CN111085255A

CN111085255A - Regular carrier catalyst with desulfurization effect and preparation and application thereof

Info

Publication number: CN111085255A
Application number: CN201811239479.9A
Authority: CN
Inventors: 田辉平; 孙言; 王鹏; 林伟; 宋海涛; 姜秋桥; 严加松
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: 2018-10-24
Filing date: 2018-10-24
Publication date: 2020-05-01

Abstract

A regular carrier catalyst with desulfurization effect and preparation and application thereof are provided, wherein the regular carrier catalyst comprises a regular carrier and an active coating attached to the outer surface of the regular carrier, the active coating comprises a IIA and IIB group metal oxide matrix, a molecular sieve and a modified metal film, the modified metal film comprises modified metal, and the modified metal is one or more of Fe, Co, Ni, Mn, Ti, Zr, V, Ge, Pb, Sn, Sb and Bi. The preparation method comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain a suspension; the suspension is contacted with the matrix particles and/or with the molecular sieve particles or with particles containing the matrix and molecular sieve, freeze-dried, and then coated on a structured carrier. The catalyst can be used for hydrodesulfurizing hydrocarbon fuel, has the characteristics of high activity and good stability, and can be used for desulfurizing gasoline and improving the octane number of the gasoline.

Description

Regular carrier catalyst with desulfurization effect and preparation and application thereof

Technical Field

The invention relates to a catalyst with a regular structure for hydrodesulphurization and a preparation method and an application method thereof.

Background

Sulfur in the fuel is combusted to generate sulfur oxide, the sulfur oxide can inhibit the activity of a noble metal catalyst in an automobile exhaust converter and can irreversibly poison the noble metal catalyst, the effect of catalyzing and converting toxic gases in the automobile exhaust cannot be realized, so that the discharged automobile exhaust contains unburned oxides of non-methane hydrocarbon and nitrogen and carbon monoxide, the toxic gases are catalyzed by sunlight to easily form photochemical smog to cause acid rain, and the sulfur oxide is also one of main reasons for forming the acid rain.

Reducing the sulfur content in fuels such as gasoline and diesel is considered to be one of the most important measures to improve air quality. With the increasing attention of people on environmental protection, environmental regulations are becoming stricter, and the sulfur content of the European V gasoline standard implemented in 2010 of the European Union is less than 10 mug/g by taking gasoline as an example. The current gasoline product standard GB 17930-2013 'automotive gasoline' in China requires that the sulfur content in gasoline must be reduced to 10 mu g/g. But also the future gasoline quality standards will be more stringent.

Currently, the main methods for desulfurizing hydrocarbon fuels are hydrodesulfurization and adsorption desulfurization. Hydrodesulfurization reacts sulfur-containing hydrocarbons, such as gasoline, in contact with hydrogen in the presence of a hydrogenation catalyst, which, with increasing fuel oil standards, requires more severe hydrogenation conditions, such as higher reaction pressure or temperature, to lower the sulfur content, but due to the high amount of olefins in the gasoline, increasing the hydrogenation severity results in higher octane number loss. The adsorption desulfurization is usually carried out by contacting an adsorbent with sulfur-containing hydrocarbon under the hydrogen condition, wherein the sulfur-containing hydrocarbon in the oil product is captured on the adsorbent, and hydrogen sulfide is generated by hydrogenation and then is combined with zinc oxide to generate a zinc sulfide compound, which can also cause the octane number of the gasoline product to be reduced; in addition, when the sulfur combined on the zinc oxide is saturated, the desulfurization activity is reduced, the sulfur must be removed through oxidation regeneration, and in the frequent oxidation regeneration-reduction process, the deactivation rate of the adsorbent is high, which affects the implementation effect of sulfur-containing hydrocarbon desulfurization.

The existing adsorption desulfurization and hydrodesulfurization are all desulfurized in the presence of hydrogen, and in order to achieve the purpose of deep desulfurization, the operation needs to be carried out under more severe conditions.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a regular carrier catalyst for hydrodesulphurization, which has higher desulphurization activity and stability. The invention aims to solve the other technical problems of providing a preparation method and a using method of the catalyst.

Therefore, the invention provides the following technical scheme:

technical scheme 1. a structured carrier catalyst with desulfurization function, wherein the structured carrier catalyst comprises a structured carrier and an active coating (also called active component coating) attached to the outer surface of the structured carrier, the active coating comprises a IIA and IIB group metal oxide matrix, a molecular sieve and a modified metal film, the modified metal film comprises modified metal, and the modified metal is one or more of Fe, Co, Ni, Mn, Ti, Zr, V, Ge, Pb, Sn, Sb and Bi.

Technical scheme 2. the structured carrier catalyst according to the technical scheme 1, wherein the modified metal membrane is located on the outer surface of the molecular sieve particle and/or the outer surface of the matrix particle and/or the outer surface of the particle containing the molecular sieve and the matrix, and the thickness of the modified metal membrane is 5-30 nm, preferably 5-20 nm.

Technical solution 3. the structured carrier catalyst according to the technical solution 1 or 2, wherein the active coating layer is contained in an amount of 5 to 50 wt%, for example, 10 to 30 wt%, or 15 to 25 wt%, or 20 to 30 wt%, and the structured carrier is contained in an amount of 50 to 95%, for example, 70 to 90 wt%, or 75 to 85 wt%, or 70 to 80 wt%, based on the total weight of the structured carrier, on a dry basis; in one embodiment, the structured carrier catalyst has an active coating in an amount of 10 to 25 wt% and the structured carrier in an amount of 75 to 90 wt%.

The technical scheme 4. the structured carrier catalyst according to any one of the technical schemes 1 to 3, wherein the active component coating comprises 4 to 50 weight percent of matrix, 30 to 95 weight percent of molecular sieve and 1 to 25 weight percent of modified metal film based on the total weight of the active component coating on a dry basis; preferably, the active component coating comprises 10-40 wt% of the substrate, 40-80 wt% of the molecular sieve and 2-20 wt%, for example 5-20 wt% of the modified metal film, and preferably, the active coating comprises 10-40 wt% of the substrate, 45-75 wt% of the molecular sieve and 8-18 wt% of the modified metal film; preferably, the outer surface of the molecular sieve particle is covered with the modified metal film; more preferably, the modified metal film is positioned on the outer surface of the molecular sieve particles, the thickness of the modified metal film on the outer surface of the molecular sieve particles is 5-30 nm, preferably 5-20 nm, and the modified metal accounts for 8-21 wt% or 10-20 wt% of the total weight of the molecular sieve and the modified metal on a dry basis;

preferably, the total content of the oxides of the group IIA and IIB metals in the matrix is 5-100 wt%, for example 40-100 wt%, on a dry basis, and other matrix components may be included; the other matrix component may be a heat resistant inorganic oxide such as one or more of an alumina matrix, a silica matrix, a zirconia matrix, a titania matrix, a silica alumina matrix such as kaolin, silica alumina gel; other matrix components are present in an amount of 0-95 wt%, such as 0-60 wt%, and in one embodiment, the matrix comprises 30-75 wt%, such as 50-70 wt%, of a refractory, non-polar oxide matrix, 25-70 wt%, such as 30-50 wt%, of an oxide of a group IIA, IIB metal;

the oxide of the metal in the IIA and IIB groups is preferably the oxide of at least one metal in magnesium, zinc and calcium, and can be one or more of calcium oxide, magnesium oxide and zinc oxide; preferably zinc oxide.

Technical solution 5. the structured carrier catalyst according to any one of technical solutions 1 to 4, wherein the structured carrier has two endsMonolithic supports (honeycomb supports) of open parallel cell structure; preferably, the pore density of the cross section of the structured carrier is 40 to 800 pores per square inch, for example 100 to 400 pores per square inch, and typically, the cross sectional area of each pore in the structured carrier is 400 μm²～1.8×10⁵μm². The regular structure carrier can be at least one of a cordierite honeycomb carrier, a mullite honeycomb carrier, a diamond honeycomb carrier, a corundum honeycomb carrier, a zirconia corundum honeycomb carrier, a quartz honeycomb carrier, a nepheline honeycomb carrier, a feldspar honeycomb carrier, an alumina honeycomb carrier or a metal alloy honeycomb carrier.

