CN112742401B

CN112742401B - FT synthesis catalyst, preparation method and application thereof

Info

Publication number: CN112742401B
Application number: CN201911053472.2A
Authority: CN
Inventors: 侯朝鹏; 徐润; 夏国富; 张荣俊; 阎振楠
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2022-07-15
Anticipated expiration: 2039-10-31
Also published as: CN112742401A

Abstract

The invention provides an FT synthetic catalyst and a preparation method and application thereof, wherein the FT synthetic catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component is selected from one or more of Co, Fe and Ru, the carrier is a raspberry type oxide microsphere, the raspberry type oxide microsphere is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, the large pore is communicated with the hollow structure to form a cavity with one open end, and the oxide in the raspberry type oxide microsphere is selected from one or more of alumina and silicon oxide. The FT synthesis catalyst of the invention can improve the conversion rate of FT synthesis and the selectivity of C5+ hydrocarbon, and reduce the selectivity of methane and CO₂And meanwhile, the methane selectivity of the catalyst is not obviously improved due to the increase of the temperature, and the problem of diffusion of the FT synthesis reaction is obviously solved.

Description

FT synthesis catalyst, preparation method and application thereof

Technical Field

The invention relates to the field of catalysts, and particularly relates to an FT synthesis catalyst, and a preparation method and application thereof.

Background

In the past decades, a great deal of literature is devoted to research and report on inorganic hollow microsphere materials. Compared with the common compact sphere, the hollow material has smaller density and larger specific surface area, and is widely applied to various fields such as drug catalyst carriers, gas adsorbents and the like, and in recent years, the research and application of the inorganic hollow microsphere material are receiving more and more attention.

The alumina composition cavity ball is a new-type high-temp. heat-insulating material made up by using industrial alumina through the processes of smelting and blowing in electric furnace, and its crystal form is a-Al₂O₃A microcrystal. The alumina hollow ball is used as main body, and can be made into various shaped products, and the product has high mechanical strength which is several times that of general light products, but the volume density is far less than that of solid products. The energy-saving furnace is widely applied to high-temperature and ultrahigh-temperature kilns such as petrochemical industry gasification furnaces, carbon black industry reaction furnaces, metallurgical industry induction furnaces and the like, and obtains a very satisfactory energy-saving effect. The existing preparation methods of alumina cavity materials include a high-temperature melting and spray reaction method, a template method, a layer-by-layer self-assembly method (L-b-L) and a microemulsion method.

The silica hollow microsphere has the advantages of good biocompatibility, easily available raw materials, low price and the like, and is widely applied to the fields of drug carriers, biological signal markers, coatings and the like, and the preparation technology of the inorganic hollow microsphere is also widely concerned by researchers. The most widely reported method is to use polystyrene microspheres as a template, wrap a silicon oxide shell layer on the surface of the polystyrene microspheres, and remove a polystyrene core to obtain the silicon oxide hollow microspheres. The preparation methods reported in the literature at present mainly comprise (1) an electrostatic adsorption method; (2) silicon cross-linking agent modification; (3) Layer-by-Layer (Layer-by-Layer) method.

Fischer-Tropsch synthesis (also called FT synthesis) is a process of synthesizing liquid hydrocarbons or hydrocarbons from synthesis gas (a mixed gas of carbon monoxide and hydrogen) as a raw material under a catalyst and appropriate conditions, and is a key step for indirectly converting non-oil-based resources such as coal, natural gas, biomass, and the like into high-grade liquid fuels and chemical raw materials.

One of the means commonly used to obtain the desired FT synthesis product distribution is to modify the FT synthesis catalyst. However, the existing preparation method of the inorganic hollow microsphere material generally has the problems of small scale and difficult expansion, meanwhile, some preparation methods have low preparation efficiency and high raw material cost, the preparation of the catalyst by using the inorganic hollow microsphere material as a carrier is also greatly limited, and the performance of the prepared catalyst can not meet the requirements.

It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.

Disclosure of Invention

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide an FT synthesis catalyst having improved performance.

In order to achieve the purpose, the invention adopts the following technical scheme:

an FT synthetic catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component is selected from one or more of Co, Fe and Ru, the carrier is raspberry type oxide microspheres, the raspberry type oxide microspheres are hollow microspheres with a large pore on the surface, a hollow structure is arranged inside the hollow microspheres, the large pore and the hollow structure are communicated to form a cavity with an opening at one end, and the oxide in the raspberry type oxide microspheres is selected from one or more of alumina and silica.

In some embodiments, the support is present in the catalyst in an amount of from 25 to 95 wt%, preferably from 30 to 90 wt%, calculated as oxide and based on the catalyst; the content of the active metal component in the catalyst is 5-75 wt%, preferably 10-70 wt%.

In some embodiments, the raspberry type oxide microspheres have a particle size of 3 to 2500 μm, preferably 10 to 500 μm, and a sphericity of 0.50 to 0.99.

In some embodiments, the diameter of the hollow structure is 1-2000 μm, preferably 1-400 μm.

In some embodiments, the macropores have a pore size of 0.2 to 1000 μm, preferably 0.5 to 200 μm.

In some embodiments, the shell thickness of the hollow microsphere is 0.2-1000 μm, preferably 0.5-200 μm.

In some embodiments, the raspberry-type oxide microspheres have a fragmentation rate of 0 to 1%.

In another aspect, the present invention also provides a method for preparing the FT synthesis catalyst, comprising the steps of:

providing raspberry type oxide microspheres and an impregnation solution of a compound containing the active metal component;

roasting the raspberry type oxide microspheres to obtain the carrier; and

and (3) impregnating the carrier by using the impregnation solution, and drying, roasting and activating to obtain the FT synthetic catalyst.

