CN110270368B

CN110270368B - Method for synthesizing carbon-chemical embedded catalyst material by solution-free method

Info

Publication number: CN110270368B
Application number: CN201810207617.9A
Authority: CN
Inventors: 张燚; 邱宝成; 刘意
Original assignee: Beijing University of Chemical Technology
Current assignee: Beijing University of Chemical Technology
Priority date: 2018-03-14
Filing date: 2018-03-14
Publication date: 2020-09-04
Anticipated expiration: 2038-03-14
Also published as: CN110270368A

Abstract

The invention discloses a method for preparing an embedded catalyst for carbon-chemical reaction by a solution-free method, which comprises the following steps: s1, preparing a precursor; s2, preparing the molecular sieve by a solution-free method; s3, exchanging molecular sieve ions; and S4, tabletting, granulating and reducing to obtain the molded embedded catalyst. The embedded catalyst prepared by the invention has good catalytic activity, high selectivity and excellent stability; no water is added in the process of preparing the catalyst, so that the generation of waste can be reduced to a great extent; the prepared molecular sieve catalyst has the advantages of cheap and easily-obtained raw materials, simple preparation process and low catalyst cost, and is suitable for industrial production.

Description

Method for synthesizing carbon-chemical embedded catalyst material by solution-free method

Technical Field

The invention relates to a novel catalyst preparation method, in particular to a method for synthesizing a carbon-chemical embedded catalyst material by a solution-free method. The preparation method of the catalyst can be widely applied to carbon-chemical reactions such as methane oxygen-free aromatization, Fischer-Tropsch synthesis, methane reforming, CO oxidation and the like, and belongs to the technical field of catalysts.

Background

Reactions in which the reactant involves only one carbon atom during the chemical reaction are collectively referred to as carbon-chemistry. The main purpose of carbon-chemical technology is to save coal and petroleum resources, and to produce a large amount of fuel from a small amount of carbon raw materials and to provide the fuel to human beings.

Carbon-one chemistry begins with a hydrocarbon reaction with methane (CH), a compound containing one carbon atom₄) Synthesis gas (CO and H)₂)、CO₂、CH₃OH, HCHO and the like are initial reactants and react to synthesize a series of important chemical raw materials and fuel chemistry. The carbon-chemical based dry substances are CO and H₂Readily available from any carbon-containing resource, which is the biggest reason why monocarbon chemistry can be at the heart of the future chemical industry.

In the last 70 th century, japan first proposed the concept of carbon-one chemistry, and at the same time, the technology of low pressure methanol carbonylation by monsanto corporation of the united states for the production of acetic acid has gained industrial application; the Mobil chemical company of America utilizes ZSM-5 molecular sieve catalyst to be successfully applied to the methanol conversion to prepare gasoline; in countries with abundant natural gas production, such as canada and middle east, the methanol market is enabled to rush into a large amount of methanol through rapid increase of the production capacity of the natural gas for preparing methanol. Therefore, in recent years, carbon-one chemistry has been studied to synthesize a series of basic organic chemical products produced from ethylene as a basic raw material, not only from synthesis gas, but also from methanol as an important basic raw material.

Carbon-chemical is actually a new generation of coal chemical and natural gas chemical. The current products mainly comprise liquid fuel, fuel additives, low-carbon olefin and synthetic low-carbon alcohol, and also comprise six types of chemical products such as methanol and series products thereof, methanol and series products thereof and the like. The key to understanding carbon-chemistry is the catalyst, and how to develop an excellent catalyst is the success or failure of carbon chemistry.

In 1949, the artificial synthesis of zeolite was successful. Subsequently, through the continuous efforts of researchers for 60 years, 60 types of thermally stable aluminosilicate zeolite molecular sieves have been synthesized. In 1982, Wilson et al reported the synthesis of aluminophosphate zeolite-like materials, and subsequently new molecular sieves of different framework structure, of different micropore compound types, of different framework element compositions were synthesized. The zeolite molecular sieve catalytic material has selective catalytic performance on the shapes, spaces and regions of reactants, intermediate states and product molecules, and the acidity, structure and other performances of the molecular sieve are easy to modulate, so that the zeolite molecular sieve can be widely applied. The earliest synthesis of molecular sieves, which required the use of large amounts of water as a solvent, followed by further development of hydrothermal synthesis using organic alcohols as solvents. Then, a dry gel conversion method is proposed, in which the aqueous solvent forming the molecular sieve gel is evaporated to dryness and then a small amount of water is added dropwise for crystallization. In recent years, ionic liquid is proposed as a solvent to synthesize the molecular sieve, and the method utilizes the ionic liquid which can be used as a template agent and a solvent to synthesize the molecular sieve, but the application range of the method is limited, so that the method is only suitable for the phosphorus-aluminum framework molecular sieve at present, and the application of the ionic liquid in an industrial process is limited due to the high price of the ionic liquid.

In addition to the hydrothermal synthesis method, the synthesis of molecular sieves by other methods is expensive and involves the use of large amounts of organic solvents, so that the hydrothermal synthesis method is still used to prepare industrially synthesized molecular sieves most commonly in the current industrial production process. However, the hydrothermal synthesis of molecular sieves uses a large amount of water as a solvent and a large amount of organic template agent, and is greatly influenced by synthesis conditions such as crystallization temperature, crystallization time, hydrothermal synthesis alkaline environment, generation of molecular sieve gel and the like, so that the applicable synthesis range is narrow, the yield of the molecular sieve is low, and the dissolution of active metals is easily caused in the synthesis process of the molecular sieve. If the method can reduce the solvent water used in the process of synthesizing the molecular sieve and reduce the use of an organic template agent to the maximum extent, simplify the steps of synthesizing the molecular sieve, reduce the loss of the molecular sieve in the synthesis process and the dissolution of active metals, not only can reduce the production cost of the molecular sieve to a great extent, but also can greatly reduce the discharge of wastes, and has great significance for protecting the environment and promoting the industrial sustainable development of the molecular sieve.

At present, the embedded catalyst used in carbon-one chemistry is generally prepared by a hydrothermal synthesis method, the catalyst yield is low, and the loaded active metal is easily dissolved in a hydrothermal synthesis solution to cause the reduction of the loading capacity of the active metal in the preparation of the embedded catalyst by the hydrothermal synthesis, and a large amount of water is used as a solvent in the hydrothermal synthesis process to cause the discharge of a large amount of waste. Therefore, the preparation of molecular sieves by solid milling has become a focus of current research.

Chinese invention patent CN201410084067.8 discloses a method for synthesizing molecular sieve by solid phase grinding, which comprises weighing silicon source, aluminum source and self-made template agent, pouring into mortar, grinding uniformly, and placing into a reaction kettle for crystallization reaction; cooling a crystallization reaction product obtained after the crystallization reaction is finished, and washing and drying the crystallization reaction product to obtain molecular sieve raw powder; and roasting the molecular sieve raw powder to obtain the molecular sieve. The method can prepare the SAPO-11 molecular sieve with better crystallinity, greatly simplifies the synthesis steps compared with the traditional method, greatly improves the yield and the single-kettle utilization rate, reduces the production cost, saves energy, reduces emission and has huge industrial application prospect. However, the method still has the following defects: the solid phase method can only prepare pure molecular sieves, but can not directly prepare the molecular sieves containing active metals, and the self-made template agent is used, so that the template agent needs to be synthesized firstly in the process of preparing the molecular sieves, and the process is complex.

Chinese invention patent application CN201610342078.0 discloses a method for preparing metal @ zeolite single crystal capsule catalytic material in solid phase. The method comprises the following steps: dissolving a metal precursor in water, adding sodium hydroxide, a template agent, a silicon source and an aluminum source, uniformly stirring, heating to volatilize water to obtain dry glue, and grinding into fine powder; putting the fine powder into a glass bottle, and then putting the glass bottle into a hydrothermal kettle, wherein the bottom of the kettle can be selected whether water is added or not; and taking out the reaction product after heating, and roasting in a muffle furnace to obtain the metal @ zeolite single crystal capsule catalytic material of zeolite encapsulated metal. In the preparation method, less template agent is used, even no template agent is used, and pore channels are not filled with a large amount of template agent, so that the preparation method is very suitable for synthesizing the metal @ zeolite single crystal catalyst. However, the method still has the following defects: the method firstly dissolves the precursor in water, and then strong base NaOH is added, so that a large amount of waste liquid is generated in the preparation process, and the catalyst yield is reduced due to twice heating evaporation in the process.