The structured carrier catalyst according to any of the claims 1 to 5, wherein the modified metal comprises one or more first metals selected from Fe, Co, Ni, Mn, Ti, Zr, Pb, Ge, Sn and optionally one or more second metals selected from V, Sb, Bi, preferably the weight ratio of the second metal to the first metal is 0 to 1:1 or 0 to 0.8:1 or 0 to 0.5:1 or 0 to 0.3: 1; in a first embodiment, the first metal is one or more of Fe, Co, Ni and Mn, optionally contains one or more of Ti, Zr, Pb, Ge and Sn, and the ratio of one or more of Fe, Co, Ni and Mn to one or more of Pb, Ge and Sn is 0.5-2: 0-1; in a second embodiment, the modified metal comprises a first metal and optionally a second metal, wherein the first metal is one or more of Pb, Ge and Sn, and the second metal is one or more of Sb and Bi, preferably, the weight ratio of the second metal to the first metal is 0.2-1: 1, such as 0.4-0.8: 1; in a third embodiment, the first metal is Ti and/or Zr and the optional second metal is preferably V, preferably Ti: Zr: the weight ratio of V is (0.8-1.2): 0.4-0.6); in a fourth embodiment, the modified metal film comprises a third element selected from one or more of Cr, Mo, W, Cu, Ag, Au, Al, Ga, Mg, B; preferably, the weight ratio of the second metal to the first metal is 0-1: 1 or 0-0.5: 1 or 0 to 0.3:1, preferably, the weight ratio of the third element to the first metal is 0-1: 1 or 0-0.5: 1 or 0 to 0.3: 1; in the fourth embodiment, it is preferable that the active coating layer of the structured carrier catalyst contains 5 to 20 wt% of the first metal, such as 8 to 17 wt% or 10 to 15 wt%, 0 to 10 wt% of the second metal, such as 0 to 5 or 0 to 3 wt%, and 0 to 10 wt% of the third element, such as 0 to 5 or 0 to 3 wt%, based on the weight of the active coating layer.

Technical scheme 7. a method for preparing a regular carrier catalyst comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain a suspension; contacting the suspension with substrate particles and/or molecular sieve particles or particles containing the substrate and the molecular sieve, freeze-drying to obtain a substrate containing a modified metal membrane and/or a molecular sieve containing the modified metal membrane and/or particles containing the substrate and the molecular sieve containing the modified metal membrane, and then coating the substrate containing the modified metal membrane and/or the molecular sieve containing the modified metal membrane or the particles containing the substrate and the molecular sieve containing the modified metal membrane on a regular carrier to obtain the regular carrier catalyst, wherein preferably the particle diameters d of the substrate particles, the molecular sieve particles and the particles containing the substrate and the molecular sieve₉₀Not more than 10 microns, for example 1 to 8 microns or 2 to 5 microns.

Technical scheme 8. the preparation method of the structured carrier catalyst according to the technical scheme 7, wherein the concentration of the modified metal in the suspension is 5-45 g/Kg, for example, 8-40 g/Kg or 10-35 mass per thousand, preferably 10-25 g/Kg.

Technical solution 9. the method for preparing a modified structured carrier catalyst according to technical solution 7 or 8, wherein the particle size D of the particles in the suspension is₉₀Is 20nm or less, for example, 3 to 20nm or 4 to 10nm or 4 to 8nm, preferably 10nm or less, more preferably 5nm or less.

Technical scheme 10. the preparation method of the structured carrier catalyst according to any one of technical schemes 7 to 9, wherein the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1, the weight ratio of the hydroxyl-containing solvent to the metal powder is preferably 5-10: 1.

technical scheme 11. the preparation method of the structured carrier catalyst according to any one of technical schemes 7 to 10, wherein the ratio of the surfactant to the hydroxyl-containing solvent is 0.001 to 100mg/mL, preferably 0.002 to 10mg/mL, or 0.05 to 5mg/mL, or 0.01 to 2mg/mL, or 0.02 to 2.5mg of the surfactant per mL of the hydroxyl-containing solvent, or 0.2 to 1.5 mg/mL.

Technical solution 12. the preparation method of the structured carrier catalyst according to any one of the technical solutions 7 to 11, wherein the ultrasonic wave is processed under the ultrasonic wave, and the power of the ultrasonic wave is 10 to 500W, such as 30 to 450W, 50 to 400W, 60 to 300W, or 160 to 400W, relative to 100ml of the solvent, and the frequency of the ultrasonic wave is 20 to 100KHz, such as 20 to 50 KHz; the ultrasonic treatment time is 3 to 15 hours, for example, 4 to 12 hours or 5 to 8 hours.

Technical scheme 13. the preparation method of the structured carrier catalyst according to any one of the technical schemes 7 to 12, wherein the average diameter of the metal powder is less than 20 μm, for example, 1 to 18 micrometers, or 2 to 17 micrometers, or 4 to 16 micrometers.

Technical scheme 14. the preparation method of the structured carrier catalyst according to any one of the technical schemes 7 to 13, wherein the metal powder can be one or more of pure metal powder or metal alloy powder; the metal powder is metal alloy powder, pure metal powder or a mixture of a plurality of the metal alloy powder and the pure metal powder; the pure metal powder is one or more of Fe powder, Co powder, Ni powder, Mn powder, Ti powder, Zr powder, V powder, Sn powder, Sb powder and Bi powder; the alloy powder is an alloy formed by a plurality of Fe, Co, Ni, Mn, Ti, Zr, V, Sn, Sb and Bi, or an alloy formed by one or more of Fe, Co, Ni, Mn, Ti, Zr, V, Sn, Sb and Bi and one or more of third elements, such as iron-cobalt alloy powder, iron-nickel alloy powder, iron-manganese alloy powder, cobalt-nickel alloy powder, cobalt-manganese alloy powder, nickel-manganese alloy powder, iron-chromium alloy powder, iron-molybdenum alloy powder, iron-tungsten alloy powder, iron-vanadium alloy powder, iron-copper alloy powder, iron-silver alloy powder, iron-gold alloy powder, iron-tin alloy powder, iron-antimony alloy powder, iron-bismuth alloy powder, iron-magnesium alloy powder, nickel-tungsten alloy powder, nickel-aluminum alloy powder, cobalt-molybdenum alloy powder, cobalt-titanium alloy powder, cobalt-gallium alloy powder, tin-antimony alloy powder, cobalt-molybdenum alloy powder, cobalt-titanium alloy powder, tin-antimony alloy powder, nickel-, One or more of tin-bismuth alloy powder, antimony-bismuth alloy powder, tin-antimony-bismuth alloy powder and titanium-zirconium-vanadium alloy powder; preferably, the content of the first metal in the alloy powder is higher than the content of the second metal. In the alloy powder, the ratio of the second metal: a third element: the weight ratio of the first metal is 0-1: 1, for example, 0-0.8: 1, or 0-0.5: 1, or 0-0.3: 1.

Technical scheme 15. the preparation method of the structured carrier catalyst according to any one of the technical schemes 7 to 14, wherein the surfactant is an anionic surfactant, a cationic surfactant or an amphoteric surfactant; for example, one of sodium glycocholate, sodium dioctyl sulfosuccinate, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, stearic acid, oleic acid, lauric acid, fatty acid amine, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, fatty acid methyl ester, and polyoxyethylene ether; the fatty acid amine carbon chain length is preferably between C8-C10 (carbon chain is C8, C9 or C10); the fatty acid methyl ester carbon chain length is preferably between C8-C10.

Technical solution 16. the method for preparing a structured carrier catalyst according to any one of technical solutions 7 to 15, wherein the hydroxyl group-containing solvent is water and/or a hydroxyl group-containing organic solvent, for example, an organic solvent having one or more hydroxyl groups in a molecule, the hydroxyl group-containing organic solvent is, for example, a monohydric alcohol, a dihydric alcohol, a trihydric alcohol or a derivative thereof, and usually, the number of carbon atoms in the molecule of the hydroxyl group-containing solvent is not more than 6, for example, 1, 2, 3 or 4; the monohydric alcohol is one or more of methanol and ethanol, and the dihydric alcohol is, for example: ethylene glycol, said glycol derivatives such as: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, glycol ethers, trihydric alcohols such as glycerol, trihydric alcohol derivatives such as triethanolamine.

