 Becomes a main factor causing global climate change and has main responsibility for global temperature rise! CH (CH) 4 Is the main component of natural gas, marsh gas, coal bed gas and shale gas, is widely distributed in nature, is also a greenhouse gas, and has the effect of CO about the greenhouse effect 2 More than 20 times of the total weight of the composition. By CH 4 High temperature reforming of CO 2 First converted into CO and H 2 Then the CO hydrogenation is carried out to synthesize the chemicals such as olefin, aromatic hydrocarbon, methanol, higher alcohol and the like, which is the solution of CH at present 4 And CO 2 The main way of exceeding the emission standard, however, the reforming reaction temperature is extremely high (more than 800 ℃), a large amount of energy input is needed, the energy consumption accounts for more than 60% of the whole process, and therefore CH is developed 4 And CO 2 The low-temperature direct coupling synthesis of high-value chemical catalyst and the industrially applicable process technology have important theoretical and practical significance.
Chinese patent literatureDiscloses a method for synergistically converting CH in one step by using low-temperature plasma and modified catalyst (molecular sieve and supported copper-based catalyst) 4 And CO 2 The method for preparing acetic acid (publication numbers CN 111672543A and CN 111675609A), on one hand, the plasma itself is high in energy consumption, and on the other hand, the process has the problems of wide product distribution, low selectivity of oxygen-containing compounds, insufficient synthesis stability and the like.
Chinese patent literature discloses a copper modified molecular sieve catalyst (publication No. CN 112973784A) for preparing methanol from methane, water vapor and oxygen, but the preparation process of the catalyst is complex and carbon dioxide is inevitably generated.
Chinese patent literature discloses 4 And CO 2 A bimetallic high-efficiency catalyst for preparing ethanol/acetaldehyde by co-transformation (publication number CN 114029061A) adopts a system of photo-thermal concerted catalysis in a batch reaction kettle, and has difficulty in application.
Chinese patent literature discloses' a CH 4 -CO 2 Catalyst and process for synthesizing acetic acid by step conversion (publication numbers CN101357313A, CN1634841A and CN 1309114A), which mainly utilizes CH 4 And CO 2 Feeding separately and using H 2 The overflow and the supplement of (2) to overcome the thermodynamic barrier, and the system also has the problem of complex process.
At present due to CO 2 The environmental problems are increasingly paid attention, and the literature utilizes a catalytic method to directly convert CH 4 And CO 2 The preparation of oxygen-containing compounds is of great interest, but most researches focus on DFT calculation, solid nuclear magnetic reaction, in-situ infrared characterization and other aspects (J. Am. Chem. Soc., 2016, 138, 10191-10198; J. Phys. Chem. C., 2018, 122, 9570-9577; ACS Catal., 2017, 7, 6719-6728; chem. Commun., 2020, 56, 3983-3986), and reports are few in experimental researches.
To sum up, current CH 4 And CO 2 Because the stability of the structure of the catalyst is difficult to activate, the scale application of the catalyst is limited, and therefore, the development of a new catalytic system and a new process is urgently needed.
Disclosure of Invention
The invention mainly aims to overcome the defects in the prior art and solve the problem of high-energy consumption CH in the prior art 4 -CO 2 The problem of mismatching of reforming technology and multi-step reaction process conditions and the problem of difficult reaction due to the double limitations of kinetics and thermodynamics of the reaction under low temperature condition are provided, and the low-temperature oxidized CH with low temperature feasibility and simple preparation process is provided 4 Coupling of CO 2 A catalyst for directly preparing oxide, a preparation method and application thereof.
In order to achieve the purpose of the invention, the invention adopts the technical scheme that:
low-temperature oxidation of CH 4 Coupling of CO 2 A catalyst for the direct production of oxygenates, wherein: the catalyst is In the form of X-Cu-ZSM-5, wherein ZSM-5 is a carrier, cu and X are active components, and X is at least two of alkali metal, zn, ce, in, co, fe, pd or Rh.