In some embodiments, the step of providing raspberry-type oxide microspheres includes:

adding nitrate, peptizing agent, pore-forming agent, aluminum source and/or silicon source into the dispersing agent and stirring to obtain dispersed slurry;

carrying out aging treatment on the dispersed slurry;

feeding the aged dispersed slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; and drying and forming under the condition that the air outlet temperature is 50-300 ℃, preferably 120-200 ℃ to obtain the raspberry type oxide microspheres.

In some embodiments, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

In some embodiments, the peptizing agent is selected from one or more of acids, bases, and salts.

In some embodiments, the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohols, and surfactants.

In some embodiments, the aluminum source is selected from one or more of pseudoboehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, and the silicon source is selected from one or more of silicate, sodium silicate, water glass, and silica sol.

In some embodiments, the dispersant is selected from one or more of water, alcohols, ketones, and acids.

In some embodiments, the mass ratio of the nitrate, the peptizing agent, the pore former, and the oxide and/or a precursor thereof is (10-500): (1-10): (10-500): (10-1000).

In some embodiments, the method further comprises adding a blasting agent to the dispersing agent, wherein the blasting agent is selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, danner explosive, hexogen and C4 plastic explosive, and the addition amount of the blasting agent is 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the aluminum source and/or the silicon source.

In some embodiments, the drying device is a flash drying device or a spray drying device.

In some embodiments, the temperature of the aging treatment is 0 to 90 ℃, preferably 20 to 60 ℃.

In some embodiments, the roasting temperature is 400-1300 ℃, preferably 450-1100 ℃, more preferably 500-700 ℃, the drying temperature is 80-200 ℃, preferably 100-150 ℃, and the roasting activation temperature is 200-800 ℃, preferably 300-600 ℃.

In a further aspect, the invention provides the use of the FT synthesis catalyst described above in the field of fischer-tropsch synthesis.

The FT synthesis catalyst has short diffusion distance and large macroscopic surface area, can improve the conversion rate of FT synthesis and the selectivity of C5+ hydrocarbons, and reduces the selectivity of methane and CO₂And meanwhile, the methane selectivity of the catalyst is not obviously improved due to the increase of the temperature, and the problem of diffusion of the FT synthesis reaction is obviously solved.

Drawings

FIG. 1 is a microphotograph of raspberry type oxide microspheres prepared in preparation example 1.

FIG. 2 is a microphotograph of the raspberry type catalyst microspheres obtained in example 1.

FIG. 3 is a microphotograph of oxide support microspheres obtained in preparation example 5.

FIG. 4 is a microphotograph of catalyst microspheres obtained in example 5.

FIG. 5 is a microphotograph of the oxide support microsphere prepared in comparative example 1.

FIG. 6 is a microphotograph of catalyst microspheres prepared in comparative example 1.

Detailed Description

The technical solution of the present invention is further explained below according to specific embodiments. The scope of protection of the invention is not limited to the following examples, which are set forth for illustrative purposes only and are not intended to limit the invention in any way.

In the present invention, anything or matters not mentioned is directly applicable to those known in the art without any change except those explicitly described. Moreover, any embodiment described herein may be freely combined with one or more other embodiments described herein, and the technical solutions or ideas thus formed are considered part of the original disclosure or original description of the present invention, and should not be considered as new matters not disclosed or contemplated herein, unless a person skilled in the art would consider such combination to be clearly unreasonable.

All features disclosed in this invention may be combined in any combination and such combinations are understood to be disclosed or described herein unless a person skilled in the art would consider such combinations to be clearly unreasonable. The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.

According to a first aspect of the present invention, there is provided an FT synthesis catalyst comprising a support and an active metal component supported on the support.

In the FT synthetic catalyst, an active metal component is a metal component in a VIII group and is selected from one or more of Co, Fe and Ru, the activity of the active metal component is Ru > Co > Fe in sequence, and the chain growth probability sequence is approximately Ru > Co & ltapprxeq.Fe.

In the FT synthetic catalyst, the carrier is raspberry type oxide microspheres, which are hollow microspheres similar to raspberry type structures, the surface of each hollow microsphere is provided with a large hole, a hollow structure is arranged inside each hollow microsphere, and the large holes and the hollow structures are communicated to form a cavity with one open end.

The oxide in the raspberry type oxide microspheres is inorganic oxide, and can be one or more of alumina and silicon oxide.

The raspberry type oxide microspheres have the particle size of 3-2500 microns, preferably 10-500 microns, the diameter of a hollow structure is 1-2000 microns, preferably 1-400 microns, and the pore diameter of surface macropores is 0.2-1000 microns, preferably 0.5-200 microns. The raspberry type oxide microsphere has a shell layer surrounding a cavity, and the thickness of the shell layer is 0.2-1000 mu m, preferably 0.5-200 mu m.

The appearance of the raspberry type oxide microspheres is close to spherical, and the sphericity of the raspberry type oxide microspheres is 0.50-0.99.

Sphericity of microbead blank is represented by formula

σ＝4πA/L²

And (6) calculating. In the formula: sigma is sphericity; a is the projected area of the microsphere in m²(ii) a L isThe projection perimeter of the microsphere is m; a and L are obtained from SEM pictures of microspheres and processed by Image processing software Image-Pro Plus.

The raspberry type oxide microspheres are roasted at 400-1300 ℃, preferably 450-1100 ℃, and more preferably 500-700 ℃ to obtain oxides, and the specific surface area of the oxides is about 0.1-900 m²A preferred range is 10 to 300m²A pore volume of about 0.01 to 3.6ml/g, preferably 0.1 to 0.9 ml/g.