Technical scheme 17. the preparation method of the structured carrier catalyst according to any one of the technical schemes 7 to 16, wherein the separation is performed by slow centrifugal separation, in one embodiment, the rotation speed of the slow centrifugal separation is 1200r/min to 3000r/min or 1500 to 2500r/min, and the time of the centrifugal separation is 5 to 50 minutes, for example, 10 to 30 minutes or 15 to 20 minutes; the container used for centrifugal separation can be cylindrical or prismatic, and the ratio of the diameter to the height of the container is 0.1-1: 1, preferably 0.25 to 1: 1.

technical scheme 18. the preparation method of the structured carrier catalyst according to any one of technical schemes 7 to 17, wherein the freeze drying method is sublimation drying at low temperature and under high vacuum, the drying temperature is lower than the freezing point temperature of the hydroxyl-containing solvent, the drying time has no special requirement, as long as the hydroxyl-containing solvent can volatilize, and the particles containing the hydroxyl-containing solvent are dried; for example, the freeze-drying time can be 24-48 h. Generally, a mixture formed by the molecular sieve and the suspension is cooled and solidified, and then the mixture is freeze-dried under the freezing point temperature (or the freezing point temperature) of the solvent and the vacuum condition, preferably, the freeze-drying temperature is-30 to 5 ℃, and the pressure (absolute pressure) is not more than 0.05MPa, such as 1Pa to 50000Pa or 2 to 20000Pa, preferably 5 to 1000Pa, such as 5 to 100Pa or 10 to 50Pa or 15 to 60 Pa.

Technical scheme 19. the preparation method of the structured carrier catalyst according to any one of the technical schemes 7 to 18, wherein the thickness of the active coating of the structured carrier catalyst is, for example, 0.5 to 500 micrometers, such as 1 to 400 micrometers, or 5 to 300 micrometers, or 8 to 200 micrometers, or 10 to 100 micrometers.

Technical solution 20. the method for preparing a structured carrier catalyst according to any one of technical solutions 7 to 19, wherein,

the structured carrier catalyst comprises 10-50 wt%, preferably 10-30 wt%, or 15-25 wt%, or 20-30 wt%, or 15-30 wt%, of an active coating layer and 50-90 wt%, preferably 70-90 wt%, or 75-85 wt%, or 70-80 wt%, or 70-85 wt%, of a structured carrier, based on the total weight of the structured carrier catalyst, calculated on a dry basis;

the active coating comprises a substrate coating, a molecular sieve and a modified metal film, wherein the content of the molecular sieve is 30-95 wt% or 50-90 wt%, the content of the substrate is 4-50 wt%, and the content of the modified metal film is 1-25 wt% on a dry basis, based on the total weight of the active coating; preferably, the content of the molecular sieve is 60 to 90 wt%, such as 70 to 90 wt% or 80 to 90 wt%, the content of the matrix is 10 to 40 wt%, such as 10 to 30 wt% or 10 to 20 wt%, and the content of the modified metal film is 5 to 20 wt%, such as 8 to 17 wt% or 10 to 20 wt%; preferably, the modified metal is present in the active coating in an amount of 1 to 25 wt%, such as 2 to 20 wt%, preferably 5 to 20 wt%, such as 8 to 17 wt% or 10 to 20 wt%, based on the weight of the active coating.

Technical solution 21. the preparation method of the structured carrier catalyst according to any one of the technical solutions 7 to 20, wherein in the matrix particles containing the modified metal film, the content of the modified metal is preferably 10 to 20 wt% not more than 20 wt% of the total weight of the matrix particles; in the molecular sieve particles containing the modified metal film, the content of the modified metal is preferably 10-20 wt% not more than 20 wt% of the total weight of the molecular sieve particles; in the particles containing the matrix and the molecular sieve and containing the modified metal film, the content of the modified metal is not more than 20 wt% of the total weight of the particles, and preferably 10-20 wt%.

Technical scheme 22. the preparation method of the structured carrier catalyst according to any one of technical schemes 7 to 20, wherein the modified metal film covers the outer surface of the molecular sieve particles (the molecular sieve containing the modified metal film is called as the modified molecular sieve for short), the thickness of the modified metal film on the outer surface of the molecular sieve particles is 5 to 30nm, preferably 5 to 20nm, and the content of the modified metal accounts for 10 to 20 wt% of the total weight of the molecular sieve and the modified metal; preferably, the active component coating comprises 50-95 wt% or 40-90 wt% of modified molecular sieve covering the modified metal film and 5-50 wt% or 10-60 wt% of matrix, based on the total weight of the active component coating.

The technical means 23 is the method for preparing a structured carrier catalyst according to any one of the technical means 7 to 22, wherein the method is the following first embodiment, second embodiment, third embodiment or fourth embodiment:

a first embodiment, comprising the steps of:

s1, contacting the suspension with a molecular sieve, and freeze-drying to obtain the modified molecular sieve; wherein the particle diameter d90 of the molecular sieve is 1-10 microns, such as 2-8 microns or 3-5 microns;

s2, mixing at least one metal oxide selected from IIA and IIB and/or at least one metal oxide precursor selected from IIA and IIB and an optional heat-resistant inorganic oxide source to prepare a matrix coating slurry;

s3, coating the slurry of the matrix coating on a regular structure carrier, drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier;

s4, forming slurry by the modified molecular sieve, coating the catalyst supporter obtained in the step S3 with the slurry, optionally drying and optionally roasting to obtain the regular carrier catalyst;

the second embodiment comprises the following steps:

s1, contacting the suspension with the molecular sieve, and freeze-drying to obtain the modified molecular sieve; wherein the particle diameter d90 of the molecular sieve is 1-10 microns, such as 2-8 microns or 3-5 microns;

s2, mixing a matrix source and the modified molecular sieve to form coating slurry, coating the regular carrier with the coating slurry, optionally drying and optionally roasting to obtain the regular carrier catalyst; the substrate source comprises an oxide of at least one metal of groups IIA and IIB and/or an oxide precursor of at least one metal of groups IIA and IIB and optionally a source of a refractory inorganic oxide;

the third embodiment comprises the following steps:

s1, mixing the matrix source and the molecular sieve, drying, optionally roasting, and preparing D₉₀A substrate having a thickness of not more than 1 to 10 microns, preferably 1 to 8 microns, for example 2 to 5 microns or 3 to 5 microns andparticles of a molecular sieve; the substrate source comprises an oxide of at least one metal of groups IIA and IIB and/or an oxide precursor of at least one metal of groups IIA and IIB and optionally a source of a refractory inorganic oxide;

s2, mixing the particles containing the matrix and the molecular sieve with the suspension, and freeze-drying to obtain particles containing the matrix and the molecular sieve and containing the metal film;

s3, mixing particles containing the matrix and the molecular sieve containing the metal film with water to prepare slurry, coating the regular carrier with the slurry, drying and roasting to obtain the regular carrier catalyst;

a fourth embodiment, comprising the steps of:

s1, forming the matrix source into slurry, drying, molding, roasting, and grinding to obtain D₉₀Substrate particles of no more than 1 to 10 microns, preferably 1 to 8 microns, for example 2 to 5 microns or 3 to 5 microns; the substrate source comprises an oxide of at least one metal of groups IIA and IIB and/or an oxide precursor of at least one metal of groups IIA and IIB and optionally a source of a refractory inorganic oxide;

s2, contacting the suspension with the matrix particles, and freeze-drying to obtain the matrix particles containing the modified metal film;

optionally S3, contacting the molecular sieve with the suspension, and freeze-drying to obtain molecular sieve particles containing the modified metal film; molecular sieve D₉₀No more than 1 to 10 microns, preferably 1 to 8 microns, for example 2 to 5 microns or 3 to 5 microns;

s4, respectively forming slurry of the matrix particles containing the modified metal film and the molecular sieve particles or the molecular sieve particles containing the modified metal film or mixing to form slurry to coat the regular carrier, and optionally drying and optionally roasting to obtain the regular carrier catalyst.

Technical solution 24. the method for preparing a structured carrier catalyst according to any one of technical solutions 7 to 23, wherein,

in the steps of the first embodiment, the second embodiment, the third embodiment and the fourth embodiment, the drying temperature is from room temperature to 150 ℃, for example, from 80 ℃ to 120 ℃, and the drying time may be 1 hour or more, for example, from 2 hours to 8 hours; the roasting temperature is 200-600 ℃, for example 200-450 ℃, and the roasting time is more than 1h, for example 2-4 h. The room temperature is 15-40 ℃.