Disclosure of Invention

The invention aims to solve the technical problem of providing a method for synthesizing a carbon-chemical embedded catalyst material by a solution-free method. Compared with the supported catalyst prepared by the traditional method, the embedded catalyst prepared by the method has higher activity and better selectivity, and the catalyst prepared by the method has better stability; the CO conversion rate of the prepared 1Ru10Mo @ HZSM-5 catalyst in the aromatization reaction of the synthesis gas is improved from 15.7 percent to 22.3 percent, and the C is₅₊The selectivity of the method is improved from 0.2 percent to 41.1 percent. The stability of the catalyst is improved to 20h from the original 2 h; no water is added in the process of preparing the catalyst, so that the generation of waste can be reduced to a great extent; the prepared molecular sieve catalyst has the advantages of cheap and easily-obtained raw materials, simple preparation process and low catalyst cost, and is suitable for industrial production.

In order to solve the first technical problem, the invention adopts the following technical scheme:

a method for preparing an embedded catalyst for carbon-chemical reaction without a solution method is characterized by comprising the following steps:

s1 preparation of precursor

Weighing a metal compound with determined metal loading capacity, preparing a solution with determined metal loading capacity, and soaking the solution on a carrier with 20-40 meshes in an equal volume when the metal loading capacity is less than 6%; when the metal loading is more than 6 percent, the catalyst is soaked on a carrier of 20-40 meshes by using an excess soaking method, the vacuum pumping is carried out for 0.5-2 h, then the drying is carried out for 12-24h at the temperature of 80-150 ℃, and then the catalyst is placed in a muffle furnace for roasting for 2-6h at the temperature of 400-600 ℃; obtaining a solid catalyst precursor, and grinding the solid catalyst precursor to be below 100 meshes for later use;

s2 preparation of molecular sieve by solution-free method

Grinding solid catalyst precursor below 100 meshes with 2-10% of seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide (TPABr), NH₄Cl, an aluminium source and/or a silicon source andor mixing and grinding the phosphorus sources for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and placing the polytetrafluoroethylene crystallization kettle in a drying oven at the temperature of 120-200 ℃ for crystallization for 12-36 h; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then placing the solution in a drying oven at the temperature of 80-120 ℃ for drying for 12-24 hours to obtain a Na-type embedded metal molecular sieve catalyst;

s3 molecular sieve ion exchange

Adding Na type embedded metal molecular sieve catalyst into 1M NH₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange for 2-8h at the temperature of 40-80 ℃; repeatedly centrifuging, vacuum filtering for 3 times, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; placing the dried catalyst into a muffle furnace at 400-600 ℃ for roasting for 2-6 h;

and S4, tabletting, granulating and reducing to obtain the molded embedded catalyst.

Preferably, in step S2, the solid catalyst precursor, seed crystal, Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Cl, aluminum source or silicon source or phosphorus source in the following weight ratio: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73.

Preferably, in step S3, the Na-type embedded metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

As a further improvement of the technical scheme, the Ni-based embedded catalyst is prepared by a solution-free method, and the method comprises the following steps:

s11, preparation of a Ni precursor:

weighing Ni metal compounds with determined Ni loading capacity, preparing a solution with determined Ni metal loading capacity, and soaking the solution on a carrier with 20-40 meshes by using equal volume when the metal loading capacity is less than 6%; when the metal loading is more than 6 percent, the catalyst is soaked on a carrier of 20-40 meshes by using an excess soaking method, the vacuum pumping is carried out for 0.5-2 h, then the drying is carried out for 12-24h at the temperature of 80-150 ℃, and then the catalyst is placed in a muffle furnace for roasting for 2-6h at the temperature of 400-600 ℃; obtaining Ni-based precursor, and grinding the Ni-based precursor to be below 100 meshes for later use;

s12, preparation of the molecular sieve by the solution-free method:

grinding Ni-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Ni-based metal molecular sieve catalyst;

s13, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Ni-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

s14, preparing the Ni-based embedded catalyst through tabletting, granulating and reducing.

Preferably, in step S11, the Ni metal compound includes one or more of nickel nitrate, nickel chloride, nickel acetate, and nickel oxalate.

Preferably, in step S12, the Ni-based precursor, seed crystal, Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:0.006-1.73.

Preferably, in step S12, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

Preferably, in step S13, the Na-type embedded Ni-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

As a further improvement of the technical scheme, the Mo-based embedded catalyst is prepared by a solution-free method, and the method comprises the following steps:

s21, preparation of a Mo precursor:

weighing Mo metal compounds determining Mo loading, and preparing a solution determining metal Mo loading; when the loading is less than 6 percent, the SiO is impregnated in a carrier SiO with 20-40 meshes by using the same volume₂When the metal loading is more than 6 percent, the catalyst is impregnated into SiO 20-40 mesh carrier by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Mo-based precursor, and grinding the Mo-based precursor to be less than 100 meshes for later use;

s22, preparation of the molecular sieve by the solution-free method:

grinding Mo-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Mo-based metal molecular sieve catalyst;

s23, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Mo-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

s24, preparing the Mo-based embedded catalyst through tabletting, granulating and reducing.

Preferably, in step S21, the Mo metal compound includes one or more of ammonium molybdate, molybdenum chloride and sodium molybdate.

Preferably, in step S22, the Mo-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:0.006-1.73.

Preferably, in step S22, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

As a further improvement of the technical scheme, the preparation of the Ru-based embedded catalyst by a solution-free method comprises the following steps:

s31, preparation of Ru precursor:

weighing a Ru metal compound with determined Ru load, and preparing a solution with determined metal Ru load by using nitric acid as a solvent; when the loading is less than 6 percent, the SiO is impregnated in a carrier SiO with 20-40 meshes by using the same volume₂When the metal loading is more than 6 percent, the catalyst is impregnated into SiO 20-40 mesh carrier by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining Ru-based precursor, and grinding the Ru-based precursor to be below 100 meshes for later use;

s32, preparation of the molecular sieve by the solution-free method:

grinding Ru-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and a solid silicon source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Ru-based metal molecular sieve catalyst;

s33, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Ru-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

s34, tabletting, granulating and reducing to obtain the Ru-based embedded catalyst.

Preferably, in step S31, the Ru metal compound includes one or more of ruthenium nitrosyl nitrate, ruthenium trichloride, and ruthenium acetate.

Preferably, in step S32, the Ru-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the solid silicon source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:1.3-1.4.

Preferably, in step S32, the solid silicon source includes one or more of crystalline silica, amorphous silica, and fumed silica.

Preferably, in step S33, the Na-type embedded Ru-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

As a further improvement of the technical scheme, the Pt-based embedded catalyst is prepared by a solution-free method, and the method comprises the following steps:

s41, preparation of a Pt precursor:

weighing a Pt metal compound with determined Pt loading capacity, and preparing a solution with determined metal Pt loading capacity by using hydrochloric acid as a solvent; when the loading is less than 6 percent, the SiO is impregnated in a carrier SiO with 20-40 meshes by using the same volume₂When the metal loading is more than 6 percent, the catalyst is impregnated into SiO 20-40 mesh carrier by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Pt-based precursor, and grinding the Pt-based precursor to be below 100 meshes for later use;

s42, preparation of the molecular sieve by the solution-free method:

grinding Pt-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl, ammonium dihydrogen phosphate and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; washing the crystallized molecular sieve with deionized water and anhydrous ethanol alternately, vacuum filtering to obtain a neutral solution, and drying at 80-150 deg.C for 12-24 hr in a drying oven to obtain the final productNa type embedded Pt-based metal molecular sieve catalyst;

s43, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Pt-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

and S44, tabletting, granulating and reducing to obtain the Pt-based embedded catalyst.

Preferably, in step S41, the Pt metal compound includes one or more of platinum diammine dimethylene, platinum chlorate and platinum nitrate.