The crushing rate of the raspberry type oxide microspheres is 0-1%, the crushing rate is measured according to a method provided by a similar strength standard number Q/SH 3360226-2010, and the specific method is as follows:

firstly, selecting sieves S1 and S2 with meshes of M1 and M2 respectively, wherein M1 is less than M2, enabling microspheres to be detected to firstly pass through the sieve S1 with the meshes of M1, then enabling the sieved microsphere powder to pass through the sieve S2 with the meshes of M2, and finally enabling the microsphere powder intercepted by the sieve S2 to serve as a sample to be detected.

Adding a sample to be tested with a certain mass into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure to microspheres through a cylinder for a certain time, screening the pressed microsphere powder by using a screen S2 with the mesh number of M2, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the total mass of the added microspheres to obtain the breaking rate of the microspheres.

In the present invention, M1 can be 100 mesh, M2 can be 150 mesh, pressure can be 100N, and time can be 10 s.

The strength of the microspheres can be evaluated by using the breakage rate; the smaller the breakage rate, the higher the strength of the microspheres

The raspberry type oxide microspheres of the present invention have low breaking rate and strength under pressurized conditions, which is significantly higher than that of the existing known oxide microspheres, such as the apple-shaped hollow molecular sieve microspheres disclosed in CN108404970A, and is determined by the differences of the raw materials and the preparation method thereof. The higher strength enables the porosity of the raspberry type oxide microspheres to be larger, the pressure drop to be greatly reduced, meanwhile, the raspberry type oxide microspheres have excellent processing performance and loss resistance, the reaction diffusion distance in the field of catalysts prepared by using the raspberry type oxide microspheres as carriers is short, the raspberry type oxide microspheres have wide application prospects, and the raspberry type oxide microspheres can also be prepared into high-temperature heat-insulating materials, biological materials and photochemical materials.

In the FT synthesis catalyst of the present invention, the catalyst is used as a catalyst for FT synthesis,

the content of the carrier in the catalyst is 25-95 wt%, preferably 30-90 wt%; the content of the active metal component in the catalyst is 5-75 wt%, preferably 10-70 wt%, and more preferably 12-30 wt%.

The FT synthetic catalyst can be applied to a micro-channel Fischer-Tropsch synthesis reaction.

The FT synthesis catalyst of the present invention can be prepared by a method comprising:

providing an impregnation solution of raspberry-type oxide microspheres and a compound containing an active metal component;

roasting the raspberry type oxide microspheres to obtain a carrier; and

and (3) impregnating the carrier by using an impregnating solution, and drying, roasting and activating to obtain the FT synthetic catalyst.

In the preparation method of the invention, the raspberry type oxide microspheres can be prepared by the following method comprising the following steps:

aging the dispersion slurry; and

feeding the aged dispersed slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; and (3) drying and forming at the air outlet temperature of 50-300 ℃, preferably at 120-200 ℃ to obtain the raspberry type oxide microspheres.

In the preparation method of the invention, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate. Nitrate ions in nitrates promote their ability to act as pore formers as oxidants at high temperatures, which undergo self-propagating combustion reactions at high temperatures to produce gases and vapors that form cavities in the oxide material.

In the preparation method of the invention, the peptizing agent is selected from one or more of acids, alkalis and salts. The acids can be selected from: inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid and the like), organic acid (formic acid, acetic acid, oxalic acid and the like) and one or more of inorganic acid or organic acid; alkalies can be selected from: inorganic bases (sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, aluminum hydroxide, lithium hydroxide, magnesium hydroxide, zinc hydroxide, copper hydroxide, iron hydroxide, lead hydroxide, cobalt hydroxide, chromium hydroxide, zirconium hydroxide, nickel hydroxide, ammonium hydroxide, soda ash (anhydrous sodium carbonate), sodium carbonate (monohydrate, heptahydrate, decahydrate), sodium bicarbonate (baking soda), potassium carbonate, potassium bicarbonate, etc.), organic bases (such as amine compounds, alkali metal salts of alcohols, alkaloids, lithium alkyl metal compounds, etc.), and one or more of inorganic acids or organic acids; the salts can be selected from: inorganic acid salt (such as hydrochloric acid, sulfate, nitrate, etc.), organic acid salt (formate, acetate, oxalate, etc.), and one or more of inorganic acid salt or organic acid salt.

In the preparation method of the invention, the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol and surfactant. Wherein the synthetic cellulose is preferably one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polymer alcohol is preferably one or more of polyethylene glycol, polypropylene alcohol, polyvinyl alcohol and polypropylene alcohol PPG; the surfactant is preferably one or more of fatty alcohol polyvinyl ether, fatty alcohol amide and derivatives thereof, acrylic acid copolymer with molecular weight of 200-2000000 and maleic acid copolymer.

In the preparation method, the aluminum source is selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, and the silicon source is selected from one or more of silicate ester, sodium silicate, water glass and silica sol.

When the aluminum source or the silicon source is used, a chemical agent for precipitating or gelling the aluminum source or the silicon source may be used, for example, an acid (e.g., an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid or an organic acid such as acetic acid) and/or a base (e.g., sodium carbonate or sodium hydroxide).

When it is necessary to prepare an oxide composition containing other components, oxides such as vanadium oxide, chromium oxide, manganese oxide, molybdenum oxide, tungsten oxide, iron oxide, cobalt oxide, nickel oxide, and copper oxide may be added, and precursors that can form these oxides may also be added.

In the preparation method, the dispersing agent is selected from one or more of water, alcohols, ketones and acids, wherein the alcohols can be methanol, ethanol, propanol and the like, the ketones can be acetone, butanone and the acids can be formic acid, acetic acid, propionic acid and the like. The preferable dispersing agent is a mixture of water and a small amount of ethanol, the small amount of ethanol can play a better dispersing effect in water and can be used as a boiling point regulator, and the water evaporation effect and the liquid drop shrinkage effect are matched and matched more through regulating the dispersing agent, so that the appearance effect of the microsphere is more regular and smooth.