Technical solution 25 the method for preparing a structured carrier catalyst according to any one of the technical solutions 7 to 24, wherein the heat-resistant inorganic oxide source is one or more of an alumina source, a silica source and a silica-alumina source, and is preferably an alumina source; for example, the alumina source is a substance that can be converted to alumina under the conditions of calcination, preferably hydrated alumina and/or an alumina sol; the hydrated alumina can be selected from one or more of boehmite, pseudo-boehmite, alumina trihydrate and amorphous aluminum hydroxide, the silica-alumina source is selected from one or more of clay and silica-alumina gel, the clay is selected from one or more of kaolin, halloysite, montmorillonite, diatomite, halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite, and the silica source is selected from one or more of silica sol and silica gel.

The process for producing a structured carrier catalyst according to any one of claims 7 to 25, wherein the heat-resistant inorganic oxide source is an alumina source, and the weight ratio of the alumina source in terms of alumina to the oxide of at least one metal of groups IIA and IIB in terms of oxide is 40 to 75: 25 to 60, for example, 50 to 70: 30-50 is preferably 60-70: 30-40 parts of; preferably, the matrix contains 50 to 70 wt% of an aluminum binder and 30 to 50 wt% of an oxide of at least one metal of group IIA or IIB on a dry basis based on the total weight of the matrix.

Technical scheme 27. according to any one of the technical schemes 1 to 25, the molecular sieve is one or more of a large-pore zeolite, a medium-pore zeolite and a non-zeolite molecular sieve; the large-pore zeolite refers to zeolite with a pore structure ring opening of at least 0.7 nanometer, and can be one or more selected from L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite, and is preferably Beta zeolite; the medium pore zeolite refers to zeolite with pore structure opening of 0.56-0.70 nm, and can be selected from ZSM-5 boiling pointOne or more of stone, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite and MCM-56 zeolite, preferably ZSM-5 zeolite; the non-zeolitic molecular sieve is selected from one or more of silicates having different silicon to metal ratios (e.g., metallosilicates, titanosilicates), metalloaluminates (e.g., germano-aluminates), metallophosphates, aluminophosphates, metalloaluminophosphates, metal-bonded silicoaluminophosphates, metal-integrated silicoaluminophosphates (MeAPSO and ELAPSO), Silicoaluminophosphates (SAPO), gallium germanates (gallogermanates), and may be, for example, one or more of SAPO-11, SAPO-34, and SAPO-31, preferably SAPO-11 molecular sieve. D of the molecular sieve₉₀The diameter is preferably 1 to 8 micrometers, for example, 2 to 6 micrometers or 3 to 5 micrometers; the modified metal forms a metal film to cover the outer surface of the molecular sieve with high silica-alumina ratio; when the molecular sieve is a silicon-aluminum molecular sieve, the molecular sieve is preferably a molecular sieve with a high silicon-aluminum ratio, and the silicon-aluminum ratio of the molecular sieve with the high silicon-aluminum ratio is (SiO)₂/Al₂O₃Molar ratio) preferably greater than 50, for example from 50 to 500 or from 100 to 500; preferably 50 to 150 or 150 to 300. When the molecular sieve is a phosphorus-aluminum molecular sieve, the silicon-aluminum ratio is (SiO)₂/Al₂O₃Molar ratio) of 0.1 to 1.5, for example 0.1 to 1.5: 1; preferably 0.2 to 0.8.

The technical scheme 28. the desulfurization method of the sulfur-containing hydrocarbon comprises the step of carrying out contact reaction on a hydrocarbon material containing a sulfur compound, a hydrogen donor and the structured carrier catalyst in any one of the technical schemes 1 to 27, wherein the reaction temperature is 150 to 350 ℃, the reaction pressure is 0.5 to 5MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon is 0.1 to 100h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01 to 1000. The preferable reaction temperature is 200-300 ℃, the reaction pressure is 1-3.5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 1-10 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500.

The desulfurization method according to claim 28, wherein the hydrogen donor is one or more of hydrogen gas, hydrogen-containing gas, and a hydrogen donor; the hydrogen may be supplied using hydrogen-containing gaseous feedstocks of various purities, typically with hydrogen content above 30% by volume; hydrogen-containing gas such as one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas; the hydrogen donor is at least one of tetrahydronaphthalene, decahydronaphthalene and indane; the hydrocarbon material is selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil, and is preferably gasoline and/or diesel oil; the above gasoline, kerosene, diesel oil and gas oil fractions are full fractions thereof and/or partially narrow fractions thereof.

Technical scheme 30. according to the desulfurization method of the technical scheme 28 or 29, the sulfur content of the hydrocarbon material containing sulfur compounds is 10-1000 mg/Kg, for example, the sulfur-containing compound material is catalytically cracked gasoline or catalytically cracked diesel oil. Typically, the catalytically cracked gasoline has an olefin content of 15 to 50 wt.%.

The structured carrier catalyst provided by the invention has one or more of the following advantages, at least one of the following effects can be realized, and preferably, a plurality of effects can be realized:

(1) may have a higher activity. Under the condition of the same active metal, the catalyst has higher desulfurization activity than the prior hydrodesulfurization catalyst and hydrodesulfurization adsorbent. For example, desulfurization at a lower reaction temperature and a lower hydrogen pressure can result in a higher desulfurization rate than existing desulfurization catalysts, thereby allowing the reaction temperature to be lowered.

(2) The metal is not easy to lose or gather, the stability of the desulfurization activity is better, frequent regeneration is not needed, the regeneration period can be prolonged, the long-period operation of a desulfurization device is facilitated, and the stability of the hydrodesulfurization is better than that of the conventional hydroabsorption desulfurization.

(3) The catalyst is used for hydrodesulfurizing gasoline containing olefin and has low hydrogen consumption.

(4) The catalyst is used for hydrodesulfurizing gasoline containing olefin, such as catalytically cracked gasoline, and has obviously lowered olefin content.

(5) The method is used for hydrodesulfurizing the gasoline containing olefin, and can improve the octane number of oil products compared with the prior desulfurizing method.

(6) The catalyst is used for hydrodesulfurizing gasoline containing olefin, and compared with the existing desulfurizing technology, the content of aromatic hydrocarbon is not increased or is slightly lower.

(7) The catalyst is used for desulfurizing the gasoline containing olefin, so that the content of isomeric hydrocarbon in the desulfurized gasoline is obviously improved, and the normal paraffin is obviously reduced.

(8) The catalyst is used for desulfurizing the gasoline containing olefin and has higher gasoline yield.

The regular carrier catalyst provided by the invention can be obtained by the preparation method of the regular carrier catalyst provided by the invention.

The desulfurization method provided by the invention can have higher desulfurization rate and higher yield of desulfurization products at the same reaction temperature, can run for a long period, and can improve the octane number of gasoline.

Detailed Description

In the present invention, the term "regular carrier catalyst" is used to refer to a catalyst comprising a regular structure carrier and an active component coating layer distributed on the inner surface and/or the outer surface of the carrier, also called regular structure catalyst; "regular structure carrier" is also called regular carrier, is a carrier with regular structure; the regular structure reactor is a fixed bed reactor filled with a regular structure catalyst as a catalyst bed layer.

The dry basis weight (dry weight for short) is the weight of the solid product obtained after the material has been calcined at 800 ℃ for one hour.

The sulfur-containing hydrocarbon feed weight hourly space velocity refers to the weight of sulfur-containing hydrocarbon feed per hour of the reactor relative to the weight of the active coating of the structured supported catalyst in the reactor. The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon (abbreviated as hydrogen-oil ratio) is the ratio of the volume of the hydrogen donor introduced into the reactor in a standard state to the volume of the hydrocarbon feed at 20 ℃ under one standard atmosphere.