Preferably, in step S42, the Pt-based precursor, seed crystal, Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl, ammonium dihydrogen phosphate and the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:6.2-6.4:0.006-1.73.

Preferably, in step S42, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

Preferably, in step S43, the Na-type embedded Pt-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

As a further improvement of the technical scheme, the Co-based embedded catalyst is prepared by a solution-free method, and the method comprises the following steps:

s51, preparation of a Co precursor:

weighing a Co metal compound with determined Co load, and preparing a solution with determined metal Co load; when the loading is less than 6 percent, the SiO is impregnated in a carrier SiO with 20-40 meshes by using the same volume₂When the metal loading is more than 6 percent, the catalyst is impregnated into SiO 20-40 mesh carrier by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Co-based precursor, and grinding the Co-based precursor to be below 100 meshes for later use;

s52, preparation of the molecular sieve by the solution-free method:

grinding Co-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Co-based metal molecular sieve catalyst;

s53, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Co-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

and S54, tabletting, granulating and reducing to obtain the Co-based embedded catalyst.

Preferably, in step S51, the Co metal compound includes one or more of cobalt nitrate, cobalt acetate, cobalt carbonyl, cobalt oxalate, and cobalt sulfate.

Preferably, in step S52, the Co-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:0.006-1.73.

Preferably, in step S52, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

Preferably, in step S53, the Na-type embedded Co-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

As a further improvement of the technical scheme, the method for preparing the Fe-based embedded catalyst by a solution-free method comprises the following steps:

s61, preparation of a Fe precursor:

weighing Fe metal compounds determining Fe load, and preparing a solution determining metal Fe load; when the loading is less than 6 percent, the SiO is impregnated in a carrier SiO with 20-40 meshes by using the same volume₂When the metal loading is more than 6 percent, the catalyst is impregnated into SiO 20-40 mesh carrier by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining Fe-based precursor, and grinding the Fe-based precursor to be below 100 meshes for later use;

s62, preparation of the molecular sieve by the solution-free method:

grinding Fe-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Fe-based metal molecular sieve catalyst;

s63, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Fe-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging for 3 times, vacuum filtering, placing the catalyst into a drying oven, and drying at 80-150 deg.C for 12-24 hr; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

and S64, tabletting, granulating and reducing to obtain the Fe-based embedded catalyst.

Preferably, in step S61, the Fe metal compound includes one or more of ferric nitrate, ferric acetate, carbonyl iron, ferric oxalate and ferric sulfate.

Preferably, in step S62, the Fe-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2:0.006-1.73。

Preferably, in step S62, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

Preferably, in step S63, the Na-type embedded Fe-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

Any range recited herein is intended to include the endpoints and any number between the endpoints and any subrange subsumed therein or defined therein.

The starting materials of the present invention are commercially available, unless otherwise specified, and the equipment used in the present invention may be any equipment conventionally used in the art or may be any equipment known in the art.

Compared with the method for synthesizing the SAPO-11 molecular sieve by solid phase grinding disclosed in the prior patent CN201410084067.8, the method is characterized in that: the silicon source used in the prior patent CN201410084067.8 is white carbon black or silica gel, while the silicon source used in the invention is silica loaded with metal, and active metal or auxiliary agent is loaded on the silica by equal volume impregnation or excessive impregnation. The used silicon dioxide raw material is cheap and has abundant sources. Secondly, the aluminum source used in the prior patent CN201410084067.8 is boehmite, the aluminum source used in the invention is one or more of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum oxide and aluminum isopropoxide, and the used aluminum source has wide sources and low price and is easy to industrialize. ③ the template agent used in the prior patent CN201410084067.8 is self-made template agent di-n-propylamine phosphate or diisopropylamine phosphate, the invention uses tetrapropylammonium bromide (TPABr), and the template agent is a solid template agent, is cheap and easy to industrialize. And fourthly, in the existing patent CN201410084067.8, no crystal seed is added in the process of synthesizing the SAPO-11 molecular sieve by solid phase grinding of carbon steel, but in the invention, the HZSM-5 molecular sieve with the ratio of silicon to aluminum of 20-300 is added as the crystal seed in the process of preparing the embedded molecular sieve catalyst, and the crystal seed is added to promote the synthesis of the molecular sieve, improve the crystallinity of the molecular sieve and shorten the crystallization time.

Compared with the prior patent CN201610342078.0, the invention discloses a method for preparing a metal zeolite single crystal capsule catalytic material in a solid phase, which is characterized in that: the existing patent is that a metal precursor is directly dissolved in water, sodium hydroxide, a template agent, a silicon source and an aluminum source are added, stirred uniformly and heated to volatilize water, and the obtained dry glue is ground into fine powder and crystallized; the invention loads the catalyst active metal on the silicon dioxide, after drying, roasting and grinding to below 100 meshes, the catalyst active metal is orderly mixed with a certain amount of seed crystal and Na2SiO₃·9H₂O、TPABr、NH₄Cl and an aluminum source are fully mixed and ground and then crystallized, and no water is added in the process of preparing the embedded catalyst, so that the waste generation is greatly reduced.

Compared with the prior art, the invention has the following beneficial effects:

(1) compared with the supported catalyst prepared by the traditional method, the embedded catalyst prepared by the invention has higher activity and better selectivity. The CO conversion rate of the prepared 1Ru10Mo @ HZSM-5 catalyst in the aromatization reaction of the synthesis gas is improved from 15.7 percent to 22.3 percent, and the C is₅₊The selectivity of the method is improved from 0.2 percent to 41.1 percent.

(2) Compared with the supported catalyst prepared by the traditional method, the catalyst prepared by the method has better stability. The prepared 1Ru10Mo @ HZSM-5 catalyst has the stability improved from the original 2h to 20h in the aromatization reaction of the synthesis gas.

(3) The method does not add any water in the process of preparing the catalyst, and can greatly reduce the generation of waste.

(4) The molecular sieve catalyst prepared by the invention has the advantages of cheap and easily available raw materials, simple preparation process and low catalyst cost, and is suitable for industrial production.

Detailed Description

In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. The method for preparing the catalyst of the present invention is not limited to any specific carbon-one chemical reaction catalyst, but the present invention will be described below with respect to at least one carbon-one chemical reaction catalyst, but the scope of the present invention is not limited thereto.

Example 1

Preparation of Ni-based Embedded catalyst (10Ni @ H β) by the following steps:

1) preparation of Ni precursor: 3.7160g of nickel nitrate hexahydrate were weighed into a beaker, diluted with 1.8017g of deionized water and immersed in 3g of SiO 20-40 mesh by equal volume immersion₂Vacuum-pumping the carrier in a vacuum drier for 0.5h, drying in a drying oven at 80 deg.C for 12h, and calcining in a muffle furnace at 400 deg.C for 2h to obtain 20Ni/SiO₂A precursor;

2) preparation of molecular sieve without solution method (Si/Al ═ 40): 1.7335g of 10Ni/SiO powder is weighed and ground to below 100 meshes in advance₂The precursor was ground in a mortar, followed by the sequential addition of 0.2g H β (Si/Al ═ 40) seed crystal, 6.60g of Na₂SiO₃·9H₂O, 1.4g of tetrapropylammonium bromide (TPABr), 2.2g of NH₄Cl and 0.4329g of Al (NO)₃)·9H₂Mixing and grinding O until a large amount of ammonia gas is generated and the mixture turns into wet mud, pouring the mixture in a mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, putting the kettle into a crystallization box at 150 ℃ for crystallization for 24 hours, alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying box for drying at 120 ℃ for 12 hours to obtain a catalyst which is a 10Ni @ Na- β metal catalyst with the silicon-aluminum ratio of 40;

3) molecular sieve ion exchange, pouring the prepared 10Ni @ Na- β catalyst into a container filled with a certain amount of 1M NH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:50g/ml]) Carrying out ion exchange for 8H at 40 ℃, centrifuging and suction-filtering for multiple times after ion exchange, putting the catalyst into a drying box, drying for 12H at 120 ℃, repeating the steps for 3 times, and roasting the dried catalyst in a muffle furnace at 400 ℃ for 6H to obtain the 10Ni @ H β embedded molecular sieve catalyst;

4) and tabletting, granulating and reducing to obtain the molded 10Ni @ H beta embedded molecular sieve catalyst.

