CN116726923B - High-load equal-volume uniform load process and application - Google Patents

High-load equal-volume uniform load process and application Download PDF

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CN116726923B
CN116726923B CN202310996880.1A CN202310996880A CN116726923B CN 116726923 B CN116726923 B CN 116726923B CN 202310996880 A CN202310996880 A CN 202310996880A CN 116726923 B CN116726923 B CN 116726923B
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carrier
metal active
active component
precursor
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CN116726923A (en
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王维新
王永涛
叶辉
韩高山
路庆学
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Shandong Jiuyuan New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/14—Inorganic carriers the catalyst containing platinum group metals or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Oil, Petroleum & Natural Gas (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The application relates to the technical field of a catalyst loading process, in particular to a high-loading equal-volume uniform loading process and application thereof. The loading process of the application comprises the following steps: firstly, matching a metal active component with an organic ligand to form a metal complex, coating the metal complex inside silicon dioxide particles, soaking the silicon dioxide particles in a carrier precursor solution for reaction, centrifuging, washing and drying to generate a dry colloid, and etching the dry colloid by hydrofluoric acid to obtain hollow carrier particles; finally, the carrier particles are immersed in the metal active component precursor and the organic ligand solution for reaction, and then dried and baked. The catalyst obtained by the loading process has the advantages of high loading amount and good dispersion uniformity of the metal active components on the carrier, and can be applied to cracking and hydrogenation reactions in the petrochemical industry.

Description

High-load equal-volume uniform load process and application
Technical Field
The application relates to the technical field of catalyst loading processes, in particular to a high-loading equal-volume uniform loading process and application thereof.
Background
In the field of petrochemical industry, the catalyst is an important reaction control agent, can improve the reaction rate, selectivity and yield, and plays a key role in catalytic cracking and hydrogenation reactions.
The catalyst commonly used in the petrochemical industry is generally a supported catalyst, namely, the active components of the catalyst are supported on inert materials or under severe conditions with strong corrosiveness, and the active components are deactivated or sintered when being directly used, so that the active components can be uniformly dispersed on a carrier through the supported catalyst, the utilization rate of the active components is improved, and meanwhile, the damage of the active components under severe conditions is reduced.
The catalytic performance of the supported catalyst is closely related to the loading and dispersion uniformity of the active components on the carrier. When the load is too low, the utilization rate of the active component is low, the amount of active sites is small, and the catalytic activity is weak; when the loading is too high, agglomeration and sintering between active components may be caused, degrading the catalytic performance of the catalyst. In addition, the active components on the carrier are uniformly dispersed, which means that the active sites are uniformly distributed and the specific surface area is large, which is favorable for the full contact and reaction of reactants, thereby improving the activity of the catalyst. Therefore, on the basis of uniform dispersion, the catalyst with high loading has high catalytic activity.
At present, a common preparation method of the supported catalyst is an impregnation method, specifically, a carrier is impregnated in a salt solution of an active component to enable the active component to be adsorbed on the carrier, and then drying and high-temperature roasting are carried out to enable the active component to be supported on the carrier. The method is simple and easy to implement, can be suitable for carriers with different shapes and sizes, and can regulate and control the loading amount of the active components through multiple times of impregnation, but when the loading amount is high, the active components loaded on the carriers are easy to agglomerate, and the dispersion uniformity is poor.
Disclosure of Invention
In order to reduce the problem of poor dispersion uniformity of active components loaded on a carrier when the load is high, the application provides a high-load equal-volume uniform loading process and application.
A high load equal volume uniform load process comprising the steps of:
s1: dissolving a metal active component precursor and an organic ligand in an ethanol solution, uniformly mixing, adding triethylamine, reacting for 4-6 hours at 30-40 ℃, centrifuging, washing and drying to obtain a metal complex; the metal active component precursor is one of platinum, nickel, molybdenum, copper, tungsten and palladium precursors, and the organic ligand is one or more of polyvinylpyrrolidone, ethylenediamine and malonic acid;
s2: adding ethanol and ethyl orthosilicate into the metal complex, stirring uniformly, slowly adding a nitric acid solution, regulating the pH of the solution to 4-6, stirring at 25-30 ℃ for reaction for 16-20h, and centrifuging, washing, drying and grinding after the reaction to obtain silicon dioxide particles coated with the metal complex;
s3: adding ethanol, a surfactant and a carrier precursor into the silicon dioxide particles coated with the metal complex, uniformly stirring, slowly adding alkali liquor, adjusting the pH of the solution to 8-10, stirring at 25-30 ℃ for reaction for 12-16 hours, and centrifuging, washing and drying after the reaction to obtain a carrier dry colloid; the carrier precursor is one of a titanium dioxide precursor, an alumina precursor and a zirconia precursor;
s4: adding the carrier dry colloid into hydrofluoric acid solution for etching, washing and drying after etching, and roasting for 2-4 hours at 400-600 ℃ to obtain carrier particles coated with metal active components;
s5: immersing the carrier particles coated with the metal active components in ethanol solution containing metal active component precursors and organic ligands, heating and stirring for 4-6h at 60-80 ℃, standing and aging for 12-18h at 25-30 ℃, drying for 12-16h at 100-110 ℃, roasting for 2-4h at 400-600 ℃, and cooling to room temperature.