The regular carrier catalyst with the desulfurization effect comprises a regular carrier and an active coating, wherein the active coating comprises a matrix, a molecular sieve and a modified metal film (metal film for short), and the metal film is positioned on the outer surface of matrix particles and/or the outer surface of molecular sieve particles or the outer surface of particles formed by the matrix and/or the molecular sieve. The metal film is coated on the outer surface of the matrix particles and/or the molecular sieve particles, and can cover part or all of the outer surface of the particles in the matrix and/or part or all of the outer surface of the molecular sieve particles, and cover part or all of the outer surface of the particles formed by the matrix and the molecular sieve; for example, the metal film may be integral with the substrate and/or the outer surface of the molecular sieve particles, or may be dispersed into a plurality of pieces, either continuous or spaced apart from one another. Preferably, the modified metal membrane is disposed on the outer surface of the molecular sieve particles (the modified molecular sieve comprising the modified metal membrane is formed and then coated on the structured carrier or the structured carrier containing the matrix, or the modified molecular sieve is mixed with the matrix and then coated on the surface of the structured carrier). The substrate and the modified molecular sieve in the active coating layer may be mixed together and then formed into a coating layer, or may be respectively located in different coating layers, for example, the modified molecular sieve and the substrate respectively form different coating layers, the modified molecular sieve coating layer forms the substrate coating layer on the outer surface of the substrate coating layer (in the active coating layer, the direction close to the regular carrier is called as the inner surface, and the direction far from the regular carrier is the outer surface), and then forms the modified molecular sieve coating layer on the surface of the substrate coating layer. The thickness of the metal film in the modified molecular sieve is 5-30 nm, preferably 5-20 nm. The metal film may be measured by transmission electron microscopy. Preferably, the structured carrier catalyst comprises 65-85 wt% of structured carrier and 15-35 wt% of active coating or comprises 70-85 wt% of structured carrier, preferably 70-80 wt% of active coating, and 15-30 wt% of active coating, preferably 20-30 wt%.

Preferably, the active coating comprises 4-50 wt% of matrix, 30-95 wt% of molecular sieve and 1-25 wt% of modified metal film based on the total weight of the active coating on a dry basis; more preferably, the active component coating comprises 10-40 wt% of the substrate, 40-80 wt% of the molecular sieve and 2-20 wt%, for example 5-20 wt% of the modified metal, and preferably, the active coating comprises 10-40 wt% of the substrate, 45-75 wt% of the molecular sieve and 8-18 wt% of the modified metal.

Preferably, the total weight of the active coating (also called active component coating) is taken as a reference, and the active coating contains 50-95 wt% of molecular sieve and modified metal and 5-50 wt% of matrix on a dry basis; preferably, the active component coating contains a substrate with the total content of the molecular sieve and the modified metal being 60-90 wt% and 10-40 wt%; for example, the total content of the molecular sieve and the metal in the active component coating is 60-85 wt%, and the content of the matrix is 15-40 wt%. The substrate comprises 40-75 wt%, such as 50-70 wt%, of a heat-resistant inorganic oxide and 25-60 wt%, such as 30-50 wt%, of an oxide of at least one metal of groups IIA and IIB, based on the total weight of the substrate; for example, the substrate contains 60 to 70 wt% of a heat-resistant inorganic oxide and 30 to 40 wt% of an oxide of at least one metal of group IIA and IIB, based on the total weight of the substrate. The refractory inorganic oxide is preferably alumina.

The regular carrier catalyst (also called regular structure catalyst) with the desulfurization function comprises a regular carrier (also called regular structure carrier), and can be used for providing a catalyst bed layer in a fixed bed reactor. The regular carrier can be a monolithic carrier block, a hollow pore channel structure is formed inside the regular carrier, a catalyst coating can be distributed on the inner wall of a pore channel, and the pore channel space can be used as a flowing space of fluid. Preferably, the regular structure carrier is selected from monolithic carriers having a parallel channel structure with two open ends, for example, the regular structure carrier may be a honeycomb type regular carrier (referred to as a honeycomb carrier) with a honeycomb-shaped opening in the cross section. The structured carrier can be at least one of cordierite honeycomb carrier, mullite honeycomb carrier, diamond honeycomb carrier, corundum honeycomb carrier, zirconia corundum honeycomb carrier, quartz honeycomb carrier, nepheline honeycomb carrier, feldspar honeycomb carrier, alumina honeycomb carrier and metal alloy honeycomb carrier.

According to the regular carrier catalyst provided by the invention, preferably, the regular carrier is a honeycomb carrier, and the pore density of the cross section of the honeycomb carrier is 40-800 poresPer square inch, preferably 100 to 400 holes per square inch; the cross-sectional area of each hole in the honeycomb structured carrier is preferably 400-1.8 multiplied by 10⁵μm²More preferably 1500 to 22500 μm²The aperture ratio of the carrier surface of the honeycomb structured carrier is 20-80%, preferably 50-80%. The shape of the hole can be one of a square, a wing square (namely, the wing with inward vertical edges is arranged at the center of four sides in the square hole, and the length of the wing is 1/5-2/5 of the side length of the square), a regular triangle, a regular hexagon, a circle and a ripple shape.

The structured carrier catalyst provided by the invention contains the oxide of at least one metal in the IIA and IIB groups in the substrate, and the oxide is a metal oxide with sulfur storage performance. Preferably, the oxide of at least one metal in group IIA, IIB is an oxide of at least one metal selected from magnesium, zinc and calcium, such as one or more of magnesium oxide, calcium oxide, zinc oxide; preferably zinc oxide.

The preparation method of the regular carrier catalyst provided by the invention comprises the step of preparing the suspension. The suspension preparation method comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and treating under ultrasonic waves to obtain an ultrasonic mixed solution; wherein, in the ultrasonic treatment process, fine metal particles stripped from metal powder are suspended in a solvent (solvent for short) containing hydroxyl; separating larger particles from the mixed liquid after ultrasonic treatment to obtain a suspension, wherein the suspension is suspended with fine particles containing the modified metal. The metal powder (also referred to as metal powder) may be a pure metal powder (in the case where the metal film contains only the modifying metal and the modifying metal is one kind), an alloy powder containing the modifying metal and boron, or an alloy powder containing a plurality of modifying metals. Wherein, there is no special requirement for the relative content of metal powder and hydroxyl-containing solvent, as long as the hydroxyl-containing solvent can contain the modified metal element with the required content after ultrasonic treatment. Thus, the amount of metal powder used may be excessive (exceeding the amount of metal contained in the suspension). Preferably, the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1 is, for example, 3 to 12:1 or 5 to 10: 1. By controlling the time and power of the ultrasonic treatment, the content of the modified metal element with the required concentration in the hydroxyl-containing solvent can be achieved.

The preparation method of the regular carrier catalyst provided by the invention leads metal powder to generate metal stripping in the presence of a surfactant through ultrasonic treatment to form fine particles suspended in a hydroxyl-containing solvent. Generally, there is no special requirement for the power and frequency of the ultrasonic wave, the power of the ultrasonic wave is small, and a long treatment time is required to achieve a certain concentration of the modified metal in the hydroxyl group-containing solvent. Preferably, the power of the ultrasonic wave in the ultrasonic wave treatment is 10 to 500W, such as 30 to 450W, 160 to 400W, 40 to 200W, or 30 to 300W, relative to 100ml of the solvent, the frequency of the ultrasonic wave is 20 to 100KHz, such as 20 to 50KHz, and the time of the ultrasonic wave treatment is 3 to 15 hours, such as 4 to 10 hours, or 5 to 8 hours. (the power of the ultrasonic waves applied to the solvent per unit volume is a specific ultrasonic power, for example, when the power applied to 100mL of solvent is 30 to 500W, the specific ultrasonic power is 0.3 to 5W/mL or 30 to 500W/100 mL).

The invention has no special requirement on the particle size of the metal powder, the particles are usually larger, and longer ultrasonic treatment time is needed to obtain a suspension with a certain metal concentration, and the average diameter of the metal powder is preferably less than 20 microns, such as 1-15 microns, or 1-18 microns, or 4-16 microns.

In the present invention, the average diameter of the metal powder, the particle size distribution of the molecular sieve and D₉₀Particle size distribution of solid particles and D₉₀The measurement is carried out by a laser particle size instrument, and the measurement method can be found in the national standard GB/T19077-2016 & lt & gt particle size distribution laser diffraction method & gt. (D)₉₀Also written as d₉₀D90 or D90, is the particle diameter at which the particle size distribution cumulatively reaches 90% by volume

The preparation method of the regular carrier catalyst provided by the invention is characterized in that ultrasonic treatment is carried out in the presence of a surfactant. The surfactant is introduced for the purpose of peeling off the metal, forming a stable suspension, and contributing to the formation and stabilization of the metal film and the improvement of the catalyst performance, forming a metal film having higher activity. The weight ratio of the surfactant to the hydroxyl group-containing solvent is 0.001 to 100mg/g, for example, 0.01 to 10mg/g, 0.05 to 5mg/g, 0.002 to 2mg/g, 0.005 to 1mg/g, or 0.2 to 1.5 mg/g.