Putting 0.3g of the 10Ni @ H β embedded molecular sieve catalyst into a quartz tube fixed bed reactor, reducing the catalyst for 3 hours at 700 ℃, and introducing reaction gas CO₂/H₂(1:1), the methane reforming reaction is started. The reaction conditions are 700 ℃, 0.1MPa and 10000h^-1The results of the (V/V) reaction are shown in Table 1.

Comparative example 1

Preparation of the supported catalyst:

1.6516g of nickel nitrate hexahydrate is weighed into a beaker, then 3g of H beta (Si/Al ═ 40) is weighed into the beaker, an appropriate amount of deionized water is added, the mixture is stirred for 24 hours and then evaporated to dryness, the mixture is dried in a drying oven at 120 ℃ for 12 hours and finally the mixture is roasted in a muffle furnace at 400 ℃ for 6 hours. The obtained product is the 10 Ni/Hbeta supported molecular sieve catalyst; and tabletting, granulating and reducing to obtain the formed 10Ni/H beta supported molecular sieve catalyst.

Placing 0.3g of the 10Ni/H β supported molecular sieve catalyst in a quartz tube fixed bed reactor, reducing the catalyst for 3H at 700 ℃, and introducing reaction gas CO₂/H₂(1:1), the methane reforming reaction is started. The reaction conditions are 700 ℃, 0.1M Pa and 10000h^-1The results of the (V/V) reaction are shown in Table 1.

TABLE 1 results of catalytic reaction for methane reforming

Example 2

1) The preparation method of the Fe-based embedded molecular sieve catalyst (10Fe @ MCM-41) comprises the following steps:

① preparation of Fe precursor 2.5091g of ferric nitrate nonahydrate was weighed into a beaker, diluted with 0.7657g of deionized water and immersed in 1.3868g of SiO 20-40 mesh by equal volume immersion₂On a carrier, vacuumizing for 1h in a vacuum drier, then drying in a drying box at 150 ℃ for 12h, and finally roasting in a muffle furnace at 400 ℃ for 2h to obtain Fe/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-200) by solution-free method, and mixing the obtained Fe/SiO₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.2g of MCM-41(Si/Al 200) seed crystal and 6.56g of Na seed crystal were sequentially added₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 1.8g of NH₄Cl and 0.0395g of Al₂(SO₄)₃Mixing and grinding until a large amount of ammonia gas is generated and the mixture becomes wet mud. Pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 120 ℃ for crystallization for 36 hours; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 24 hours at 120 ℃, wherein the obtained catalyst is an embedded Fe-based metal catalyst containing Na and having a silicon-aluminum ratio of 200;

③ molecular Sieve ion exchange by pouring the prepared Na-containing 10Fe @ MCM-41 catalyst into a container containing a certain amount of 1MNH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:20 g/ml]) Ion exchange is carried out for 4 hours at the temperature of 60 ℃; after ion exchange, performing repeated centrifugation and suction filtration, putting the catalyst into a drying oven, and drying for 24 hours at 120 ℃; after repeating the steps for 3 times, roasting the dried catalyst in a muffle furnace at the temperature of 600 ℃ for 2 hours to obtain the 10Fe @ MCM-41 embedded molecular sieve catalyst;

and fourthly, tabletting, granulating and reducing to obtain the molded 10Fe @ MCM-41 embedded molecular sieve catalyst.

Putting 0.5g of the 10Fe @ MCM-41 embedded molecular sieve catalyst in a fixed bed reactor, reducing the catalyst for 3 hours at 300 ℃ by using hydrogen, and introducing reaction gas CO/H₂(1:1), starting the Fischer-Tropsch synthesis reaction. The reaction conditions are 300 ℃, 1MPa and 4500h^-1The (V/V) reaction results are shown in Table 2.

2) Preparation of Fe-based embedded molecular sieve catalyst added with auxiliary agent

The method for preparing the Fe-based embedded molecular sieve is the same as the method, and the three steps of Fe precursor preparation, solution-free molecular sieve catalyst preparation and molecular sieve ion exchange are required, and then auxiliary agents (Mg, Ag, Pt and K) required by loading are impregnated and loaded on the prepared Fe-based embedded molecular sieve catalyst in excess.

Taking the addition of 1% of Mg additive as an example:

0.3165g of magnesium nitrate is weighed in a beaker, a proper amount of deionized water is added, then 3g of Fe-based embedded catalyst is weighed in the beaker, stirred for 24 hours and evaporated to dryness, the beaker is placed in a drying box at 120 ℃ for drying for 24 hours, and finally the beaker is placed in a muffle furnace at 400 ℃ for roasting for 2 hours. The obtained Fe-based embedded molecular sieve catalyst is the 1Mg-10Fe/MCM-41 added Mg additive.

The addition method of other adjuvants is similar to that described above.

Putting 0.5g of the Fe-based embedded molecular sieve catalyst added with the auxiliary agent into a fixed bed reactor, reducing the Fe-based embedded molecular sieve catalyst with hydrogen at 300 ℃ for 3H, and introducing reaction gas CO/H₂(1:1), starting the Fischer-Tropsch synthesis reaction. The reaction conditions are 300 ℃, 1MPa and 4500h^-1The (V/V) reaction results are shown in Table 2.

Comparative example 2

Preparation of the supported catalyst:

2.4126g of ferric nitrate nonahydrate is weighed in a beaker, then 3g of MCM-41(Si/Al ═ 200) is weighed in the beaker, an appropriate amount of deionized water is added, stirring is carried out for 24h, then evaporation is carried out, drying is carried out for 24h in a drying oven at 120 ℃, and finally roasting is carried out for 2h in a muffle furnace at 600 ℃. The obtained product is the 10Fe/MCM-41 supported molecular sieve catalyst. Then tabletting, granulating and reducing to obtain the formed 10Fe/MCM-41 supported molecular sieve catalyst

Placing 0.5g of the 10Fe/MCM-41 supported molecular sieve catalyst in a fixed bed reactor, reducing the catalyst for 10 hours at 300 ℃ by using hydrogen, and introducing reaction gas CO/H₂(1:1), the Fischer-Tropsch synthesis reaction was started. The reaction conditions are 300 ℃, 1MPa and 4500h^-1The (V/V) reaction results are shown in Table 2.

TABLE 2 Fischer-Tropsch Synthesis catalyst reaction results

Example 3

1) The preparation of the Co-based embedded molecular sieve catalyst (10Co @ MCM-22) comprises the following steps:

① Co precursor preparation, 1.7213g of cobalt nitrate hexahydrate is weighed in a beaker, diluted with 0.8328g of deionized water, and immersed in 1.3868g of SiO 20-40 mesh by equal volume immersion₂On the carrier, vacuumizing for 1h in a vacuum drier, then drying in a drying box at 120 ℃ for 12h, and finally roasting in a muffle furnace at 400 ℃ for 2h to obtain Co/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-40) by solution-free method, and preparation method thereof₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.06g of MCM-22(Si/Al ═ 40) seed crystal and 6.40g of Na were sequentially added₂SiO₃·9H₂O, 1.4g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.2360g of aluminum isopropoxide were mixed and ground until a large amount of ammonia gas was generated and the mixture became wet sludge; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 200 ℃ for crystallization for 12 hours; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12 hours at 120 ℃, wherein the obtained catalyst is an embedded Co-based metal catalyst containing Na and the silicon-aluminum ratio of which is 40;

③ molecular Sieve ion exchange by pouring the prepared Na-containing 10Co @ MCM-22 catalyst into a container with a certain amount of 1MNH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:20 g/ml]) Ion exchange at 80 ℃ for 2 h. After ion exchange, the catalyst is put into a drying oven after several times of centrifugation and suction filtration, and dried for 12h at 120 ℃. Repeating the steps for 3 times, and roasting the dried catalyst in a muffle furnace at 500 ℃ for 3 hours to obtain the 10Co @ MCM-22 embedded molecular sieve catalyst;

and tabletting, granulating and reducing to obtain the formed 10Co @ MCM-22 embedded molecular sieve catalyst.