By adopting the technical scheme, firstly, triethylamine is used as a reaction catalyst, and a metal active component precursor and an organic ligand are used as reactants to react to obtain a metal complex; then, mixing the metal complex with ethanol and tetraethoxysilane, adding nitric acid solution to adjust the pH of the solution to form silica gel, dispersing the metal complex in the silica gel, drying and grinding to obtain silica particles, and uniformly coating the metal complex in the silica particles.
Then mixing silicon dioxide particles with ethanol and surfactant, adding alkali liquor to adjust the pH of the solution to form carrier gel, dispersing the silicon dioxide particles in the carrier gel, and drying to obtain carrier dry colloid, wherein the silicon dioxide particles coated with the metal complex are uniformly dispersed in the dry colloid.
Then adding hydrofluoric acid into the carrier dry colloid, enabling hydrofluoric acid molecules to enter the dry colloid through pores of the carrier dry colloid, reacting with silicon dioxide uniformly dispersed in the dry colloid to generate silicon tetrafluoride gas and water, etching the silicon dioxide, washing and drying for multiple times after etching, removing etching agent and impurities, and roasting to obtain carrier particles loaded with metal active components. At this time, the carrier particles carrying the metal active ingredient have a porous structure and a large specific surface area. Meanwhile, the silicon dioxide is removed by etching, holes with uniform size and uniform dispersion are formed in the carrier particles, the specific surface area of the carrier is further increased by the formation of the holes, the loading capacity of the carrier is further increased, the holes contain metal active components, and the dispersion uniformity of the metal active components on the carrier is also improved while the loading capacity is improved.
Finally, the carrier particles loaded with the metal active components are immersed into the metal active component precursor and the organic ligand solution for reaction, so that the metal active components are adsorbed in the pore channels and the holes of the carrier particles in the form of a complex, the metal active components can be stabilized to a certain extent, agglomeration among the metal active components is not easy to occur, the specific surface area of the catalyst and the dispersion uniformity of the metal active components on the carrier are improved, the loading capacity of the catalyst is improved, and the catalytic performance of the catalyst is further improved.
Preferably, in step S2, the mass ratio of the metal complex to the tetraethoxysilane is 1 (1.97-3.50).
By adopting the technical scheme, in order to better coat the metal complex with silicon dioxide and obtain silicon dioxide particles with proper size, the addition amount of the tetraethoxysilane needs to be controlled. When the addition amount of the tetraethoxysilane is large, the content of silicon dioxide in the silicon dioxide particles is large, holes which are uniformly dispersed in the carrier particles loaded with the metal active components are large, the specific surface area of the holes is reduced, the loading amount of the metal active components on the surfaces of the holes is reduced, and the catalytic effect of the catalyst is further reduced; when the addition amount of the tetraethoxysilane is small, the metal complex cannot be completely wrapped by the silicon dioxide, and in the subsequent reaction process, the metal complex can migrate to the outside of the silicon dioxide, so that the uniform dispersion of the metal active components on the carrier is not facilitated, and the specific surface area and the loading capacity of the catalyst are reduced.
Preferably, in step S5, the mass ratio of the carrier particles coated with the metal active component to the metal active component precursor is 1 (3.5-5.0).
In the above technical solution, in step S5, the addition amount of the precursor of the metal active component has a larger influence on the content of the metal active component in the pore canal of the carrier. Generally, in a certain range, as the addition amount of the metal active component precursor increases, the content of the metal active component in the pores of the support increases, but in order to make the dispersion of the metal active component in the pores and pores of the support more uniform, the addition amount of the metal active component precursor is controlled within a certain range.