According to the preparation method of the regular carrier catalyst, undissolved particles after ultrasonic treatment are separated through separation, so that a suspension is obtained. The suspension contains fine particles including the modifying metal. The separation method of the invention is preferably a centrifugal separation method, larger particles are settled at the bottom of the container through centrifugal separation, smaller particles which are not separated exist in the solvent, namely in the suspension, the suspension at the upper layer is led out from the separation container, and the settled metal particles can be recycled. In one embodiment, the separation is performed by slow centrifugation at a rotation speed of 1200-3000 rpm, preferably 1500-2500 r/min, for 10-30 min, for example 15-20 min. In one embodiment, the container for centrifugal separation is cylindrical, and the ratio of the diameter to the height of the container is 0.1-1: 1, for example, 0.1 to 0.5: 1.

preferably, the particle size D of the particles in the suspension obtained after centrifugation₉₀Is 20nm or less, preferably 10nm or less, more preferably 5nm or less, for example, 3 to 20nm, 3 to 10nm, or 3 to 5 nm.

Particle size distribution of the suspension and D₉₀Analysis can be performed using a nanoparticle analyzer, such as the Zetasizer NanoZSP nanoparticle analyzer from Malvern.

The preparation method of the regular carrier catalyst provided by the invention can cover the modified metal film on the outer surface of the matrix particle, the outer surface of the oxide particle of at least one metal in IIA and IIB groups, the outer surface of the heat-resistant inorganic oxide particle, the outer surface of the molecular sieve particle and the outer surface of the particle formed by the molecular sieve and the matrix, and then mix the particles or respectively coat the particles on the regular carrier in sequence.

The invention provides a preparation method of a structured carrier catalyst, which comprises the following steps:

s1, mixing the molecular sieve with water, and performing wet ball milling to obtain the molecular sieve with the particle diameter D₉₀A slurry of 1 to 10 microns, for example 2 to 8 microns, preferably 2 to 5 microns; then mixing with the suspension, and freeze-drying to obtain the modified molecular sieve;

s2, mixing an oxide of at least one metal selected from IIA and IIB groups with an alumina source to prepare a matrix coating slurry;

s3, coating the slurry of the matrix coating on a regular structure carrier (also called a regular carrier), drying and roasting to form a matrix coating on the inner surface and/or the outer surface of the regular structure carrier to obtain a catalyst carrier;

s4, forming modified molecular sieve slurry from the modified molecular sieve obtained in the step S1, coating the modified molecular sieve slurry on the catalyst carrier obtained in the step S3, drying and roasting to form a modified molecular sieve coating on the inner surface and/or the outer surface of the regular structure carrier, and obtaining the regular carrier catalyst.

The first embodiment of the method for preparing a structured carrier catalyst according to the present invention, wherein the alumina source is a substance that can be converted into alumina under the calcination conditions described in the aforementioned step S3, and is preferably hydrated alumina and/or alumina sol; the hydrated alumina is at least one of boehmite (also called boehmite, boehmite), pseudoboehmite (also called pseudoboehmite), alumina trihydrate and amorphous aluminum hydroxide.

In the first embodiment of the method for preparing a structured carrier catalyst according to the present invention, the substrate coating slurry preferably contains 40 to 75 wt%, for example 50 to 70 wt%, of the alumina source calculated as alumina and 25 to 60 wt%, for example 30 to 50 wt%, of the oxide of at least one metal of groups IIA and IIB, based on the dry weight of the substrate coating slurry. Preferably, the alumina source is contained in an amount of 60 to 70 wt% in terms of alumina, and the oxide of at least one metal of group IIA or IIB is contained in an amount of 30 to 40 wt% in terms of alumina.

According to a first embodiment of the method for preparing a structured carrier catalyst of the present invention, the matrix coating and the modified molecular sieve coating formed on the structured carrier are collectively referred to as an active component coating. Preferably, the total content of the matrix coating layer and the modified molecular sieve coating layer (i.e., the active coating layer) is 10 to 50 wt%, preferably 15 to 30 wt%, and more preferably 20 to 30 wt%, based on the total weight of the structured supported catalyst; and the total content of the modified molecular sieve is 50-95 wt%, such as 60-90 wt%, and the content of the matrix is 5-50 wt%, such as 10-40 wt%, based on the total weight of the active component coating; preferably, the content of the modified molecular sieve is 70-90 wt%, and the content of the matrix is 10-30 wt%.

According to the first embodiment of the preparation method of the structured carrier catalyst, there is no special requirement for the solid content of the coating slurry prepared in steps S2 and S4, however, too high solid content of the slurry may increase the difficulty of coating the slurry, and too low solid content of the slurry may decrease the adhesion of each coating, thereby increasing the coating times. Preferably, the solid content of the coating slurry in the steps S2 and S4 is 10 to 45 wt%, preferably 20 to 40 wt%.

According to the first embodiment of the method for preparing a structured carrier catalyst of the present invention, preferably, the step S2 may further include a step of pretreating the alumina source, wherein the step of pretreating the alumina source includes mixing the alumina source with water and pulping, adding an acid solution to the obtained slurry to make the slurry in a gel state, and then aging the slurry in the gel state. By subjecting the alumina source to the foregoing pretreatment steps, dispersion and bonding of other matrix components is facilitated.

According to the first embodiment of the preparation method of the regular carrier catalyst, the step of pretreating the alumina source is preferably performed by adding one or more acid solutions selected from hydrochloric acid, dilute nitric acid, oxalic acid, acetic acid and dilute sulfuric acid, wherein the concentration of the acid solution is preferably 15-37 wt%; in the step of adding the acid solution to the obtained slurry, the pH value of the slurry after the acid is added is preferably 1-5, preferably 2-4, and the control of the pH value of the slurry is beneficial to simply and conveniently mastering the gel state of the slurry. Preferably, in the step of aging the slurry in the gel state, the temperature of the aging treatment is 50-80 ℃ and the time is 0.5-2 h.

According to the first embodiment of the method for preparing a structured carrier catalyst of the present invention, the particle diameter d of the oxide of at least one metal of groups IIA and IIB is preferably the same₉₀Not more than 10 μm, for example, 50nm to 10 μm, or 0.5 to 10 μm, or 1 to 5 μm, or 50nm to 500 nm. The diameter of the added alumina source particles is 100nm or less, and the diameter d of the added alumina source particles is more preferable₉₀10 to 50 nm. The particle diameter of the raw materials is controlled to be more beneficial to the dispersion and mixing of the slurry, so that a matrix material with more uniform distribution is formed.

According to the first embodiment of the method for preparing a structured carrier catalyst of the present invention, the coating slurry may be distributed on the inner and/or outer surfaces of the structured carrier by various coating methods in the steps S3 and S4. The coating method may be a water coating method, a dipping method or a spraying method. The specific operation of coating can be carried out with reference to the method described in CN 1199733C. Preferably, the coating is carried out by a water coating method, namely, a carrier is coated by a dispersion liquid obtained by beating the coating material and water, one end of the carrier is immersed in the slurry liquid in the coating process, and the other end of the carrier is vacuumized so that the slurry liquid continuously passes through the pore channels of the carrier. The volume of the slurry passing through the carrier pore channel is 2-20 times of the volume of the carrier, the applied vacuum pressure is-0.1 MPa to-0.01 MPa, the coating temperature is 10-70 ℃, and the coating time is 0.1-100 seconds.

According to the first embodiment of the method for preparing a structured carrier catalyst of the present invention, the drying and calcining method and conditions in step S3 are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in step S3, the drying temperature is between room temperature and 300 ℃, preferably between 100 and 200 ℃, and the drying time is more than 0.5h, preferably between 1 and 10 h. The roasting temperature is 400-800 ℃, and preferably 500-700 ℃; the roasting time is at least 0.5 hour, and preferably 1-10 hours.

According to the first embodiment of the method for preparing a structured carrier catalyst of the present invention, the drying and calcining method and conditions in step S4 are well known to those skilled in the art. For example, the drying method may be air drying, oven drying, forced air drying; the method of calcination may also be a method known in the art. Preferably, in step S4, the drying temperature is between room temperature and 150 ℃, preferably between 80 and 120 ℃, and the drying time is more than 1 hour, preferably between 2 and 8 hours; the roasting temperature is 200-600 ℃, preferably 200-350 ℃ or 250-450 ℃, and the roasting time is more than 1 hour, preferably 2-4 hours.