In the preparation method, the mass ratio of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof is (10-500): (1-10): (10-500): (10-1000).

In the preparation method, the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof can be sequentially added into the dispersing agent or simultaneously added, the adding sequence can be adjusted according to the dissolution condition of the raw materials, and the raw materials are stirred to be uniformly mixed while being added.

The preparation method of the invention can also comprise adding a blasting agent into the dispersing agent, wherein the blasting agent can be added before or after the oxide. The blasting agent is selected from one or more of picric acid, trinitrotoluene, mercury fulminate, digested glycerol, nitrocotton, danner explosive, hexogen, lead azide and C4 plastic explosive. Before drying and forming, the blasting agent is mixed with other materials uniformly. The addition amount of the blasting agent is 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the aluminum source and/or the silicon source.

In the preparation method, the nitrate, the peptizing agent, the pore-forming agent and the precursor of the oxide are sequentially added into the dispersing agent for pulping, and the slurry is pumped into a sand mill or a colloid mill for grinding after being uniformly stirred to obtain the dispersed slurry. The slurry solids content during pulping is generally between 5 and 60% by weight and the grinding time is between 1 and 30 minutes. After mixing and grinding, the average particle size of the aluminum source, silicon source, zirconium source and titanium source particles in the slurry can be ground to 0.01-10 μm.

After the raw materials are mixed and ground, the raw materials are fully dissolved and dispersed, so that the dispersed slurry is uniform. The milling equipment used may be a colloid mill, sand mill or other equipment, the criterion being selected to achieve the desired average particle size of the catalyst fines after milling thereof, i.e. less than 10 μm.

And then aging the dispersion slurry at 0-90 ℃ for 0.1-24 hours, preferably 0.5-2 hours.

And (3) after aging treatment, feeding the dispersed slurry into a drying device, drying and forming at the air inlet temperature of 400-1200 ℃, preferably 450-700 ℃, the air outlet temperature of 50-300 ℃, preferably 120-200 ℃, and the pressure in a spray tower is similar to that of conventional spraying, so that the raspberry type oxide microspheres can be obtained.

The drying apparatus used in the present invention may be a flash drying apparatus and a spray drying apparatus, preferably a spray drying apparatus. Flash drying and spray drying are common methods applied for material drying. After the wet material is dispersed in a drying tower, the moisture is quickly vaporized in the contact with hot air, and a dry product is obtained. The spray drying method can directly dry the solution and emulsion into powder or granular products, and can omit the procedures of evaporation, pulverization and the like.

The working principle of spray drying is to disperse the material to be dried into fine mist-like particles by mechanical action (such as pressure, centrifugation, air-flow type spraying), increase the water evaporation area, accelerate the drying process, contact with hot air, remove most of the water in a short time, and dry the solid matter in the material into powder.

The spray drying apparatus used in the present invention is a conventional apparatus in the existing flow path, and the present invention is not particularly limited thereto. Spray drying apparatus generally comprises: the system comprises a feeding system, a hot air system, a drying tower system, a receiving system and a sealing system. The feeding system is connected with the drying tower system in the middle of the top end, the hot air system is connected with the side face of the top end of the drying tower system, the receiving system is connected with the bottom end of the drying tower system, and the sealing system is connected with the hot air system. In the spray drying process, it is essentially necessary to have a spray of the stock solution; drying the tiny droplets in the spray; three functions of separating and recovering fine powder products are realized. In the spray drying apparatus, an atomizer, a drying chamber, and a fine powder recoverer corresponding to the above-described functions are generally equipped.

Because the control parameters in the spray drying process are more and the factors are complex, the particle size and the particle shape after spray drying are very complex. The size range of the product is generally in micron order, and the product is generally a mixture of shapes including a sphere, a disc, an apple shape, a grape shape, a cavity shape, a meniscus shape and the like, and how to selectively form an ideal single shape, such as a cavity shape, is a difficulty in the formation of the product.

One method in the prior art is to form spherical emulsion under the action of surface tension of a surfactant, and then at the moment of spray forming at a lower temperature, a pore-forming agent is vaporized or pyrolyzed in the spherical emulsion, and gas generated by vaporization and pyrolysis can cause a cavity in the microsphere emulsion; and forming secondary stacking holes to become mesopores on the surface of the molecular sieve microspheres in the spray forming process of the molecular sieve particles, and combining the subsequent roasting process to obtain the large-particle hollow molecular sieve microspheres.

Under the high temperature of 400-1200 ℃, the oxide and the reducing agent in the slurry undergo strong oxidation-reduction self-propagating combustion reaction to instantly generate a large amount of gas; at the same time, the droplet spray enters a high temperature zone, strongly evaporates, and the surface tension formed by the thickened slurry causes the droplets to shrink sharply. The strong explosion of the inside and the strong contraction of the outside form a raspberry type hollow material with good strength. The prepared raspberry type oxide microspheres have high strength, high sphericity and high yield.

The raspberry type oxide microspheres can be used as a carrier after being roasted, and can be prepared into various catalysts after being loaded with corresponding active components. The roasting temperature can be 400-1300 ℃, the preferable temperature is 450-1100 ℃, and the preferable temperature is 500-700 ℃; the roasting time can be 1-12 h, preferably 2-8 h, and more preferably 3-4 h.

In the impregnation solution of the compound containing the active metal component, the compound containing the active metal component is selected from one or more soluble compounds thereof, such as one or more soluble complexes of cobalt nitrate, cobalt acetate, cobalt carbonate hydroxide, cobalt chloride and cobalt, and preferably cobalt nitrate and cobalt carbonate hydroxide.