Preferably, in step S1, the mass ratio of the metal active component precursor to the organic ligand is 1 (2.0-4.2), and in step S5, the mass ratio of the metal active component precursor to the organic ligand is 1 (2.0-5.7).
In the above technical scheme, the mass ratio of the metal active component precursor to the organic ligand needs to be comprehensively determined according to the specifically selected metal active component and organic ligand, but the mass ratio of the metal active component precursor to the organic ligand needs to be controlled within a certain range. When the addition amount of the metal active component precursor is small, the content of the metal active component in the solution is low, the metal active component coated in the holes of the carrier and adsorbed in the pore channels of the carrier is naturally low, and the load of the metal active component on the carrier is reduced; when the addition amount of the metal active component precursor is large, the content of the metal active component in the solution is high, and part of the metal active component cannot be matched with the organic ligand and is directly coated in the holes of the carrier and adsorbed in the pore channels of the carrier, so that the metal active component is easy to migrate outwards along with the evaporation of the solvent in the drying process, and the agglomeration phenomenon can occur, so that the dispersion uniformity of the metal active component on the carrier is poor, and the specific surface area and the loading capacity of the catalyst are reduced.
Preferably, in step S3, the mass ratio of the silica particles coated with the metal active component to the carrier precursor is 1 (2.6-6.5).
By adopting the technical scheme, when the addition amount of the carrier precursor is large, the density of uniformly dispersed holes in the carrier is reduced, so that the metal active components in the holes are relatively reduced, the overall dispersion uniformity of the catalyst is poor, the specific surface area is reduced, and the load is reduced; when the addition amount of the carrier precursor is small, the silica particles coated with the metal active component may not be completely coated, and when the silica is etched, holes and pore channels formed in the carrier are large, so that the specific surface area is reduced, the load amount is reduced, and therefore, the mass ratio of the silica particles coated with the metal active component to the carrier precursor is controlled within a certain range.
Preferably, the loading of the metal active component on the carrier in the catalyst obtained by the loading process is 8.5-10%.
In the technical scheme, when the loading amount of the metal active component on the carrier in the catalyst is small, the active component on the carrier is less, the active site is less, and the catalytic efficiency is reduced; when the loading of the metal active component in the catalyst on the carrier is large, the loading capacity of the carrier is exceeded, the active component is easy to agglomerate on the carrier, so that the amount of effective active component is reduced, and the catalytic efficiency is also reduced, so that the loading of the metal active component in the catalyst on the carrier is controlled within a proper range.
Preferably, the catalyst obtained by the loading process is used in petroleum cracking and hydrogenation reactions.
The catalyst obtained by the loading process belongs to a loaded catalyst, a metal active component is loaded on a carrier, and a metal active site is introduced on the surface of the carrier, so that the activation energy is reduced, the reaction rate is promoted, and the catalytic efficiency is improved. Moreover, cracking, hydrogenation reactions are often required to be carried out at high temperatures, pressures, or corrosive environments, with bare metal catalysts being prone to aggregation, shedding, or deactivation, reducing catalyst life. By loading the metal active component on the carrier, the metal active site can be highly dispersed, so that the metal active component is uniformly dispersed on the carrier, aggregation or falling of the metal active component is reduced, the deactivation rate of the metal active component is slowed down, the catalytic efficiency is improved, and the service life of the catalyst is prolonged. In addition, the selectivity of the catalyst can be adjusted by selecting different carriers, and for cracking and hydrogenation reactions, the selectivity control of the catalytic reaction is realized by adjusting the type of the metal active component and the properties of the carriers, so that the generation of specific products is selectively promoted, and the occurrence of side reactions is reduced or eliminated.
The technical scheme of the application at least comprises the following beneficial effects:
1. according to the application, the metal complex is coated in the silicon dioxide, so that the outward migration of the metal complex is limited, and the dispersion uniformity of the active component on the carrier is improved.
2. According to the application, the metal complex is coated with silicon dioxide, then the silicon dioxide is coated with carrier gel, and finally the silicon dioxide is etched, so that the carrier obtained by the method is uniformly dispersed with a plurality of holes, and the holes contain metal active components, so that the specific surface area of the carrier is increased, the dispersion uniformity of the active components on the carrier is improved, and the loading capacity of the carrier is improved.
3. According to the application, the carrier particles coated with the metal active components are immersed in the metal precursor and the organic ligand solution, so that the metal active components are adsorbed on the surfaces of the pore channels and the pores of the carrier in the form of a complex, the metal active components can be stabilized to a certain extent, agglomeration and migration of the metal active components are not easy to occur, the specific surface area of the catalyst is improved, and meanwhile, the loading capacity and the dispersion uniformity of the metal active components on the carrier are improved.