Further, the mass fractions of Cu and X in the catalyst are both less than or equal to 5%, and the molar ratio of Cu to X is (10; the carrier is H-ZSM-5 molecular sieve, and the mass percentage of Si element and Al element in the molecular sieve is 15wt.%~100 wt.%。
The preparation method of the catalyst comprises the following steps:
s1, first ion exchange: adding a first X metal salt into deionized water to prepare a mixed solution with the concentration of 0.01 to 1 mol/L, then adding an H-ZSM-5 molecular sieve into the mixed solution to prepare a suspension, stirring at the water bath temperature of 50-80 ℃ for 6-12H, and sequentially filtering, washing, drying and roasting after the first ion exchange to prepare ZSM-5 solid powder subjected to ion exchange;
s2, second ion exchange: adding a second X metal salt into deionized water to prepare a solution with the concentration of 0.05-0.5 mol/L, then adding the ion-exchanged ZSM-5 solid powder prepared in the step S1 into the mixed solution to prepare a suspension, stirring at the water bath temperature of 50-80 ℃ for 6-12 h, and sequentially filtering, washing, drying, roasting and granulating after the second ion exchange to prepare catalyst powder, wherein the particle size of the catalyst powder is 40-60 meshes;
s3, catalyst reduction: and (3) placing the catalyst powder prepared in the step (S2) in a tubular heating furnace, blowing for 0-1 h under an inert atmosphere, then heating to 400-800 ℃ from room temperature under a mixed atmosphere of hydrogen and inert gas, wherein the heating rate is 1-10 ℃/min, and reducing for 3-8 h to obtain a catalyst finished product.
Further, the metal salt is nitrate, acetate or chloride.
Further, in the step S3, H in mixed atmosphere 2 The volume fraction of the gas is 5-50%, and the inert gas in the mixed atmosphere is Ar, he or N 2 One or more of them.
The application of the catalyst comprises the following steps: the catalyst is applied to a trickle bed reactor, the reaction pressure is normal pressure to 10 MPa, the reaction temperature is room temperature to 100 ℃, and GHSV =1000 to 20000 h -1 ，CH 4 /CO 2 Volume ratio of (10 2 O 2 The flow rate of the solution is 0.01 to 1.0 mL/min, H 2 O 2 The concentration is 0.01 to 8M.
Compared with the prior art, the invention has the beneficial effects that:
(1) The catalyst provided by the invention has the advantages that the active components only contain metal Cu and metal X, the preparation process is simple, and the repeatability is good;
(2) When the catalyst provided by the invention is applied to a continuous trickle bed reaction process, the reaction temperature is low (less than 100 ℃), and the selectivity of the oxygen-containing compound is high;
(3) The invention is due to H 2 O 2 Presence of a solution of CH 4 -CO 2 The thermodynamically unfavorable reaction for the conversion to the oxygen-containing compound becomes feasible 4 -CO 2 The conversion of two greenhouse gases into a practical process.
Detailed Description
The following specific examples are given to the low temperature oxidation of CH provided by the present invention 4 Coupling of CO 2 The preparation method and application of the catalyst for directly preparing the oxide are further detailedAnd (4) explanation. The described cases are a part of the embodiments of the present invention, and not all embodiments. The embodiments in the present invention, and other embodiments obtained by persons skilled in the art without invasive labor, belong to the scope of the present invention.
Example 1
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: weighing 2.0 g of KNO 3 Adding the mixture into 100mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al =25 in the H-ZSM-5 molecular sieve; stirring for 10 h at the water bath temperature of 80 ℃, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 110 ℃, grinding, and roasting for 6h at 550 ℃ to obtain K ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 12.1 g of Cu (NO) was weighed 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, then adding the K ion exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 10 hours at the water bath temperature of 80 ℃, filtering, washing and drying the suspension in sequence after the second ion exchange, and roasting for 6 hours at 550 ℃ to prepare K-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the K-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at 10% H at a total flow rate of 100 mL/min 2 -90% by weight of the product, reduced at 450 ℃ for 3 hours in Ar atmosphere, to obtain the finished K-Cu-ZSM-5 catalyst.
The finished K-Cu-ZSM-5 catalyst prepared in example 1 was evaluated in a self-made continuous trickle bed under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 1,H 2 O 2 The solution flow rate is 0.1 mL/min, the concentration is 0.2M, the reaction temperature is 50 ℃, the reaction pressure is 3 MPa, and the airspeed is 4800 h -1 And (3) as a result: methanol yield 320 mu mol/g cat H, selectivity 100%.