The supporting method of the present invention is preferably an impregnation method comprising preparing an impregnation solution of the compound containing the active metal component, and thereafter impregnating the support with the solution. The impregnation method is a conventional method, and for example, it may be an excess liquid impregnation method, a pore saturation method impregnation method. Wherein the concentration, amount or carrier amount of the impregnation solution containing the active metal component can be adjusted and controlled to produce a catalyst of a specified content, as will be readily understood and accomplished by those skilled in the art.

After impregnation, the product needs to be dried, the drying temperature is 80-200 ℃, preferably 100-150 ℃, the used drying device and the operating conditions thereof are conventional equipment and operating parameters in the prior drying technology, and the invention has no special limitation on the drying device and the operating parameters.

And roasting and activating the dried product to obtain the catalyst, wherein the roasting and activating temperature is 200-800 ℃, and the preferable temperature is 300-600 ℃. The roasting apparatus used and its operating conditions are conventional equipment and operating parameters in the prior art roasting, and the present invention is not particularly limited thereto.

The application of the raspberry type oxide microspheres can reduce the waste of the carrier and the catalyst and save materials; meanwhile, due to the improvement of the shape efficiency factor, the diffusion can be promoted, and the reaction efficiency and the selectivity of a target product are improved. In the reaction with larger heat effect, the hollow carrier can also reduce the generation of hot spots, and has good intrinsic safety.

Due to short diffusion distance and large macroscopic surface area, the FT synthesis catalyst of the invention has FT synthesisThe performance is better, the conversion rate of FT synthesis and the selectivity of C5+ hydrocarbon can be improved, and the selectivity of methane and CO can be reduced₂And meanwhile, the methane selectivity of the catalyst is not obviously improved due to the temperature rise, and the problem of diffusion of the FT synthesis reaction is obviously solved. In addition, the preparation method of the invention has lower cost and can be applied in large-scale industry.

The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.

Examples

Reagents, instruments and tests

In the following examples, preparations and comparative examples, some of the raw material specifications used were as follows:

pseudo-boehmite powder (produced by Changling catalyst plant, solid content 69.5 wt%; gamma-Al)₂O₃Content of not less than 98 wt%);

sodium silicate (chemical Limited, module 3.1-3.4, insoluble less than 0.4%);

ammonia, hydrochloric acid, nitric acid, sulfuric acid, aluminum nitrate, aluminum sulfate, aluminum chloride (national chemical group, ltd., industrial grade);

polyethylene glycol PEG4000 powder (Wenzhou Shuanghoi rubber and plastic materials Co., Ltd.);

methylcellulose (Hubei Jiangtiantai chemical Co., Ltd.);

tetraethoxysilane (TEOS, jonan hua special chemical limited, content about 99%);

zirconium nitrate, yttrium nitrate (Yutai qixin chemical Co., Ltd., industrial grade)

The breakage of the support and the catalyst can be measured according to the following method:

the microspheres to be detected firstly pass through a 100-mesh sieve, then the sieved microsphere powder passes through a 150-mesh sieve, and finally the microsphere powder intercepted by the 150-mesh sieve is used as a sample to be detected. Adding microspheres with a certain mass (the granularity is 100-150 meshes) into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure (100N) to the microspheres through a cylinder for a certain time (10 seconds), screening the pressed microsphere powder by using a 150-mesh screen, recording the mass of the microsphere powder under the screen, and dividing the mass of the microsphere powder under the screen by the mass of the total added microspheres to obtain the breaking rate of the microspheres.

Preparation example 1

20kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated nitric acid is added into the reaction kettle, 2.3kg of PEG4000 is added into the reaction kettle, and finally 4kg of pseudo-boehmite powder is added into the reaction kettle, and the mixture is stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 35 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 580 ℃, and the air outlet temperature of drying termination is 160 ℃.

The microscopic photograph of the raspberry type oxide microsphere is shown in FIG. 1.

Preparation example 2

20kg of water is added into a reaction kettle, 0.5kg of zirconium nitrate is added into the reaction kettle, 175g of concentrated nitric acid is added into the reaction kettle, 2kg of PEG4000 and 5g of digestive glycerin are added into the reaction kettle, and finally 4.6kg of pseudo-boehmite powder is added into the reaction kettle, and the mixture is uniformly stirred and ground to obtain dispersed slurry.

The dispersion slurry was aged at 25 ℃ for 0.5 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 140 ℃.

Preparation example 3

30kg of water is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated nitric acid and 4.5kg of sodium carbonate are added into the reaction kettle, 2.3kg of methyl cellulose and 10g of picric acid are added into the reaction kettle, and finally 14kg of aluminum sulfate is added into the reaction kettle, is uniformly stirred and is ground to obtain dispersed slurry.

The dispersion slurry was aged at 30 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 580 ℃, and the air outlet temperature of drying termination is 130 ℃.

Preparation example 4

40kg of water is added into a reaction kettle, 1.2kg of yttrium nitrate is added into the reaction kettle, 230g of concentrated nitric acid and 4.8kg of sodium carbonate are added into the reaction kettle, 2.8kg of methyl cellulose and 15g of nitrocotton are added into the reaction kettle, and finally 12.5kg of aluminum chloride is added into the reaction kettle, stirred uniformly and ground to obtain dispersed slurry.

The dispersion slurry was aged at 30 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 141 ℃.

Preparation example 5

40kg of water was added to a reaction kettle, 1.2kg of aluminum nitrate was added thereto, 200g of concentrated nitric acid was then added, 2kg of PEG4000 and 2g of digestive fiber were then added, and 5.5kg of sodium silicate was finally added, stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 120 ℃.