Drawings
Fig. 1 is a graph showing the trend of the load of the metal active component on the carrier of the catalysts obtained by the loading process of examples 1 to 9 and comparative examples 1 to 5.
FIG. 2 is a graph showing the trend of the specific surface area of the catalyst obtained by the loading process of examples 1 to 9 and comparative examples 1 to 5.
Detailed Description
The present application will be described in further detail with reference to examples.
The raw materials of the examples and comparative examples of the present application are commercially available in general except for the specific descriptions.
Examples
Example 1
The high-load equal-volume uniform load process of the embodiment comprises the following steps:
s1: 67g of copper chloride, 260mL of ethylenediamine and 1.5L of ethanol are weighed, placed in a reaction kettle provided with a stirrer, stirred for 30min, 10mL of triethylamine is added dropwise into the reaction kettle while stirring, then 2.0L of acetone is added into the reaction kettle for reaction for 4h at 30 ℃, the mixture is centrifuged to obtain a product, washed 3 times with ethanol and placed in a baking oven at 70 ℃ for drying for 12h, and a metal complex is obtained;
s2: weighing 100g of metal complex, 1.8L of ethanol and 372mL of tetraethoxysilane, placing the mixture in a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 4, continuously stirring for 16 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 264g of pseudo-boehmite, placing into a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH value of the mixed solution to 8, continuously stirring at 25 ℃ for 12 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying in a 70 ℃ oven for 12 hours to obtain an alumina dry colloid;
s4: weighing 50g of alumina dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the alumina dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2h, centrifuging the mixed solution, washing 3 times with ethanol, placing into a 70 ℃ oven for drying for 12h, placing into a muffle furnace, and roasting for 4h at 400 ℃ to obtain alumina particles coated with metal active components;
s5: weighing 20g of aluminum oxide particles coated with metal active components, 100g of copper chloride, 638mL of ethylenediamine and 1.8L of ethanol, placing in a reaction kettle with a stirrer, stirring for 4 hours at 80 ℃, placing in a 25 ℃ for standing and aging for 12 hours, placing in a 100 ℃ oven for drying for 12 hours, placing in a muffle furnace for roasting for 4 hours at 400 ℃, and cooling to room temperature.
Example 2
The high-load equal-volume uniform load process of the embodiment comprises the following steps:
s1: weighing 137g of molybdenum pentachloride, 274g of malonic acid and 1.5L of ethanol, placing the materials into a reaction kettle provided with a stirrer, stirring for 30min, dropwise adding 10mL of triethylamine into the reaction kettle while stirring, then reacting for 6h at 40 ℃, adding 2.0L of acetone into the reaction kettle, centrifuging the mixture to obtain a product, washing 3 times with ethanol, and drying for 12h in a baking oven at 70 ℃ to obtain a metal complex;
s2: weighing 100g of metal complex, 1.8L of ethanol and 372mL of tetraethoxysilane, placing the mixture in a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 6, continuously stirring for 20 hours at 30 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260g of zirconium oxychloride octahydrate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 10, continuously stirring at 30 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain an alumina dry colloid;
s4: weighing 50g of zirconia dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the zirconia dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2 hours, centrifuging the mixed solution, washing the mixed solution with ethanol for 3 times, placing the mixed solution into a 70 ℃ oven for drying for 12 hours, placing the dried mixed solution into a muffle furnace, and roasting the dried mixed solution for 2 hours at 600 ℃ to obtain zirconia particles coated with metal active components;
s5: weighing 20g of zirconia particles coated with metal active components, 70g of molybdenum pentachloride, 280g of molybdenum pentachloride and 1.8L of ethanol, placing the mixture in a reaction kettle provided with a stirrer, stirring the mixture at 60 ℃ for 6 hours, placing the mixture at 30 ℃ for standing aging for 18 hours, placing the mixture in a 110 ℃ oven for drying for 16 hours, placing the mixture in a muffle furnace for roasting for 2 hours at 600 ℃, and cooling the mixture to room temperature.