Putting 0.5g of the 10Co @ MCM-22 embedded molecular sieve catalyst into a slurry bed reactor, reducing the catalyst for 12 hours at 400 ℃ under normal pressure by using hydrogen, and introducing reaction gas CO/H₂(1:2), starting the Fischer-Tropsch synthesis reaction.The reaction conditions are 240 ℃, 3M Pa and 5000h^-1The results of the (V/V) reaction are shown in Table 3.

2) Preparation of Co-based embedded molecular sieve catalyst added with auxiliary agent

The method for preparing the Co-based embedded molecular sieve is the same as the method, and the method comprises three steps of Fe precursor preparation, solution-free molecular sieve catalyst preparation and molecular sieve ion exchange, and then auxiliary agents (Zn, Cu, Zr, Ce, K, Pd and Rh) required by the prepared Co-based embedded molecular sieve catalyst are loaded by excessive impregnation. Taking the addition of 1% of Zn auxiliary agent as an example:

0.1365g of Zn (NO) were weighed out₃)₂·6H₂And O, adding a proper amount of deionized water into a beaker, weighing 3g of Fe-based embedded catalyst in the beaker, stirring for 24h, evaporating to dryness, drying in a drying oven at 120 ℃ for 24h, and finally roasting in a muffle furnace at 400 ℃ for 2 h. The obtained Fe-based embedded molecular sieve catalyst is the 1Mg-10Fe/MCM-22 added with the Zn auxiliary agent.

Other methods of addition of the adjuvant are similar to those described above.

Placing 0.5g of the Co-based embedded molecular sieve catalyst added with the auxiliary agent into a slurry bed reactor, reducing the catalyst for 12 hours at 400 ℃ under normal pressure, and introducing reaction gas CO/H₂(1:2), starting the Fischer-Tropsch synthesis reaction. The reaction conditions are 240 ℃, 3M Pa and 5000h^-1The results of the (V/V) reaction are shown in Table 3.

Comparative example 3

Preparation of the supported catalyst:

1.6461g of cobalt nitrate hexahydrate is weighed into a beaker, then 3g of MCM-22(Si/Al ═ 40) is weighed into the beaker, an appropriate amount of deionized water is added, the mixture is stirred for 24 hours and then evaporated to dryness, the mixture is dried in a drying oven at 120 ℃ for 12 hours and finally the mixture is roasted in a muffle furnace at 500 ℃ for 3 hours. The obtained product is the 10Co/MCM-22 supported molecular sieve catalyst. Then tabletting, granulating and reducing to obtain the formed 10Fe/MCM-22 supported molecular sieve catalyst

Placing 0.5g of the 10Fe/MCM-22 supported molecular sieve catalyst in a slurry bed reactor, reducing the catalyst for 12 hours at 400 ℃ under normal pressure by using hydrogen, and introducing reaction gas CO/H₂(1:2), start to advancePerforming Fischer-Tropsch synthesis reaction. The reaction conditions are 240 ℃, 3M Pa and 5000h^-1The results of the (V/V) reaction are shown in Table 3.

TABLE 3 Fischer-Tropsch Synthesis catalyst reaction results

Example 4

The preparation method of the Pt-based embedded molecular sieve based catalyst (1Pt @ SAPO-34) comprises the following steps:

① preparation of Pt precursor 0.0745g of chloroplatinic acid was weighed into a beaker, diluted with 2.9443g of hydrochloric acid and immersed in 1.3868g of SiO 20-40 mesh by equal volume immersion₂On a carrier, vacuumizing for 1h in a vacuum drier, then drying in a drying box at 120 ℃ for 12h, and finally roasting in a muffle furnace at 400 ℃ for 2h to obtain the Pt/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-40) by solution-free method, prepared Pt/SiO₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.15g of SAPO-34(Si/Al ═ 40) seed crystal and 6.20g of Na were added in this order₂SiO₃·9H₂O, 6.1914g of ammonium dihydrogen phosphate, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.4329g of Al (NO)₃)·9H₂O is mixed and ground until a large amount of ammonia gas is generated and the mixture becomes a wet sludge. Pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 36 hours; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then drying the solution in a drying oven at 100 ℃ for 12 hours to obtain an embedded Pt-based metal catalyst containing Na with the silicon-aluminum ratio of 40;

③ ion exchange with molecular sieve, pouring the prepared Na-containing 1Pt @ SAPO-34 catalyst into a container filled with a certain amount of 1MNH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:20 g/ml]) Ion exchange was carried out at 60 ℃ for 4 h. After ion exchange, the catalyst is put into the reactor after several times of centrifugation and suction filtrationDrying at 120 deg.C for 12 hr. After repeating the steps for 3 times, roasting the dried catalyst in a muffle furnace at 500 ℃ for 3 hours to obtain the 1Pt @ SAPO-34 embedded molecular sieve catalyst;

and fourthly, tabletting, granulating and reducing to obtain the molded 1Pt @ SAPO-34 embedded molecular sieve catalyst.

Putting 0.3g of the 1Pt @ SAPO-34 embedded molecular sieve catalyst into a fluidized bed reactor, reducing the catalyst for 2 hours at 400 ℃ under normal pressure, and introducing reaction gas CH₄/N₂(9:1), the methane oxygen-free aromatization reaction was started. The reaction conditions are 550 ℃, 0.1MPa and 2000h^-1The (V/V) reaction results are shown in Table 4.

Comparative example 4

Preparation of the supported catalyst:

0.8913g dinitroso diammineplatinum is weighed in a beaker, then 3g SAPO-34(Si/Al ═ 40) is weighed in the beaker, an appropriate amount of deionized water is added, stirring is carried out for 24h, then evaporation is carried out, drying is carried out for 12h in a drying oven at 120 ℃, and finally, the drying is carried out for 2h in a muffle furnace at 400 ℃. The obtained product is the 1Pt/SAPO-34 supported molecular sieve catalyst. Then tabletting, granulating and reducing to obtain the formed 1Pt/SAPO-34 supported molecular sieve catalyst

Placing 0.3g of the formed 1Pt/SAPO-34 supported molecular sieve catalyst in a fluidized bed reactor, reducing the catalyst for 2 hours at 400 ℃ under normal pressure by using hydrogen, and introducing reaction gas CH₄/N₂(9:1), the methane oxygen-free aromatization reaction was started. The reaction conditions are 550 ℃, 0.1MPa and 2000h^-1The (V/V) reaction results are shown in Table 4.

TABLE 4 reaction results of methane oxygen-free aromatization catalyst

Example 5

Preparation of Mo-based Embedded molecular sieve catalyst (6Mo @ HZSM-5)

① preparation of Mo precursor 0.3480g ammonium heptamolybdate tetrahydrate was weighed into a beaker, diluted with 0.6856g deionized water and leached by an equal volumeImpregnating it with 1.3868g of SiO of 20-40 mesh₂On a carrier, vacuumizing for 1h in a vacuum drier, then drying in a drying box at 120 ℃ for 12h, and finally roasting in a muffle furnace at 550 ℃ for 2h to obtain the Mo/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-20) by solution-free method, Mo/SiO obtained₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.2g of HZSM-5(Si/Al ═ 20) seed crystal and 6.56g of Na were added in this order₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.8670g of Al (NO)₃)·9H₂O is mixed and ground until a large amount of ammonia gas is generated and the mixture becomes a wet sludge. Pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours. Alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying box for drying at 110 ℃ for 12 hours to obtain the Na-type embedded Mo-based metal catalyst with the silicon-aluminum ratio of 20;

③ molecular sieve ion exchange, pouring the prepared 6Mo @ Na-ZSM-5 catalyst into a container containing a certain amount of 1M NH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:50g/ml]) Ion exchange is carried out for 8 hours at 40 ℃; after ion exchange, the catalyst is put into a drying oven after several times of centrifugation and suction filtration, and dried for 12h at 120 ℃. After repeating the steps for 3 times, roasting the dried catalyst in a muffle furnace at 550 ℃ for 3 hours to obtain the 6Mo @ HZSM-5 embedded molecular sieve catalyst;

and fourthly, tabletting and granulating to obtain the molded 6Mo @ HZSM-5 embedded molecular sieve catalyst.