The raw materials, raw material components and process methods related to the second embodiment, the third embodiment and the fourth embodiment of the preparation method provided by the invention can refer to the related description in the preparation method, and are not repeated herein. For example, the drying temperature is from room temperature to 150 ℃, preferably from 80 to 120 ℃, and the drying time is usually more than 5min, for example, more than 1 hour, for example, from 2 to 8 hours; the roasting temperature is 200-600 ℃, preferably 200-350 ℃ or 250-450 ℃, and the roasting time is more than 1 hour, preferably 2-4 hours.

The preparation method of the regular carrier catalyst provided by the invention is that the suspension is uniformly mixed with the matrix and/or the molecular sieve, and then the mixture is frozen and dried, usually, the mixture is frozen firstly and then dried under vacuum and freezing conditions. In one embodiment, the temperature of the mixture is lower than the solidification temperature of the solvent, so that the mixture is solidified into a solid, and then the solvent is sublimated and volatilized under the vacuum condition of the temperature lower than the solidification point or the freezing point of the solvent to obtain the matrix and/or the molecular sieve particles wrapping the modified metal film.

According to the preparation method of the present invention, the suspension may be contacted with the molecular sieve, the matrix or the particles comprising the molecular sieve and the matrix by any method suitable for contacting a solid and a liquid with each other. Such as mixing, spraying, soaking. .

In order to facilitate freezing and drying, the hydroxyl-containing solvent (solvent for short) with a high freezing point (freezing point) is preferably selected, preferably, the solvent is not lower than-25 ℃, so that the freezing and drying are carried out at the temperature of-20-5 ℃, and therefore, the solvent with the freezing point temperature of-20-5 ℃ is preferably used. Preferably, the drying is carried out under vacuum at a pressure of 10 to 10000Pa (absolute), for example 5 to 1000Pa, 10 to 100Pa, 10 to 50Pa, or 15 to 35 Pa.

The hydroxyl-containing solvent is preferably one or more of water, ethylene glycol, glycerol and methanol. In one embodiment, the mixture comprises water and a hydroxyl group-containing organic solvent at a weight ratio of water to hydroxyl group-containing organic solvent of 0.2 to 4:1, such as 0.4 to 3.6:1 or 0.3 to 2:1 or 0.025 to 0.4:1 or 0.03 to 0.3: 1.

the preparation method of the regular carrier catalyst provided by the invention comprises the following steps: uniformly mixing metal powder and a hydroxyl-containing solvent, then carrying out ultrasonic treatment for 4-10 hours, for example, 5-8 hours at the power of 50-250W/(100 g of hydroxyl-containing solvent), preferably 100-150W/(100 g of hydroxyl-containing solvent), and then carrying out centrifugal separation on the mixed liquid after ultrasonic treatment at the rotation speed of 1200-3000 r/min, preferably 1500-2500 r/min to obtain a suspension after separation; then mixing the substrate and/or the molecular sieve and/or the particles containing the substrate and the molecular sieve with the suspension, after uniform dispersion, freeze-drying, and coating the regular carrier to obtain the regular carrier catalyst. The average particle size of the metal powder is less than 20 micrometers, preferably 1-15 micrometers or 3-18 micrometers; the metal powder: a hydroxyl group-containing solvent in a weight ratio of 1:2 to 15, preferably 1:5 to 10; the surfactant: 1mL of a solvent (0.001-100 mg). The metal powder is one or more of metal simple substance powder and alloy powder, the freeze drying temperature is preferably-20-5 ℃, the freeze drying is carried out in vacuum, and the freeze drying pressure is 5-1000 Pa. The freeze-drying time is, for example, 24 to 48 hours.

Preferably, in the preparation method of the regular carrier catalyst provided by the invention, the amounts of the matrix, the molecular sieve and the modified metal are such that, in the obtained active coating, based on the total weight of the active coating, the content of the molecular sieve is 30-95 wt%, for example, 50-90 wt%, the content of the matrix is 4-50 wt%, and the content of the modified metal is 1-25 wt% on a dry basis; preferably, the content of the molecular sieve is 60 to 90 wt%, such as 70 to 90 wt% or 80 to 90 wt%, the content of the matrix is 10 to 40 wt%, such as 10 to 30 wt% or 10 to 20 wt%, and the content of the modified metal is 5 to 20 wt%, such as 8 to 17 wt% or 10 to 20 wt%.

The desulfurization method provided by the invention can be carried out at a lower reaction temperature and has a better desulfurization effect. For example, in one embodiment, the reaction temperature is 250-300 ℃, the reaction pressure is 1-3.5 MPa, the hydrogen partial pressure is preferably 0.5-2 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feed is 1-10 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500.

In the present invention, all pressures referred to are expressed in absolute terms unless otherwise stated.

The method for desulfurizing the sulfur-containing hydrocarbon can regenerate the sulfur-containing hydrocarbon at intervals after the desulfurization effect of the sulfur-containing hydrocarbon does not meet the requirement; and active metal can be aggregated without repeatedly undergoing oxidation regeneration-reduction, which is beneficial to improving the desulfurization activity of the catalyst and the stability of the desulfurization process of the sulfur-containing hydrocarbon. The regeneration method can refer to the existing method, for example, an oxidation method can be adopted, the invention has no special requirement, and the invention is not described again.

In the following examples and comparative examples,

XRD analysis was carried out by measuring cell constants and relative crystallinity by means of XRD analysis on a Japanese D/Max-IIIA X-ray diffractometer (Cu-K α target) by the RIPP146-90 method (see "analytical methods in Petroleum and chemical industries (RIPP laboratory methods), eds of Yankee and the like, published by scientific publishers, 1990).

The regular carrier and the metal content in the regular carrier catalyst are calculated according to the charge ratio.

Analysis of the thickness of the metal film: the transmission electron microscope method is adopted, and the specific analysis method is as follows: randomly selecting 30 particles from a sample, measuring the thickness of the metal film at any position of each particle, and then taking the average value of all the thicknesses to obtain the thickness of the metal film of the sample;

the product composition is calculated according to the feed ratio.

Laser particle size analysis: a Malvern Mastersizer 2000 laser particle size analyzer is adopted;

and (3) nano-particle size analysis: zetasizer NanoZSP Analyzer from Malvern;

motor Octane Number (MON) and Research Octane Number (RON) of gasoline: measured by GB/T503-1995 and GB/T5487-1995;

and (3) measuring the sulfur content: measuring by an off-line chromatographic analysis method, and measuring by adopting a GC6890-SCD instrument of the agilent company;

a centrifugal separator: model DT5-4B, Beijing times Beili centrifuge, Inc., container diameter and height ratio 1: 1;

an ultrasonic cleaner: model KQ-400DB, frequency 40 KHZ;

solvents, surfactants, not specified, used in the examples were purchased from national pharmaceutical group chemical agents, ltd, grades: and AR.

In the following examples and comparative examples, the method for coating the substrate slurry on the regular structure carrier is a water coating method, and the specific process method comprises the following steps: in each coating process, one end of the regular structure carrier is immersed in the matrix coating slurry, and the other end of the regular structure carrier is vacuumized to enable the slurry to continuously pass through the pore channel of the carrier; wherein the volume of the slurry passing through the carrier pore channel is 2.5 times of the volume of the carrier, the applied vacuum pressure is-0.03 MPa (the difference between absolute pressure and standard atmospheric pressure), the coating temperature is 35 ℃, and the coating time is 60-300 seconds.

Example 1

(1) Preparation of the structured Carrier containing the matrix:

0.31kg of pseudoboehmite (produced by Shandong aluminum plant, solid content 65%, alumina 0.2kg, particle diameter d)₉₀35nm, same below) and 0.7kg of deionized water (pH 7, the same applies hereinafter) was mixed and beaten uniformly, 100mL of hydrochloric acid having a concentration of 18% by weight was added dropwise, the pH of the slurry was adjusted to 1.8 to make the slurry in a gel state, and aging was carried out at 60 ℃ for 1 hour to obtain a pretreated pseudoboehmite.

0.21kg of zinc oxide powder (from Beijing chemical plant, particle diameter d) was added to the pretreated pseudoboehmite obtained as described above₉₀Is 75 nm; 0.2kg of dry basis, the same below)) are mixed and stirred, wet-milled for 5 hours by a ball mill (the ball-milling liquid is distilled water) to prepare matrix coating slurry with the solid content of 30wt percent, and then coated on a cylindrical honeycomb cordierite structured carrier (a product of Jiangsu Yixing non-metal chemical mechanical factory Co., Ltd., the size of which is the size of

The open porosity was 70%, the cell density of the cross section was 200 cells/square inch, and the cross sectional area of the cells was 5625 μm²The same applies below). The coated catalyst was dried at 120 ℃ for 120min, calcined at 550 ℃ for 180min, and coated twice to achieve the target weight of the matrix coating (the weight ratio of the matrix coating to the structured carrier on a dry basis was 5:70), yielding a catalyst support, noted ZT 1.