Example 2
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: 1.6 g of Fe (NO) are weighed out 3 ) 3 ·9H 2 Adding O into 150mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al =30 in the H-ZSM-5 molecular sieve; stirring for 5h at 70 ℃ water bath temperature, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 100 ℃, grinding, and roasting for 6h at 500 ℃ to obtain Fe ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 12.1 g of Cu (NO) was weighed 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, adding the Fe ion-exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 10 hours at the water bath temperature of 80 ℃, filtering, washing and drying the suspension in sequence after the second ion exchange is finished, and roasting for 6 hours at the temperature of 450 ℃ to prepare Fe-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the Fe-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at 50% H at a total flow rate of 100 mL/min 2 -50% by weight of the resulting product, at 450 ℃ for 5 hours in an Ar atmosphere, to obtain the finished Fe-Cu-ZSM-5 catalyst.
The finished product of the Fe-Cu-ZSM-5 catalyst prepared in the example 2 was placed in a self-made continuous trickle bed for evaluation under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 2 2 O 2 The solution flow rate is 0.2 mL/min, the concentration is 0.2M, the reaction temperature is 75 ℃, the reaction pressure is 4 MPa, and the space velocity is 1000 h -1 And (3) as a result: methanol yield 105. Mu. Mol/g cat H, selectivity 36.8%, acetic acid yield 180. Mu. Mol/g cat H, selectivity 63.2%.
Example 3
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: 0.89 g of Zn (NO) was weighed 3 ) 2 ·6H 2 Adding O into 200 mL deionized water, adding 4.0 g of H-ZSM-5 molecular sieve to prepare suspension, and adding H-ZSM-5 moleculesSi/Al =38 in sieve; stirring for 5h at 70 ℃ water bath temperature, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 100 ℃, grinding, and roasting for 6h at 450 ℃ to obtain Zn ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 8.2 g of Cu (NO) are weighed out 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, adding the Zn ion exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 10 hours at the water bath temperature of 80 ℃, filtering, washing and drying at 100 ℃ in sequence after the second ion exchange is finished, and roasting for 6 hours at 500 ℃ to prepare Zn-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the Zn-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at 10% H at a total flow rate of 100 mL/min 2 -90% of the Zn-Cu-ZSM-5 catalyst was reduced at 400 ℃ for 6 hours in He atmosphere.
The finished Zn-Cu-ZSM-5 catalyst prepared in example 3 was evaluated in a self-made continuous trickle bed under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 10 2 O 2 The solution flow rate is 1.0 mL/min, the concentration is 5.0M, the reaction temperature is 25 ℃, the reaction pressure is 5 MPa, and the space velocity is 10000 h -1 And (3) as a result: methanol yield 220 mu mol/g cat H, selectivity 78.6%, acetic acid yield 60. Mu. Mol/g cat H, selectivity 21.4%.
Example 4
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: weighing 1.7275g of cobalt acetate, adding the cobalt acetate into 100mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al =25 in the H-ZSM-5 molecular sieve; stirring for 20 h at the water bath temperature of 50 ℃, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 110 ℃, grinding, and roasting for 6h at 550 ℃ to obtain Co ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 2.3 g of Cu (NO) are weighed out 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, adding the Co ion-exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 10 hours at the water bath temperature of 80 ℃, filtering, washing and drying the suspension in sequence after the second ion exchange is finished, and roasting for 6 hours at the temperature of 550 ℃ to prepare Co-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the Co-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at 40% H at a total flow rate of 100 mL/min 2 -60%rN 2 Reducing for 5h at 450 ℃ in the atmosphere to obtain the finished product of the Co-Cu-ZSM-5 catalyst.
The finished Co-Cu-ZSM-5 catalyst prepared in example 4 was placed in a self-made continuous trickle bed for evaluation under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 8 2 O 2 The solution flow rate is 0.25 mL/min, the concentration is 3.0M, the reaction temperature is 50 ℃, the reaction pressure is 3 MPa, and the space velocity is 3000 h -1 And (3) as a result: methanol yield 105 mu mol/g cat H, selectivity 29.6%, acetic acid yield 250. Mu. Mol/g cat H, selectivity 70.4%.