Placing 0.3g of the formed 6Mo @ HZSM-5 embedded molecular sieve catalyst in a quartz tube reactor, and introducing reaction gas CH₄/N₂(9:1) carbonizing at 650 ℃ for 30min, and then heating to 700 ℃ to start methane anaerobic aromatization reaction. The reaction conditions are 700 ℃, 0.1MPa and 2000h^-1The results of the (V/V) reaction are shown in Table 5.

Comparative example 5

Preparation of the supported catalyst:

0.3524g of ammonium heptamolybdate tetrahydrate is weighed into a beaker, then 3g of HZSM-5(Si/Al ═ 40) is weighed into the beaker, an appropriate amount of deionized water is added, the mixture is stirred for 24 hours and then evaporated to dryness, the mixture is dried in a drying oven at 120 ℃ for 12 hours and finally the mixture is calcined in a muffle furnace at 550 ℃ for 2 hours. The obtained product is the 6Mo/HZSM-5 supported molecular sieve catalyst. And tabletting and granulating to obtain the molded 6Mo/HZSM-5 supported molecular sieve catalyst.

Placing 0.3g of the formed 6Mo/HZSM-5 supported molecular sieve catalyst in a quartz tube reactor, and introducing reaction gas CH₄/N₂(9:1) carbonizing at 650 ℃ for 30min, and then heating to 700 ℃ to start methane anaerobic aromatization reaction. The reaction conditions are 700 ℃, 0.1MPa and 2000h^-1The results of the (V/V) reaction are shown in Table 5.

TABLE 5 results of the methane oxygen-free aromatization catalyst reaction

Example 6

The preparation method of the Ru-based embedded molecular sieve catalyst (0.5Ru @ HZSM-5) comprises the following steps:

① Ru precursor is prepared by weighing 1.00945g of ruthenium nitrosyl nitrate solution in a beaker, diluting with a certain amount of deionized water, dipping the solution on 0.2356g of 20-40 mesh alumina carrier by excessive dipping, vacuumizing for 1h in a vacuum drier, then drying for 12h in a drying oven at 120 ℃, and finally roasting for 2h at 400 ℃ in a muffle furnace to obtain 0.5Ru/Al₂O₃A precursor;

② preparation of molecular sieve (Si/Al 10) by solution-free method, 0.5Ru/Al obtained₂O₃The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.2g of HZSM-5(Si/Al ═ 10) seed crystal and 6.56g of Na were added in this order₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 1.3868g of crystalline SiO₂Mixing and grinding until a large amount of ammonia gas is generated and the mixture becomes wet mud; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12 hours at 100 ℃, wherein the obtained catalyst is a Na-type embedded Ru-based metal catalyst with the silicon-aluminum ratio of 40;

③ molecular sieve ion exchange by pouring prepared 0.5Ru @ Na-ZSM-5 catalyst into a container containing a certain amount of 1MNH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:20 g/ml]) Ion exchange was carried out at 60 ℃ for 4 h. After ion exchange, the catalyst is put into a drying oven after several times of centrifugation and suction filtration, and dried for 12h at 120 ℃. Repeating the steps for 3 times, and roasting the dried catalyst in a muffle furnace at 500 ℃ for 3 hours to obtain the 0.5Ru @ HZSM-5 embedded molecular sieve catalyst;

and fourthly, tabletting, granulating and reducing to obtain the molded 0.5Ru @ HZSM-5 embedded molecular sieve catalyst.

Placing 0.3g of the formed 0.5Ru @ HZSM-5 embedded molecular sieve catalyst in a quartz tube reactor, reducing for 2H under 300 ℃ hydrogen, then heating to 330 ℃, and introducing synthesis gas (H)₂3:1) starting the synthesis gas methanation reaction. The reaction conditions are 330 ℃, 0.1MPa and 6000h^-1The results of the (V/V) reaction are shown in Table 6.

Comparative example 6

Preparation of the supported catalyst:

1.0808g of ruthenium nitrosyl nitrate solution is weighed into a beaker, then 3g of HZSM-5(Si/Al ═ 10) is weighed into the beaker, an appropriate amount of deionized water is added, the mixture is stirred for 24 hours and then evaporated to dryness, the mixture is dried in a drying oven at 120 ℃ for 12 hours, and finally the mixture is calcined in a muffle furnace at 400 ℃ for 2 hours. The obtained product is the 0.5Ru/HZSM-5 supported molecular sieve catalyst. And tabletting, granulating and reducing to obtain the formed 0.5Ru/HZSM-5 supported molecular sieve catalyst.

Placing 0.3g of the formed 0.5Ru/HZSM-5 supported molecular sieve catalyst in a quartz tube reactor, reducing for 2H under 300 ℃ hydrogen, then heating to 330 ℃, and introducing synthesis gas (H)₂3:1) starting the synthesis gas methanation reaction. The reaction conditions are 330 ℃, 0.1MPa and 6000h^-1The results of the (V/V) reaction are shown in Table 6.

TABLE 6 Synthesis gas methanation catalyst reaction results

Example 7

The preparation method of the Ru-Mo embedded bimetallic molecular sieve catalyst (1Ru10Mo @ HZSM-5) comprises the following steps:

① preparation of Ru-Mo precursor comprises weighing 2.5365g of ruthenium nitrosyl nitrate in a beaker, adding appropriate amount of deionized water for dilution, and soaking in 1.3868g of SiO with 20-40 meshes by excessive soaking₂Stirring the carrier on a magnetic stirrer for 24 hours, evaporating to dryness, then drying the carrier in a 120 ℃ drying box for 12 hours, then roasting the carrier in a muffle furnace at 400 ℃ for 2 hours, then weighing 0.6544g of ammonium heptamolybdate tetrahydrate in a beaker, adding 1.4332g of deionized water for dilution, soaking the diluted product on the roasted sample through equal-volume soaking, then drying the sample in a 120 ℃ drying box for 12 hours, and finally roasting the product in a 550 ℃ muffle furnace for 2 hours to obtain Ru-Mo/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-40) by solution-free method, Ru-Mo/SiO prepared by the method₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.2774g of HZSM-5(Si/Al ═ 40) seed crystal and 6.56g of Na were added in this order₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.1541g of aluminum chloride were mixed and ground until a large amount of ammonia gas was generated and the mixture became wet sludge; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours. Washing the crystallized molecular sieve alternately with deionized water and anhydrous alcohol, vacuum filtering until the solution is neutral, and washing with deionized water and anhydrous alcoholDrying in a drying oven at 100 deg.C for 12h to obtain Na-type embedded 1Ru10Mo bimetallic catalyst with Si/Al ratio of 40;

③ molecular sieve ion exchange by pouring prepared 1Ru10Mo @ Na-ZSM-5 catalyst into a container containing a certain amount of 1MNH₄NO₃The solution was mixed well in a beaker (catalyst mass with 1M NH)₄NO₃The volume ratio of the solution is 1:20 g/ml]) Ion exchange is carried out for 4 hours at the temperature of 60 ℃; after ion exchange, performing repeated centrifugation and suction filtration, putting the catalyst into a drying oven, and drying for 12 hours at 120 ℃; repeating the steps for 3 times, and roasting the dried catalyst in a muffle furnace at 500 ℃ for 3 hours to obtain the 1Ru10Mo @ HZSM-5 embedded molecular sieve catalyst;

and fourthly, tabletting, granulating and reducing to obtain the molded 1Ru10Mo @ HZSM-5 embedded molecular sieve catalyst.

Placing 0.3g of the formed 1Ru10Mo @ HZSM-5 embedded molecular sieve catalyst in a quartz tube reactor, reducing the catalyst for 2 hours under 300 ℃ hydrogen, then heating the catalyst to 330 ℃, and introducing synthesis gas (H)₂3:1) the syngas aromatization reaction was started. The reaction conditions are 330 ℃, 0.1MPa and 6000h^-1The results of the (V/V) reaction are shown in Table 7.