Preparation example 6

40kg of water is added into a reaction kettle, 0.5kg of aluminum nitrate is added into the reaction kettle, 200g of concentrated sulfuric acid is added into the reaction kettle, 1kg of PEG4000 and 5g of picric acid are added into the reaction kettle, and 3kg of sodium silicate is added into the reaction kettle, stirred uniformly and ground to obtain dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 600 ℃, and the air outlet temperature of drying termination is 180 ℃.

Preparation example 7

20L of a mixed solution of water and ethanol (wherein the volume ratio of the water to the ethanol is 3: 1) is added into a reaction kettle, 1.2kg of aluminum nitrate is added into the reaction kettle, 7L of concentrated ammonia water is then added, 7g of 2kg of ethyl cellulose and nitroglycerin are then added, and 5kg of TEOS is finally added, stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1.5 hours with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 700 ℃, and the air outlet temperature of drying termination is 160 ℃.

Preparation example 8

20L of a mixed solution of water and ethanol (wherein the volume ratio of the water to the ethanol is 4: 1) is added into a reaction kettle, 0.3kg of zirconium nitrate is added into the reaction kettle, 3L of concentrated ammonia water is added into the reaction kettle, 0.5kg of PEG4000 and 6g of picric acid are added into the reaction kettle, and 2.6kg of TEOS is added into the reaction kettle, stirred uniformly and ground to obtain a dispersion slurry.

The dispersion slurry was aged at 25 ℃ for 1 hour with stirring.

Feeding the aged dispersed slurry into a spray drying device for drying and forming to obtain raspberry type oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in a tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 660 ℃, and the air outlet temperature of drying termination is 140 ℃.

Example 1

The raspberry type oxide microspheres obtained in preparation example 1 were calcined at 600 ℃ to obtain a carrier ZT1, and the physical properties thereof are shown in table 1.

The carrier ZT1 was immersed in cobalt nitrate solution to prepare a catalyst with a Co content of 16.0%, dried at 120 ℃ and calcined at 420 ℃ to obtain catalyst CAT1, the physical properties of which are shown in Table 2.

A photomicrograph of the raspberry catalyst microspheres is shown in FIG. 2.

Example 2

The raspberry type oxide microspheres obtained in preparation example 2 were calcined at 500 ℃ to obtain a carrier ZT2, and the physical properties thereof are shown in table 1.

The carrier ZT2 was immersed in cobalt nitrate solution to prepare a catalyst with a Co content of 16.0%, dried at 110 ℃ and calcined at 350 ℃ to obtain catalyst CAT2, the physical properties of which are shown in Table 2.

Example 3

The raspberry type oxide microspheres obtained in preparation example 3 were calcined at 500 ℃ to obtain a carrier ZT3, and the physical properties thereof are shown in table 1.

The carrier ZT3 was immersed in ferric nitrate solution to prepare a catalyst with Fe content of 15.0%, dried at 120 deg.C and calcined at 420 deg.C to obtain catalyst CAT3, the physical properties of which are shown in Table 2.

Example 4

The raspberry type oxide microspheres obtained in preparation example 4 were calcined at 700 ℃ to obtain a carrier ZT4, and the physical properties thereof are shown in table 1.

The carrier ZT4 was immersed in a ferric nitrate solution to prepare a catalyst with a Fe content of 15.0%, dried at 130 ℃ and calcined at 370 ℃ to obtain catalyst CAT4, the physical properties of which are shown in Table 2.

Example 5

The carrier ZT3 was immersed in ruthenium nitrosyl nitrate solution to prepare a catalyst with a Ru content of 3.0%, dried at 120 ℃ and calcined at 420 ℃ to obtain catalyst CAT5, the physical properties of which are shown in Table 2.

Example 6

The carrier ZT4 was immersed in ruthenium nitrosyl nitrate solution to prepare a catalyst with a Ru content of 3.0%, dried at 130 deg.C and calcined at 380 deg.C to obtain catalyst CAT6, the physical properties of which are shown in Table 2.

Example 7

The raspberry type oxide microspheres obtained in preparation example 5 were calcined at 600 ℃ to obtain a carrier ZT5, and the physical properties thereof are shown in table 1.

The carrier ZT5 was immersed in cobalt nitrate solution to prepare a catalyst with a Co content of 16.0%, dried at 120 ℃ and calcined at 420 ℃ to obtain catalyst CAT7, the physical properties of which are shown in Table 2.

Example 8

The raspberry type oxide microspheres obtained in preparation example 6 were calcined at 500 ℃ to obtain carrier ZT6, and the physical properties thereof are shown in table 1.

The carrier ZT6 was immersed in cobalt nitrate solution to prepare a catalyst with a Co content of 16.0%, dried at 110 ℃ and calcined at 350 ℃ to obtain catalyst CAT8, the physical properties of which are shown in Table 2.

Example 9

The raspberry type oxide microspheres obtained in preparation example 7 were calcined at 500 ℃ to obtain carrier ZT7, and the physical properties thereof are shown in table 1.

The carrier ZT7 was immersed in ferric nitrate solution to prepare a catalyst with Fe content of 15.0%, dried at 120 deg.C and calcined at 420 deg.C to obtain catalyst CAT9, the physical properties of which are shown in Table 2.

Example 10

The raspberry type oxide microspheres obtained in preparation example 8 were calcined at 700 ℃ to obtain carrier ZT8, and the physical properties thereof are shown in table 1.

The carrier ZT8 was immersed in a ferric nitrate solution to prepare a catalyst with a Fe content of 15.0%, dried at 130 ℃ and calcined at 370 ℃ to obtain catalyst CAT10, the physical properties of which are shown in Table 2.

Example 11

The carrier ZT7 was immersed in ruthenium nitrosyl nitrate solution to prepare a catalyst with a Ru content of 3.0%, dried at 120 ℃ and calcined at 420 ℃ to obtain catalyst CAT11, the physical properties of which are shown in Table 2.