Example 3
The high-load equal-volume uniform load process of the embodiment comprises the following steps:
s1: weighing 25.9g of chloroplatinic acid hexahydrate, 108.8g of polyvinylpyrrolidone and 1.5L of ethanol, placing the solution in a reaction kettle provided with a stirrer, stirring for 30min, dropwise adding 10mL of triethylamine into the reaction kettle while stirring, then reacting for 6h at 40 ℃, adding 2.0L of acetone into the reaction kettle, centrifuging the mixture to obtain a product, washing 3 times with ethanol, and drying in a baking oven at 70 ℃ for 12h to obtain a metal complex;
s2: weighing 100g of metal complex, 1.8L of ethanol and 372mL of tetraethoxysilane, placing the mixture in a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain a titanium dioxide dry colloid;
s4: weighing 50g of titanium dioxide dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the titanium dioxide dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2h, centrifuging the mixed solution, washing 3 times with ethanol, placing into a 70 ℃ oven for drying for 12h, placing into a muffle furnace, and roasting for 3h at 500 ℃ to obtain titanium dioxide particles coated with metal active components;
s5: weighing 20g of titanium dioxide particles coated with metal active components, 78g of chloroplatinic acid hexahydrate, 327.6g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer, reacting for 6 hours at 60 ℃, then placing the titanium dioxide particles in a 30 ℃ oven for standing and ageing for 18 hours, placing the titanium dioxide particles in the 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
Example 4
The high-load equal-volume uniform load process of this example is different from that of example 3 in that:
s2: weighing 100g of metal complex, 1.8L of ethanol and 210mL of tetraethoxysilane, placing the mixture into a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
the remaining steps were the same as in example 3.
Example 5
The high-load equal-volume uniform load process of this example is different from that of example 3 in that:
s2: weighing 100g of metal complex, 1.8L of ethanol and 320mL of ethyl orthosilicate, placing the mixture in a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after stirring uniformly, regulating the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
the remaining steps were the same as in example 3.
Example 6
The high-load equal-volume uniform load process of this example is different from that of example 5 in that:
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 650mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain a titanium dioxide dry colloid;
the remaining steps were the same as in example 5.
Example 7
The high-load equal-volume uniform load process of this example is different from that of example 5 in that:
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 450mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16h, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12h to obtain a titanium dioxide dry colloid;
the remaining steps were the same as in example 5.
Example 8
The high-load equal-volume uniform load process of this example is different from that of example 7 in that:
s5: weighing 20g of titanium dioxide particles coated with metal active components, 100g of chloroplatinic acid hexahydrate, 420g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer, reacting for 6 hours at 60 ℃, then placing the titanium dioxide particles in a 30 ℃ for standing and ageing for 18 hours, placing the titanium dioxide particles in a 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
The remaining steps were the same as in example 7.
Example 9
The high-load equal-volume uniform load process of this example is different from that of example 7 in that:
s5: weighing 20g of titanium dioxide particles coated with metal active components, 84g of chloroplatinic acid hexahydrate, 352.8g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer, reacting for 6 hours at 60 ℃, then placing the titanium dioxide particles in a 30 ℃ for standing and ageing for 18 hours, placing the titanium dioxide particles in a 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
The remaining steps were the same as in example 7.
Comparative example
Comparative example 1
The high-load equal-volume uniform load process of the comparative example comprises the following steps:
s1: weighing 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing into a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying in a 70 ℃ oven for 12 hours to obtain titanium dioxide dry colloid;
s2: weighing 50g of titanium dioxide dry colloid, putting into a muffle furnace, and roasting for 3 hours at 500 ℃ to obtain titanium dioxide particles;