Comparative example 7

Preparation of the supported catalyst:

2.4045g of ruthenium nitrosyl nitrate is weighed in a beaker, an appropriate amount of deionized water is added for dilution, the ruthenium nitrosyl nitrate is soaked on a 20-40 mesh 3g of HZSM-5(Si/Al ═ 40) carrier through excessive impregnation, the mixture is stirred for 24h on a magnetic stirrer and then evaporated to dryness, then the dried mixture is placed in a 120 ℃ drying oven for drying for 12h, then the dried mixture is placed in a muffle furnace for roasting for 2h at 400 ℃, then 0.6203g of ammonium heptamolybdate tetrahydrate is weighed in the beaker and is diluted with an appropriate amount of deionized water, the diluted mixture is soaked on the roasted sample through excessive impregnation, the dried sample is placed in a 120 ℃ drying oven for drying for 12h, and finally the dried sample is placed in a 550 ℃ muffle furnace for roasting for 2h, and the obtained catalyst is the 1Ru10Mo/HZSM-5 supported bimetallic molecular sieve catalyst. Then tabletting, granulating and reducing to obtain the formed 1Ru10Mo/HZSM-5 supported bimetallic molecular sieve catalyst

Taking the molded 1Ru10Mo/HZSM-5 supported bimetallic molecular sieve catalyst 0.3g is placed in a quartz tube reactor, reduced for 2H under hydrogen at 300 ℃, then heated to 330 ℃ and introduced with synthesis gas (H)₂3:1) the syngas aromatization reaction was started. The reaction conditions are 330 ℃, 0.1MPa and 6000h^-1The results of the (V/V) reaction are shown in Table 7.

Table 7 syngas aromatization catalyst reaction results

Example 8

② preparation of molecular sieve (Si/Al-40) by solution-free method, Ru-Mo/SiO prepared by the method₂The precursor was ground in a mortar to a particle size of 100 mesh or less, and then 0.2774g of HZSM-5(Si/Al ═ 40) seed crystal and 6.56g of Na were added in this order₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.1541g of aluminum chloride were mixed and ground until a large amount of ammonia gas was generated and the mixture became wet sludge; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours. Washing the crystallized molecular sieve alternately with deionized water and anhydrous alcohol, vacuum filtering to obtain neutral solution, drying at 100 deg.C for 12 hr in drying oven to obtain the catalystThe catalyst is a Na-type embedded 1Ru10Mo embedded bimetallic catalyst with a silicon-aluminum ratio of 40;

Placing 0.3g of the formed 1Ru10Mo @ HZSM-5 embedded molecular sieve catalyst in a quartz tube reactor, reducing the catalyst for 2 hours under 300 ℃ hydrogen, then heating the catalyst to 330 ℃, and introducing synthesis gas (H)₂3:1) the syngas aromatization reaction was started. The reaction conditions are 330 ℃, 0.1MPa and 6000h^-1The (V/V) reaction results are shown in Table 8.

Comparative example 8-1

Preparation of 1Ru10Mo @ HZSM-5 catalyst with aluminum source of boehmite

② preparation of molecular sieve (Si/Al-40) by solution-free method, Ru-Mo/SiO prepared by the method₂Grinding the precursor in a mortar to below 100 meshes, and sequentially adding0.2774g of HZSM-5(Si/Al ═ 40) seed crystal and 6.56g of Na were added₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.0823g of boehmite were mixed and ground until a large amount of ammonia gas was generated and the mixture became wet sludge; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours. Alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then drying the solution in a drying oven at 100 ℃ for 12 hours to obtain a Na-type embedded 1Ru10Mo embedded bimetallic catalyst with the Si/Al ratio of 40;

Comparative examples 8 to 2

Preparation of 1Ru10Mo @ HZSM-5 catalyst without seeding:

① preparation of Ru-Mo precursor comprises weighing 2.5365g of ruthenium nitrosyl nitrate in a beaker, adding appropriate amount of deionized water for dilution, and soaking in 1.3868g of SiO with 20-40 meshes by excessive soaking₂Stirring on carrier for 24 hr, evaporating to dry, and drying at 120 deg.C in drying ovenDrying for 12h, then placing the dried sample into a muffle furnace for roasting for 2h at 400 ℃, then weighing 0.6544g ammonium heptamolybdate tetrahydrate in a beaker, adding 1.4332g deionized water for dilution, dipping the diluted sample onto the roasted sample through equal-volume dipping, then placing the sample into a 120 ℃ drying box for drying for 12h, and finally placing the sample into a 550 ℃ muffle furnace for roasting for 2h to obtain Ru-Mo/SiO₂A precursor;

② preparation of molecular sieve (Si/Al-40) by solution-free method, Ru-Mo/SiO prepared by the method₂The precursor was ground in a mortar to below 100 mesh, followed by the sequential addition of 6.56g of Na₂SiO₃·9H₂O, 1.2g of tetrapropylammonium bromide (TPABr), 2g of NH₄Cl and 0.1541g of aluminum chloride were mixed and ground until a large amount of ammonia gas was generated and the mixture became wet sludge; pouring the mixture in the mortar into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a crystallization box at 180 ℃ for crystallization for 24 hours. Alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then drying the solution in a drying oven at 100 ℃ for 12 hours to obtain a Na-type embedded 1Ru10Mo embedded bimetallic catalyst with the Si/Al ratio of 40;

Placing 0.3g of the formed 1Ru10Mo @ HZSM-5 embedded molecular sieve catalyst in a quartz tube reactor, reducing the catalyst for 2 hours under 300 ℃ hydrogen, then heating the catalyst to 330 ℃, and introducing synthesis gas (H)₂3:1) the syngas aromatization reaction was started. The reaction conditions are 330 ℃, 0.1MPa, 6000h-1(V/V)The reaction results are shown in Table 8.

TABLE 8 synthetic gas aromatization catalyst reaction results

It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.

Claims

1. A method for preparing an embedded catalyst for carbon-one chemical reaction without a solution method is characterized by comprising the following steps:

s1 preparation of precursor

Weighing a metal compound with determined metal loading capacity, preparing a solution with determined metal loading capacity, and soaking the metal compound solution on a carrier with 20-40 meshes by using equal-volume soaking when the mass fraction of the metal loading capacity is less than 6%; when the mass fraction of the metal loading is higher than 6%, the metal compound is impregnated on a 20-40 mesh carrier by using an excess impregnation method, the carrier is vacuumized for 0.5-2 h, then dried for 12-24h at the temperature of 80-150 ℃, and then placed in a muffle furnace for roasting for 2-6h at the temperature of 400-600 ℃; obtaining a solid catalyst precursor, and grinding the solid catalyst precursor to be below 100 meshes for later use;

s2 preparation of molecular sieve by solution-free method

Grinding a solid catalyst precursor to be less than 100 meshes, and a seed crystal and Na which account for 2-10% of the mass of the solid catalyst₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl, an aluminum source and/or a silicon source and/or a phosphorus source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and placing the polytetrafluoroethylene crystallization kettle in a drying oven at the temperature of 120-200 ℃ for crystallization for 12-36 h; will crystallizeWashing and filtering the good molecular sieve by using deionized water and absolute ethyl alcohol alternately until the solution is neutral, and then placing the good molecular sieve in a drying oven at 80-120 ℃ for drying for 12-24 hours to obtain a Na-type embedded metal molecular sieve catalyst;

s3 molecular sieve ion exchange

s4, tabletting, granulating and reducing to obtain a molded embedded catalyst;

in step S2, the solid catalyst precursor, the seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Cl, aluminum source or silicon source or phosphorus source in the following weight ratio: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S3, the mass of the Na-type embedded metal molecular sieve catalyst and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml;

in step S1, the carrier is silica or alumina;

in step S2, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide;

in step S2, the silicon source is one or more of crystalline silica, amorphous silica, and fumed silica;

in step S2, the phosphorus source includes ammonium dihydrogen phosphate;

in step S2, in step 2), the molecular sieve includes H beta, MCM-41, MCM-22, SAPO-34 or HZSM-5.