Example 12

The carrier ZT8 was immersed in ruthenium nitrosyl nitrate solution to prepare a catalyst with a Ru content of 3.0%, dried at 130 deg.C and calcined at 380 deg.C to obtain catalyst CAT12, the physical properties of which are shown in Table 2.

Comparative example 1

Adding 20kg of water into a reaction kettle, adding 4.5kg of pseudo-boehmite powder, and stirring and mixing uniformly; adding 200g of concentrated hydrochloric acid, mixing and grinding; adding 2.3kg of PEG4000, continuing pulping, stirring and aging at 25 ℃ for 1 hour, and drying and forming by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in the tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 560 ℃, and the air outlet temperature of drying termination is 145 ℃.

The microphotograph of the obtained oxide microspheres is shown in fig. 6, which shows that the oxide microspheres are substantially solid, and a hollow structure communicating with the outside rarely exists in the central part.

The oxide microspheres are roasted at 600 ℃ to obtain a carrier DBZT1, and the physical properties of the carrier are shown in Table 1. The microscopic photograph of the supported oxide microspheres is shown in FIG. 3.

The carrier DBZT1 is dipped in cobalt nitrate solution to prepare a catalyst with Co content of 16.0%, and the catalyst DBCAT-Co-1 is obtained by drying at 120 ℃ and roasting at 420 ℃, and the physical properties of the catalyst are shown in Table 2. The microscopic photograph of the catalyst microspheres is shown in FIG. 4.

The carrier DBZT1 is dipped in ferric nitrate solution to prepare a catalyst with Fe content of 15.0%, the catalyst is dried at 120 ℃ and roasted at 420 ℃ to obtain the catalyst DBCAT-Fe-1, and the physical properties of the catalyst are shown in Table 2.

The carrier DBZT1 is dipped in a nitrosyl ruthenium nitrate solution to prepare a catalyst with the Ru content of 3.0 percent, the catalyst is dried at the temperature of 120 ℃ and roasted at the temperature of 420 ℃ to obtain the catalyst DBCAT-Ru-1, and the physical properties of the catalyst are shown in Table 2.

Comparative example 2

Adding 30kg of water and 5.5kg of sodium silicate into a reaction kettle, and stirring and mixing uniformly; adding 200g of concentrated hydrochloric acid; the resulting dispersion was filtered and the precipitate was washed 2 times with ethanol and deionized water, respectively, to remove unreacted inorganic and organic impurities.

Adding 20kg of water and 2.0kg of PEG4000, continuing pulping, stirring and aging for 1 hour at 25 ℃, and drying and molding by using a spray drying device to obtain oxide microspheres, wherein the atomization pressure of spray drying is 0.3-3.0 MPa, and the pressure in the tower is-0.0010-0.0090 MPa; the initial air inlet temperature of drying is 450 ℃, and the air outlet temperature of drying termination is 120 ℃.

When observed under a microscope, the structure of the material is similar to that of the comparative example 1, and the material is basically solid, and a hollow structure communicated with the outside rarely exists in the central part.

The oxide microspheres are roasted at 600 ℃ to obtain a carrier DBZT2, and the physical properties of the carrier are shown in Table 1.

The carrier DBZT2 was dipped in cobalt nitrate solution to make a catalyst with Co content of 16.0%, dried at 120 deg.C and calcined at 420 deg.C to obtain catalyst DBCAT-Co-2, the physical properties of which are shown in Table 2.

The carrier DBZT2 is dipped in ferric nitrate solution to prepare a catalyst with Fe content of 15.0%, the catalyst is dried at 120 ℃ and roasted at 420 ℃ to obtain the catalyst DBCAT-Fe-2, and the physical properties of the catalyst are shown in Table 2.

The carrier DBZT2 is dipped in nitrosyl ruthenium nitrate solution to prepare a catalyst with Ru content of 3.0%, the catalyst is dried at 120 ℃ and roasted at 420 ℃ to obtain the catalyst DBCAT-Ru-2, and the physical properties of the catalyst are shown in Table 2.

TABLE 1 physical Properties of the support

TABLE 2 physical Properties of the catalysts

The catalysts of the examples of the invention and of the comparative example were tested for their performance in a fischer-tropsch synthesis reaction by the following application examples.

Application example

The catalysts of examples 1-12 and comparative examples 1-2 were evaluated for their fischer-tropsch (FT) synthesis reaction performance in a fixed bed reactor. The FT synthesis catalyst needs to be reduced to a metallic state before use. Catalyst reduction reaction conditions: the pressure is normal pressure, the heating rate is 5 ℃/min, and the air speed of hydrogen is 600h^-1The reduction temperature was 400 ℃ and the reduction time was 5 hours.

After reduction, a reaction performance test is carried out, and specific reaction conditions are as follows:

reaction conditions of the cobalt-based catalyst: feed gas composition H₂/CO/N₂45%/45%/10% (volume/volume) pressure 2.5MPa, temperature 200 ℃, 210 ℃ and 220 ℃, respectively, and synthesis gas (raw gas) space velocity 24000 h-1. Each reaction temperature point was analyzed by chromatography using a gas sample after 12 hours. The main indicators of the reaction performance are: CO conversion, methane selectivity and C5+ hydrocarbon selectivity.

Reaction conditions of the iron-based catalyst: feed gas composition H₂/CO/N₂45%/45%/10% (volume in% parts) pressure 2.5MPa, temperature 260 ℃, 270 ℃ and 280 ℃, respectively, and synthesis gas (feed gas) space velocity 15000 h-1. Gas samples were taken for chromatography after 12 hours for each reaction temperature point. The main indicators of the reaction performance are: conversion of CO, methane selectivity, C5+ hydrocarbon selectivity and CO₂And (4) selectivity.