s3: weighing 20g of titanium dioxide particles, 78g of hexa-hydrated chloroplatinic acid, 327.6g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer for reaction at 60 ℃ for 6 hours, then placing the titanium dioxide particles in a 30 ℃ for standing aging for 18 hours, placing the titanium dioxide particles in a 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
Comparative example 2
The high-load equal-volume uniform load process of the comparative example comprises the following steps:
s1: 1.8L of ethanol and 210mL of tetraethoxysilane are weighed and placed in a reaction kettle provided with a stirrer, nitric acid solution with the concentration of 10% is slowly dripped after uniform stirring, the pH value of the mixed solution in the reaction kettle is regulated to be 5, stirring is continued for 20 hours at 25 ℃, the mixture in the reaction kettle is centrifuged, the product is washed 3 times by ethanol, and the product is dried for 12 hours in a baking oven at 70 ℃ and then ground to obtain silicon dioxide particles;
s2: weighing 100g of silicon dioxide particles, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing the silicon dioxide particles, the 5.0g of sodium dodecyl sulfate, the 1.8L of ethanol and the 260mL of tetrabutyl titanate into a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH value of the mixed solution to 9, continuously stirring for 16h at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12h to obtain a titanium dioxide dry colloid;
s3: weighing 50g of titanium dioxide dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the titanium dioxide dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2h, centrifuging the mixed solution, washing 3 times with ethanol, placing into a 70 ℃ oven for drying for 12h, then placing into a muffle furnace, and roasting for 3h at 500 ℃ to obtain titanium dioxide particles;
s4: weighing 20g of titanium dioxide particles, 78g of hexa-hydrated chloroplatinic acid, 327.6g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer for reaction at 60 ℃ for 6 hours, then placing the titanium dioxide particles in a 30 ℃ for standing aging for 18 hours, placing the titanium dioxide particles in a 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
Comparative example 3
The high-load equal-volume uniform load process of the comparative example comprises the following steps:
s1: weighing 25.9g of chloroplatinic acid hexahydrate, 108.8g of polyvinylpyrrolidone and 1.5L of ethanol, placing the solution in a reaction kettle provided with a stirrer, stirring for 30min, dropwise adding 10mL of triethylamine into the reaction kettle while stirring, then reacting for 6h at 40 ℃, adding 2.0L of acetone into the reaction kettle, centrifuging the mixture to obtain a product, washing 3 times with ethanol, and drying in a baking oven at 70 ℃ for 12h to obtain a metal complex;
s2: weighing 100g of metal complex, 1.8L of ethanol and 210mL of tetraethoxysilane, placing the mixture into a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 5% after stirring uniformly, regulating the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain a titanium dioxide dry colloid;
s4: weighing 50g of titanium dioxide dry colloid, putting into a muffle furnace, and roasting for 3 hours at 500 ℃ to obtain titanium dioxide particles coated with metal active components;
s5: weighing 20g of titanium dioxide particles coated with metal active components, 78g of chloroplatinic acid hexahydrate, 327.6g of polyvinylpyrrolidone and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer, reacting for 6 hours at 60 ℃, then placing the titanium dioxide particles in a 30 ℃ oven for standing and ageing for 18 hours, placing the titanium dioxide particles in the 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
Comparative example 4
The high-load equal-volume uniform load process of the comparative example comprises the following steps:
s1: weighing 25.9g of chloroplatinic acid hexahydrate, 108.8g of polyvinylpyrrolidone and 1.5L of ethanol, placing the solution in a reaction kettle provided with a stirrer, stirring for 30min, dropwise adding 10mL of triethylamine into the reaction kettle while stirring, then reacting for 6h at 40 ℃, adding 2.0L of acetone into the reaction kettle, centrifuging the mixture to obtain a product, washing 3 times with ethanol, and drying in a baking oven at 70 ℃ for 12h to obtain a metal complex;
s2: weighing 100g of metal complex, 1.8L of ethanol and 210mL of tetraethoxysilane, placing the mixture into a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain a titanium dioxide dry colloid;
s4: weighing 50g of titanium dioxide dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the titanium dioxide dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2h, centrifuging the mixed solution, washing 3 times with ethanol, placing into a 70 ℃ oven for drying for 12h, placing into a muffle furnace, and roasting for 3h at the temperature of 500 ℃ to obtain the titanium dioxide.