Example 5
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: weighing 1.4 g of palladium chloride, adding the palladium chloride into 150mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al =15 in the H-ZSM-5 molecular sieve; stirring for 12 h at the water bath temperature of 30 ℃, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 100 ℃, grinding, and roasting for 4h at 500 ℃ to obtain Pd ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 3.5 g of Cu (NO) are weighed out 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, adding the Pd ion exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 10 hours at the water bath temperature of 30 ℃, filtering, washing and drying the suspension in sequence after the second ion exchange, and roasting for 6 hours at the temperature of 450 ℃ to prepare Pd-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the Pd-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at a rate of 20% H at a total flow rate of 100 mL/min 2 80 percent of the catalyst, at 450 ℃ for 5 hours in Ar atmosphere, to prepare the finished Pd-Cu-ZSM-5 catalyst.
The finished Pd-Cu-ZSM-5 catalyst prepared in example 5 was evaluated in a self-made continuous trickle bed under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 1 2 O 2 The solution flow rate is 0.25 mL/min, the concentration is 2.0M, the reaction temperature is 50 ℃, the reaction pressure is 3.0 MPa, and the airspeed is 5000 h -1 As a result: methanol yield 52 mu mol/g cat H, selectivity 13.4%, acetic acid yield 336. Mu. Mol/g cat H, selectivity 86.6%.
Example 6
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: weighing 1.1 g of rhodium chloride, adding the rhodium chloride into 200 mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al =25 in the H-ZSM-5 molecular sieve; stirring for 6h at the water bath temperature of 80 ℃, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 120 ℃, grinding, and roasting for 2 h at 400 ℃ to prepare Rh ion-exchanged ZSM-5 solid powder;
s2, second ion exchange: 3.5 g of Cu (NO) are weighed out 3 ) 2 ·3H 2 Dissolving O in 100mL of deionized water, adding the Rh ion-exchanged ZSM-5 solid powder prepared in the step S1 to prepare a suspension, stirring for 6 hours at the water bath temperature of 80 ℃, filtering, washing and drying at 100 ℃ in sequence after the second ion exchange is finished, and roasting for 3 hours at 400 ℃ to prepare Rh-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: putting the Rh-Cu-ZSM-5 catalyst powder obtained in step S2 in a tube furnace at 30% H at a total flow rate of 100 mL/min 2 -70%N 2 Reducing for 3h at 400 ℃ in the atmosphere to obtain the finished Rh-Cu-ZSM-5 catalyst.
Rh-Cu-ZSM-5 prepared in example 6 was used for catalysisThe finished product of the agent is placed in a self-made continuous trickle bed for evaluation, and the evaluation conditions are as follows: CH (CH) 4 /CO 2 The volume ratio is 1 2 O 2 The flow rate of the solution is 0.3 mL/min, the concentration is 4.0M, the reaction temperature is 50 ℃, the reaction pressure is 1.0 MPa, and the space velocity is 10000 h -1 And (3) as a result: methanol yield 96 mu mol/g cat H, selectivity 27.4%, acetic acid yield 254. Mu. Mol/g cat H, selectivity 72.6%.
Example 7
Low-temperature oxidation of CH 4 Coupling of CO 2 A method for preparing a catalyst for direct production of oxygenates, comprising the steps of:
s1, first ion exchange: weighing 2.8 g of indium nitrate, adding the indium nitrate into 100mL of deionized water, and then adding 4.0 g of H-ZSM-5 molecular sieve to prepare a suspension, wherein Si/Al in the H-ZSM-5 molecular sieve =100; stirring for 6h at the water bath temperature of 80 ℃, sequentially filtering and washing for three times after the first ion exchange, drying for 12 h at 100 ℃, grinding, and roasting for 3h at 500 ℃ to obtain In ion exchanged ZSM-5 solid powder;
s2, second ion exchange: 6.5 g of Cu (NO) are weighed out 3 ) 2 ·3H 2 Dissolving O In 100mL of deionized water, then adding the In ion exchanged ZSM-5 solid powder prepared In the step S1 to prepare a suspension, stirring for 6 hours at the water bath temperature of 80 ℃, filtering, washing and drying at 100 ℃ In sequence after the second ion exchange is finished, and roasting for 5 hours at 400 ℃ to prepare In-Cu-ZSM-5 catalyst powder;
s3, catalyst reduction: placing the In-Cu-ZSM-5 catalyst powder obtained In step S2 In a tubular furnace at 10% H with a total flow rate of 100 mL/min 2 -90% by weight of Ar atmosphere at 400 ℃ for 3 hours to obtain the In-Cu-ZSM-5 catalyst finished product.