Reaction conditions of ruthenium-based catalyst: feed gas composition H₂/CO/N₂45%/45%/10% (volume/volume) pressure 2.5MPa, temperature 200 ℃, 210 ℃ and 220 ℃, respectively, and space velocity of synthesis gas (feed gas) 15000 h-1. Each reaction temperature point was analyzed by chromatography using a gas sample after 12 hours. The main indicators of the reaction performance are: CO conversion, methane selectivity and C5+ hydrocarbon selectivity.

The results of the reaction performance test are shown in table 3.

TABLE 3 reaction Performance test results of the catalysts

The test results in Table 3 show that the Fischer-Tropsch synthesis catalyst prepared by using the raspberry type oxide microspheres as the catalyst carrier has better FT synthesis performance under the same other conditions, namely higher CO conversion rate and C5+ hydrocarbon selectivity, and lower methane selectivity and CO selectivity₂Selectivity; moreover, the methane selectivity of the catalyst is not obviously improved due to the temperature rise, and the problem of diffusion of the FT synthesis reaction is obviously solved.

It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims

1. An FT synthesis catalyst is characterized by comprising a carrier and an active metal component loaded on the carrier, wherein the active metal component is selected from one or more of Co, Fe and Ru, the carrier is a raspberry-type oxide microsphere, the raspberry-type oxide microsphere is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, the large pore and the hollow structure are communicated to form a cavity with one open end, and the oxide in the raspberry-type oxide microsphere is selected from one or more of alumina and silica; the breakage rate of the raspberry type oxide microspheres is 0-1%;

the raspberry type oxide microsphere comprises the following steps:

aging the dispersed slurry;

feeding the aged dispersed slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃; drying and forming under the condition that the air outlet temperature is 50-300 ℃ to obtain the raspberry type oxide microspheres;

the method further comprises the step of adding a blasting agent into the dispersing agent, wherein the blasting agent is selected from one or more of picric acid, trinitrotoluene, digested glycerol, nitrocotton, dynamite, hexogen and C4 plastic explosive, and the adding amount of the blasting agent is 0-1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the aluminum source and/or the silicon source.

2. The FT synthesis catalyst according to claim 1, wherein the content of the carrier in the catalyst is 25 to 95 wt% and the content of the active metal component in the catalyst is 5 to 75 wt%, calculated as an oxide and based on the catalyst.

3. The FT synthesis catalyst according to claim 2, wherein the content of the carrier in the catalyst is 30 to 90 wt%; the content of the active metal component in the catalyst is 10-70 wt%.

4. The FT synthesis catalyst according to claim 1, wherein the raspberry-type oxide microspheres have a particle size of 3 to 2500 μm and a sphericity of 0.50 to 0.99.

5. The FT synthesis catalyst of claim 4, wherein the raspberry-type oxide microspheres have a particle size of 10 to 500 μm.

6. The FT synthesis catalyst according to claim 1, wherein the hollow structure has a diameter of 1 to 2000 μm.

7. The FT synthesis catalyst according to claim 6, wherein the hollow structure has a diameter of 1 to 400 μm.

8. The FT synthesis catalyst according to claim 1, wherein the macropores have a pore diameter of 0.2 to 1000 μm.

9. The FT synthesis catalyst of claim 8, wherein the macropores have a pore size of 0.5 to 200 μ ι η.

10. The FT synthesis catalyst according to claim 1, wherein the shell layer thickness of the hollow microsphere is 0.2 to 1000 μm.

11. The FT synthesis catalyst according to claim 10, wherein the shell layer thickness of the hollow microsphere is 0.5 to 200 μm.

12. The method of producing an FT synthesis catalyst according to any one of claims 1 to 11, characterized by comprising the steps of:

providing an impregnation solution of the raspberry type oxide microspheres and the compound comprising the active metal component;

roasting the raspberry type oxide microspheres to obtain the carrier; and

and impregnating the carrier by using the impregnation solution, and drying, roasting and activating to obtain the FT synthetic catalyst.

13. The preparation method of claim 12, wherein the inlet air temperature is 450-700 ℃; the air outlet temperature is 120-200 ℃.

14. The method according to claim 12, wherein the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

15. The method of claim 12, wherein the peptizing agent is selected from one or more of acids, bases, and salts.

16. The method of claim 12, wherein the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and a surfactant.

17. The preparation method of claim 12, wherein the aluminum source is selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, and the silicon source is selected from one or more of silicate ester, sodium silicate, water glass and silica sol.

18. The method of claim 12, wherein the dispersant is one or more selected from the group consisting of water, alcohols, ketones, and acids.

19. The preparation method according to claim 12, wherein the mass ratio of the nitrate, the peptizing agent, the pore-forming agent, and the aluminum source and/or the silicon source is (10-500): (1-10): (10-500): (10-1000).

20. The method of claim 12, wherein the drying device is a flash drying device or a spray drying device.

21. The method according to claim 12, wherein the temperature of the aging treatment is 0 to 90 ℃.

22. The method according to claim 21, wherein the temperature of the aging treatment is 20 to 60 ℃.

23. The preparation method of claim 12, wherein the roasting temperature is 400 ℃ to 1300 ℃, the drying temperature is 80 ℃ to 200 ℃, and the roasting activation temperature is 200 ℃ to 800 ℃.

24. The preparation method of claim 23, wherein the roasting temperature is 450-1100 ℃; the drying temperature is 100-150 ℃; the roasting activation temperature is 300-600 ℃.

25. Use of an FT synthesis catalyst according to any one of claims 1 to 11 in the field of fischer-tropsch synthesis.