2. The method for preparing an embedded catalyst for a carbon-one chemical reaction without a solution according to claim 1, wherein the Ni-based embedded catalyst is prepared without a solution by the steps of:

s11, preparation of a Ni precursor:

weighing Ni metal compounds with determined Ni load, and preparing a solution with determined metal Ni load; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; when the metal loading mass fraction is higher than 6%, the metal loading mass fraction is impregnated in a carrier SiO of 20-40 meshes by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining Ni-based precursor, and grinding the Ni-based precursor to be below 100 meshes for later use;

s12, preparation of the molecular sieve by the solution-free method:

s13, molecular sieve ion exchange:

s14, preparing the Ni-based embedded catalyst through tabletting, granulating and reducing;

in step S11, the Ni metal compound includes one or more of nickel nitrate, nickel chloride, nickel acetate, and nickel oxalate;

in step S12, the Ni-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S12, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide;

in step S13, the Na-type embedded Ni-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

3. The method for preparing an embedded catalyst for a carbon-one chemical reaction without a solution according to claim 1, wherein the Mo-based embedded catalyst is prepared without a solution by the following steps:

s21, preparation of a Mo precursor:

weighing Mo metal compounds determining Mo loading, and preparing a solution determining metal Mo loading; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; when the metal loading mass fraction is higher than 6%, the metal loading mass fraction is impregnated in a carrier SiO of 20-40 meshes by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Mo-based precursor, and grinding the Mo-based precursor to be less than 100 meshes for later use;

s22, preparation of the molecular sieve by the solution-free method:

s23, molecular sieve ion exchange:

adding 1M NH into the prepared Na-type embedded Mo-based metal molecular sieve catalyst₄NO₃Fully mixing and stirring the solution, and carrying out ion exchange at 40-80 ℃ for 2-8 h; centrifuging and extracting for 3 timesAfter filtering, putting the catalyst into a drying box, and drying for 12-24h at the temperature of 80-150 ℃; roasting the dried catalyst in a muffle furnace at 400-600 ℃ for 2-6 h;

s24, preparing the Mo-based embedded catalyst through tabletting, granulating and reducing;

in step S21, the Mo metal compound includes one or more of ammonium molybdate, molybdenum chloride, and sodium molybdate;

in step S22, the Mo-based precursor, the seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S22, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide.

4. The method for preparing an embedded catalyst for a carbon-one chemical reaction according to claim 1, wherein the step of preparing the Ru-based embedded catalyst according to the solution-free method comprises:

s31, preparation of Ru precursor:

weighing Mo metal compounds with determined Ru loading capacity, and diluting with a determined amount of nitric acid solution; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; when the metal loading mass fraction is higher than 6%, the metal loading mass fraction is impregnated in a carrier SiO of 20-40 meshes by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining Ru-based precursor, and grinding the Ru-based precursor to be below 100 meshes for later use;

s32, preparation of the molecular sieve by the solution-free method:

grinding Ru-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and a solid silicon source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; crystallizing the well crystallized molecular sieveAlternately washing and filtering the solution by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry the solution for 12 to 24 hours at the temperature of between 80 and 150 ℃ to prepare the Na-type embedded Ru-based metal molecular sieve catalyst;

s33, molecular sieve ion exchange:

s34, preparing the Ru-based embedded catalyst through tabletting, granulating and reducing;

in step S31, the Ru metal compound includes one or more of ruthenium nitrosyl nitrate, ruthenium trichloride, and ruthenium acetate;

in step S32, the Ru-based precursor, the seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the solid silicon source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 1.3-1.4;

in step S32, the solid silicon source includes one or more of crystalline silica, amorphous silica, and fumed silica;

in step S33, the Na-type embedded Ru-based metal molecular sieve catalyst has a mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

5. The method for preparing an embedded catalyst for a carbon-one chemical reaction without a solution according to claim 1, wherein the method for preparing the Pt-based embedded catalyst without a solution comprises the following steps:

s41, preparation of a Pt precursor:

weighing a Pt metal compound with a determined Pt loading amount, and diluting with a determined amount of hydrochloric acid; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; and when the mass fraction of the metal loading is higher than 6%, the metal loading is impregnated by using an excessive impregnation methodIn 20-40 mesh SiO carrier₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Pt-based precursor, and grinding the Pt-based precursor to be below 100 meshes for later use;

s42, preparation of the molecular sieve by the solution-free method:

grinding Pt-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl, ammonium dihydrogen phosphate and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; alternately washing and filtering the crystallized molecular sieve by using deionized water and absolute ethyl alcohol until the solution is neutral, and then putting the solution into a drying oven to dry for 12-24h at the temperature of 80-150 ℃ to prepare the Na-type embedded Pt-based metal molecular sieve catalyst;

s43, molecular sieve ion exchange:

s44, preparing the Pt-based embedded catalyst through tabletting, granulating and reducing;

in step S41, the Pt metal compound includes one or more of diammine platinum dimethylene, platinum chlorate and platinum nitrate;

in step S42, the Pt-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl, ammonium dihydrogen phosphate and the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S42, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide;

in step S43, the Na-type embedded Pt-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

6. The method for preparing an embedded catalyst for a carbon-one chemical reaction without a solution according to claim 1, wherein the Co-based embedded catalyst is prepared without a solution by the following steps:

s51, preparation of a Co precursor:

weighing a Co metal compound with determined Co load, and preparing a solution with determined metal Co load; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; when the metal loading mass fraction is higher than 6%, the metal loading mass fraction is impregnated in a carrier SiO of 20-40 meshes by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining a Co-based precursor, and grinding the Co-based precursor to be below 100 meshes for later use;

s52, preparation of the molecular sieve by the solution-free method:

s53, molecular sieve ion exchange:

s54, preparing the Co-based embedded catalyst through tabletting, granulating and reducing;

in step S51, the Co metal compound includes one or more of cobalt nitrate, cobalt acetate, cobalt carbonyl, cobalt oxalate, and cobalt sulfate;

in step S52, the Co-based precursor, the seed crystal, and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S52, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide;

in step S53, the Na-type embedded Co-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.

7. The method for preparing an embedded catalyst for a carbon-one chemical reaction according to claim 1, wherein the method for preparing the Fe-based embedded catalyst comprises the following steps:

s61, preparation of a Fe precursor:

weighing Fe metal compounds determining Fe load, and preparing a solution determining metal Fe load; when the mass fraction of the metal loading is less than 6%, impregnating the metal compound solution on a 20-40 mesh carrier by using equal volume impregnation; when the metal loading mass fraction is higher than 6%, the metal loading mass fraction is impregnated in a carrier SiO of 20-40 meshes by using an excessive impregnation method₂Vacuumizing for 0.5-2 h, drying at 80-150 ℃ for 12-24h, and roasting in a muffle furnace at 400-600 ℃ for 2-6 h; obtaining Fe-based precursor, and grinding the Fe-based precursor to be below 100 meshes for later use;

s62, preparation of the molecular sieve by the solution-free method:

grinding Fe-based precursor with the particle size of less than 100 meshes, seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄Sequentially mixing and grinding Cl and an aluminum source for a period of time; pouring the ground mixture into a polytetrafluoroethylene crystallization kettle provided with a steel sleeve, and putting the polytetrafluoroethylene crystallization kettle into a drying oven at the temperature of 120-; washing the crystallized molecular sieve with deionized water and anhydrous ethanol alternately, vacuum filtering until the solution is neutral, drying in a drying oven at 80-150 deg.C for 12-24 hr,preparing a Na-type embedded Fe-based metal molecular sieve catalyst;

s63, molecular sieve ion exchange:

s64, preparing the Fe-based embedded catalyst through tabletting, granulating and reducing;

in step S61, the Fe metal compound includes one or more of ferric nitrate, ferric acetate, carbonyl iron, ferric oxalate, and ferric sulfate;

in step S62, the Fe-based precursor, the seed crystal and Na₂SiO₃·9H₂O, tetrapropylammonium bromide, NH₄The weight ratio of Cl to the aluminum source is as follows: 1.2-1.5:0.06-0.3:6.2-6.6:1.2-1.4:1.8-2.2: 0.006-1.73;

in step S62, the aluminum source includes one or more of aluminum nitrate, aluminum chloride, aluminum oxide, and aluminum isopropoxide;

in step S63, the Na-type embedded Fe-based metal molecular sieve catalyst mass and 1M NH₄NO₃The volume ratio of the solution is 1:20-1:50 g/ml.