Comparative example 5
The high-load equal-volume uniform load process of the comparative example comprises the following steps:
s1: weighing 25.9g of chloroplatinic acid hexahydrate, 108.8g of polyvinylpyrrolidone and 1.5L of ethanol, placing the solution in a reaction kettle provided with a stirrer, stirring for 30min, dropwise adding 10mL of triethylamine into the reaction kettle while stirring, then reacting for 6h at 40 ℃, adding 2.0L of acetone into the reaction kettle, centrifuging the mixture to obtain a product, washing 3 times with ethanol, and drying in a baking oven at 70 ℃ for 12h to obtain a metal complex;
s2: weighing 100g of metal complex, 1.8L of ethanol and 210mL of tetraethoxysilane, placing the mixture into a reaction kettle provided with a stirrer, slowly dripping nitric acid solution with the concentration of 10 percent after uniform stirring, adjusting the pH value of the mixed solution in the reaction kettle to be 5, continuously stirring for 20 hours at 25 ℃, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, drying the product in a baking oven at 70 ℃ for 12 hours, and grinding to obtain silicon dioxide particles coated with the metal complex;
s3: weighing 100g of silicon dioxide particles coated with a metal complex, 5.0g of sodium dodecyl sulfate, 1.8L of ethanol and 260mL of tetrabutyl titanate, placing the silicon dioxide particles in a reaction kettle provided with a stirrer, slowly adding 28% ammonia water, adjusting the pH of the mixed solution to 9, continuously stirring at 25 ℃ for 16 hours, centrifuging the mixture in the reaction kettle, washing the product with ethanol for 3 times, and drying the product in a baking oven at 70 ℃ for 12 hours to obtain a titanium dioxide dry colloid;
s4: weighing 50g of titanium dioxide dry colloid and 350mL of hydrofluoric acid solution with the concentration of 10%, placing the titanium dioxide dry colloid and 350mL of hydrofluoric acid solution into a plastic cup with a stirrer, stirring for 2h, centrifuging the mixed solution, washing 3 times with ethanol, placing into a 70 ℃ oven for drying for 12h, placing into a muffle furnace, and roasting for 3h at 500 ℃ to obtain titanium dioxide particles coated with metal active components;
s5: weighing 20g of titanium dioxide particles coated with metal active components, 78g of chloroplatinic acid hexahydrate and 1.8L of ethanol, placing the titanium dioxide particles in a reaction kettle with a stirrer, reacting for 6 hours at 60 ℃, then placing the titanium dioxide particles in a 30 ℃ condition for standing and aging for 18 hours, placing the titanium dioxide particles in a 105 ℃ oven for drying for 16 hours, placing the titanium dioxide particles in a muffle furnace for roasting for 3 hours at 500 ℃, and cooling to room temperature.
Performance test
Detection method
1. Method for measuring load of metal active component on carrier
The instrument is used: ICPS-1000 IV type inductively coupled plasma atomic emission spectrometer (Shimadzu corporation);
instrument working conditions: the working frequency is 27.12MHz, the incident power is 1.2kW, the carrier gas flow is 1.0L/min, the observation height is 15mm, and the integration time is 5s;
(1) respectively taking standard solutions of copper, molybdenum and platinum for stepwise dilution, preparing standard solutions with the concentration of 10 mug/mL, 5 mug/mL, 2 mug/mL, 1 mug/mL and 0.5 mug/mL, then injecting the standard solutions into an ICPS-1000 IV type inductively coupled plasma atomic emission spectrometer for measurement, and establishing a standard curve;
(2) accurately weighing 0.200-0.400g of each catalyst sample obtained by adopting the loading process of examples 1-9 and comparative examples 1-5, placing the catalyst samples in a 100mL plastic beaker, adding 2mL hydrofluoric acid and 10mL deionized water, uniformly stirring, standing for 24h, and after the samples are completely dissolved, fixing the volume in a volumetric flask;
(3) injecting the sample solution with the fixed volume into an ICPS-1000 IV type inductively coupled plasma atomic emission spectrometer for measurement;
(4) the measured data is processed and calculated. The measurement results are shown in FIG. 1.
2. Method for measuring specific surface area of catalyst
The catalysts obtained in the loading processes of examples 1 to 9 and comparative examples 1 to 5 were subjected to vacuum treatment at 200℃for 2 hours, and the specific surface area of the catalysts was measured and calculated using an ASAP 2020 PLUS type full-automatic multifunctional gas adsorber, manufactured by America microphone instruments, as an adsorbent. The measurement results are shown in FIG. 2.
Analysis of results
The analysis was performed by combining fig. 1 and 2 as follows:
in comparative examples 3 to 5, the catalyst loading and specific surface area were increased and then decreased with increasing amounts of ethyl orthosilicate, because silica was insufficient to completely coat the metal complex when the amount of ethyl orthosilicate added was small, and the internal metal complex was migrated outward with evaporation of the solvent, resulting in poor dispersion uniformity, decreased specific surface area, and decreased loading; when the addition amount of the tetraethoxysilane is large, the silicon dioxide layer coated with the metal complex is thick, and after the silicon dioxide is etched by hydrofluoric acid, the left holes are large, so that the specific surface area is reduced, and the load capacity is also reduced.
In comparative examples 5 to 7, the catalyst loading and specific surface area were increased and then decreased with the increase of the tetrabutyl titanate addition amount, because the titanium dioxide layer was insufficient to completely coat the silica when the tetrabutyl titanate addition amount was small, and the pore and hole on the titanium dioxide were large, the specific surface area was decreased, and the loading was decreased after the silica layer was etched away; when the adding amount of tetrabutyl titanate is more, the pores in the titanium dioxide are less dispersed, so that the active components in the pores are relatively reduced, the overall dispersion uniformity of the catalyst is poor, the specific surface area is reduced, and the load is reduced.