The finished In-Cu-ZSM-5 catalyst prepared In example 7 was evaluated In a self-made continuous trickle bed under the following conditions: CH (CH) 4 /CO 2 The volume ratio is 1 2 O 2 The solution flow rate is 0.1 mL/min, the concentration is 0.5M, the reaction temperature is 75 ℃, the reaction pressure is normal pressure, and the space velocity is 5000 h -1 And (3) as a result: methanol yield 220 mu mol/g cat H, selectivity72.1 % acetic acid yield 85. Mu. Mol/g cat H, selectivity 27.9%.
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.

Claims (6)

1. Low-temperature oxidation of CH 4 Coupling of CO 2 A catalyst for directly producing an oxide, characterized in that: the catalyst is In the form of X-Cu-ZSM-5, wherein ZSM-5 is a carrier, cu and X are active components, and X is at least two of alkali metal, zn, ce, in, co, fe, pd or Rh.
2. A low temperature oxidation of CH as claimed in claim 1 4 Coupling of CO 2 A catalyst for directly producing an oxide, characterized in that: the mass fractions of Cu and X in the catalyst are both less than or equal to 5%, and the molar ratio of Cu to X is (10); the carrier is H-ZSM-5 molecular sieve, and the mass percentage of Si element and Al element in the molecular sieve is 15wt.%~100 wt.%。
3. A process for preparing a catalyst according to claim 1 or 2, comprising the steps of:
s1, first ion exchange: adding a first X metal salt into deionized water to prepare a mixed solution with the concentration of 0.01 to 1 mol/L, then adding an H-ZSM-5 molecular sieve into the mixed solution to prepare a suspension, stirring at the water bath temperature of 50-80 ℃ for 6-12H, and sequentially filtering, washing, drying and roasting after the first ion exchange to prepare ZSM-5 solid powder subjected to ion exchange;
s2, second ion exchange: adding a second X metal salt into deionized water to prepare a solution with the concentration of 0.05-0.5 mol/L, then adding the ion-exchanged ZSM-5 solid powder prepared in the step S1 into the mixed solution to prepare a suspension, stirring at the water bath temperature of 50-80 ℃ for 6-12 h, and sequentially filtering, washing, drying, roasting and granulating after the second ion exchange to prepare catalyst powder, wherein the particle size of the catalyst powder is 40-60 meshes;
s3, catalyst reduction: and (3) placing the catalyst powder prepared in the step (S2) in a tubular heating furnace, blowing for 0 to 1 h under an inert atmosphere, heating to 400 to 800 ℃ from room temperature under a mixed atmosphere of hydrogen and the inert gas, wherein the heating rate is 1 to 10 ℃/min, and reducing for 3 to 8 h to prepare a catalyst finished product.
4. The method for preparing a catalyst according to claim 3, characterized in that: the metal salt is nitrate, acetate or chloride.
5. The method for preparing a catalyst according to claim 3, characterized in that: in said step S3, H in a mixed atmosphere 2 The volume fraction of the gas is 5-50%, and the inert gas in the mixed atmosphere is Ar, he or N 2 One or more of them.
6. Use of a catalyst according to claim 1 or 2, wherein: the catalyst is applied to a trickle bed reactor, the reaction pressure is normal pressure to 10 MPa, the reaction temperature is room temperature to 100 ℃, and GHSV =1000 to 20000 h -1 ，CH 4 /CO 2 Volume ratio of (10 2 O 2 The flow rate of the solution is 0.01 to 1.0 mL/min, H 2 O 2 The concentration is 0.01 to 8M.
CN202211635986.0A 2022-12-20 2022-12-20 Low-temperature oxidation of CH 4 Coupling of CO 2 Catalyst for directly preparing oxide and preparation method and application thereof Pending CN115970742A (en)

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