Comparative examples 7 to 9, in step S5, as the addition amount of the metal active component precursor increases, the loading amount of the active component on the support and the specific surface area of the catalyst remain substantially unchanged after the increase, which means that the loading amount of the metal active component on the support has reached the maximum value at this time.
In comparative example 3 and comparative examples 1 to 5, the metal complex is coated with the silica layer, and the outward migration of the metal complex is limited due to the coating of the silica layer, so that the inside and outside dispersion uniformity of the catalyst is better, and the loading capacity is higher; the carrier is made into a hollow structure, so that the specific surface area of the carrier can be increased to a certain extent, and the loading capacity of the active components on the carrier is improved; in addition, the carrier particles coated with the metal active components are immersed in the metal active component precursor and the organic ligand solution, so that the metal active components are adsorbed on the surfaces of the carrier pore channels and holes in a complex mode, and the organic ligand can enable the metal active components to be more stably loaded on the carrier, so that agglomeration and migration phenomena are not easy to occur, and the loading capacity and the dispersion uniformity of the metal active components on the carrier are improved.
The present embodiment is only for explanation of the present application and is not to be construed as limiting the present application, and modifications to the present embodiment, which may not creatively contribute to the present application as required by those skilled in the art after reading the present specification, are all protected by patent laws within the scope of claims of the present application.

Claims (6)

1. The high-load equal-volume uniform load process is characterized by comprising the following steps of:
s1: dissolving a metal active component precursor and an organic ligand in an ethanol solution, uniformly mixing, adding triethylamine, reacting for 4-6 hours at 30-40 ℃, centrifuging, washing and drying to obtain a metal complex; the metal active component precursor is one of platinum, nickel, molybdenum, copper, tungsten and palladium precursors, and the organic ligand is one or more of polyvinylpyrrolidone, ethylenediamine and malonic acid;
s2: adding ethanol and ethyl orthosilicate into the metal complex, stirring uniformly, slowly adding a nitric acid solution, regulating the pH of the solution to 4-6, stirring at 25-30 ℃ for reaction for 16-20h, and centrifuging, washing, drying and grinding after the reaction to obtain silicon dioxide particles coated with the metal complex; the mass ratio of the metal complex to the tetraethoxysilane is 1 (1.97-3.50);
s3: adding ethanol, a surfactant and a carrier precursor into the silicon dioxide particles coated with the metal complex, uniformly stirring, slowly adding alkali liquor, adjusting the pH of the solution to 8-10, stirring at 25-30 ℃ for reaction for 12-16 hours, and centrifuging, washing and drying after the reaction to obtain a carrier dry colloid; the carrier precursor is one of a titanium dioxide precursor, an alumina precursor and a zirconia precursor; the mass ratio of the silicon dioxide particles coated with the metal complex to the carrier precursor is 1 (2.6-6.5);
s4: adding the carrier dry colloid into hydrofluoric acid solution for etching, washing and drying after etching, and roasting for 2-4 hours at 400-600 ℃ to obtain carrier particles coated with metal active components;
s5: immersing the carrier particles coated with the metal active components in ethanol solution containing metal active component precursors and organic ligands, heating and stirring for 4-6h at 60-80 ℃, standing and aging for 12-18h at 25-30 ℃, drying for 12-16h at 100-110 ℃, roasting for 2-4h at 400-600 ℃, and cooling to room temperature.
2. The high-loading isovolumetric homogeneous loading process according to claim 1, wherein in step S5, the mass ratio of the metal active component coated carrier particles to the metal active component precursor is 1 (3.5-5.0).
3. The high-loading isovolumetric homogeneous loading process according to claim 1, wherein in step S1, the mass ratio of the metal active component precursor to the organic ligand is 1 (2.0-4.2), and in step S5, the mass ratio of the metal active component precursor to the organic ligand is 1 (2.0-5.7).
4. A catalyst, characterized in that it is obtained by the loading process according to any one of claims 1 to 3.
5. The catalyst according to claim 4, wherein the loading of the metal active component on the carrier in the catalyst is 8.5 to 10%.
6. Use of a catalyst according to claim 4, in petroleum cracking, hydrogenation reactions.
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CN104971759A (en) * 2015-06-24 2015-10-14 东华大学 Preparation method of supported palladium-carbon catalyst
CN105665027A (en) * 2015-12-29 2016-06-15 四川大学 Preparation method of high-dispersing supported metal nano catalyst
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