(2) Preparing a modified molecular sieve:

firstly, 10g of nickel powder (average particle size of the nickel powder is 10 microns, source: national drug group) and 100ml of ethylene glycol (national drug group, purity AR) are added into a 200ml wide-mouth bottle, mixed uniformly, and then 60mg of surfactant sodium glycocholate (purity AR, source: Nanjing Paels Biotech limited) is added; then, the reaction vessel (jar) was placed in an ultrasonic cleaner and sonicated at 160W power for 6h (frequency 40 KHz); centrifuging the liquid after ultrasonic treatment in a centrifugal separator at 1500r/min for 20min, taking out supernatant (suspension) with a pipette, wherein the concentration of metallic nickel in the suspension is 15g/Kg, and D₉₀Is 5 nm;

13.5 g (dry basis) of SAPO-11 molecular sieve powder (Si: Al: P molar ratio ═ 1:9:10, D)₉₀14 μm, relative crystallinity 91%, technical grade, product of the Qilu division, China petrochemical catalyst, Inc., the same below), and10g of deionized water, and wet grinding to obtain a molecular sieve slurry, wherein the particle diameter D of the molecular sieve slurry₉₀5 microns; adding the molecular sieve slurry into 100g of the suspension; stirring for 10 min; the obtained slurry is marked as JY-1,

finally, pre-freezing the slurry JY-1 at the temperature of-40 ℃, and then drying the slurry for 24 hours at the temperature of-30 ℃ and under the vacuum condition of the pressure of 50Pa, wherein the modified molecular sieve is obtained as the final product, namely ZA1, the thickness of the metal film is 5nm, the nickel content is 10 weight percent, and D₉₀Is 5 microns.

(3) Preparation of regular Supported catalysts

Mixing ZA1 with water and pulping to prepare slurry with solid content of 35 wt%; taking a diameter of 30mm and a length of 50mm (expressed as

) And coating ZT1 with the slurry, drying at 120 ℃ for 2 hours, roasting at 450 ℃ for 2 hours, and repeatedly coating for 2 times to enable the dry basis weight of the modified molecular sieve to account for 25 wt%, wherein the final product is the regular carrier catalyst and is marked as A1.

The structured carrier catalyst A1 contained, by dry weight, cordierite 70%, zinc oxide 2.5%, alumina 2.5%, molecular sieve 22.5%, and metallic nickel 2.5%.

Comparative example 1

10g of nickel nitrate (calculated as nickel) is dissolved in 100ml of ethylene glycol, then the reaction vessel is placed in an ultrasonic cleaning machine, ultrasonic treatment is carried out for 6h at the power of 160W, mixed impregnation is carried out on the nickel nitrate and ZT1 (same as the example 1), then drying is carried out at 120 ℃, and roasting is carried out at 450 ℃ for 2 hours, thus obtaining the structured carrier catalyst product DB 1. A1 contained, by dry weight, cordierite 70%, zinc oxide 2.5%, alumina 2.5%, molecular sieve 22.5% and nickel 2.5%.

Comparative example 1

A structured supported catalyst was prepared as in example 1, except that the modified molecular sieve was dried by a drying method of drying at 120 ℃ without said freeze-drying to obtain a structured supported catalyst, which was defined as BJ 1.

Example 2

This example serves to illustrate the structured support catalyst of the invention and its preparation.

(1) Preparing a regular carrier containing a matrix, which is the same as example 1 except that the weight ratio of zinc oxide to cordierite is 1:80, and the weight ratio of aluminum oxide to cordierite is 2: 80; is marked as ZT 2;

(2) preparing a modified molecular sieve:

50g of iron powder (average particle size 15 μm, purity AR, manufacturing company: Shanghai Kefeng industries Co., Ltd.) and 400ml of ethylene glycol (analytical grade) were added to a 500ml jar, mixed uniformly, and 120mg of sodium lauryl sulfate (analytical grade, national drug group) as a surfactant was added; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 4h at 200W; centrifuging the liquid after ultrasonic treatment at 2000r/min for 10min, taking out suspension with iron concentration of 25g/Kg and iron particle size D₉₀Is 10 nm;

40g of SAPO-11 molecular sieve powder (same as in example 1) was mixed with 40g of deionized water and wet ball milled into a slurry having a particle diameter D₉₀5 microns; then, 400g of the suspension is added into the whole molecular sieve slurry; stirring for 10 min; pre-freezing the slurry at-40 ℃, and then drying the slurry for 24 hours at-30 ℃ under 20Pa vacuum, wherein the final product is the SAPO-11 molecular sieve wrapped with the iron metal membrane, the modified molecular sieve is marked as ZA2, the thickness of the metal membrane is 15nm, and the iron content accounts for 20 wt% of the total weight of the modified molecular sieve.

(3) Preparation of regular Supported catalysts

A section with the diameter of 30mm and the length of 50mm is cut out of ZT2, slurry (solid content is 35 weight percent) is prepared by ZA2 and water, ZT2 is coated by the slurry of ZA2, the drying is carried out for 2 hours at 120 ℃, the baking is carried out for 2 hours at 450 ℃, and the coating is repeated for 1 time, so that the regular carrier catalyst is obtained and is marked as A2. Composition of the structured catalyst a 2: based on the dry weight of a2, the catalyst contained cordierite 80 wt%, zinc oxide 1 wt%, alumina 2 wt%, molecular sieve 13.6 wt%, and metallic iron 3.4 wt%.

Example 3

(1) Preparing a structured carrier containing a matrix: reference example 1, denoted ZT 3; wherein, the weight ratio of cordierite: zinc oxide weight ratio 75:4, cordierite: 75:6 weight ratio of alumina;

(2) preparing a modified molecular sieve:

30g of cobalt powder (average particle size 5 μm, purity 99%, gumbo) and 150ml of ethylene glycol (same as used in example 1) were added to a 250ml jar, mixed well, and 200mg of stearic acid (purchased from gumbo, purity AR) as a surfactant was added; then, putting the mixture into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 10 hours at the power of 280W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 30min, and taking out the suspension; co concentration in the suspension 10g/Kg, particle size D of Co₉₀Is 4 nm;

17 g of SAPO-11 molecular sieve powder (same as in example 1) was mixed with 60 g of deionized water and wet ball milled into a slurry having a particle diameter D₉₀5 microns; then 300g of the above suspension was added thereto; stirring for 10 min; pre-freezing the slurry at-40 deg.C, and drying at-30 deg.C under 50Pa pressure (absolute pressure) for 48h to obtain final product, i.e. SAPO-11 molecular sieve coated with cobalt metal membrane, wherein the modified molecular sieve is ZA3, the thickness of the metal membrane is 10nm, and the metal content is 15 wt%. D of modified molecular sieve ZA3₉₀Is 5 microns.

(3) Preparation of regular Supported catalysts

Will be provided with

ZT3 (g) was coated with a slurry of ZA3 (30 wt% solids), dried at 130 ℃ for 1 hour, calcined at 450 ℃ for 2 hours, and coated twice to give a structured supported catalyst, designated as A3.

Composition of a 3: based on the dry weight of a3, the catalyst contained 75 wt% cordierite, 4 wt% zinc oxide, 6 wt% alumina, 12.75 wt% molecular sieve, and 2.25 wt% metallic cobalt.

Example 4

This example serves to illustrate the desulfurization catalyst of regular structure and the preparation method thereof according to the present invention.

(1) Preparation of the structured Carrier containing the matrix: referring to example 1, the difference is that magnesium oxide (product of Beijing chemical plant, particle diameter d)₉₀Is 500 nm; ) Instead of said oxidationZinc powder;

(2) attaching a modified molecular sieve: referring to example 1, except that the matrix-containing structured carrier obtained in the foregoing step (1) was used in place of the matrix-containing structured carrier prepared in step (1) of example 1;

composition of the structured catalyst a 4:

the a4 contained, by dry weight, cordierite 70 wt%, magnesia 2.5 wt%, alumina 2.5 wt%, molecular sieve 22.5 wt%, and metallic nickel 2.5 wt%.

Example 5

(1) Preparation of the structured Carrier containing the matrix: referring to example 1, the difference is that calcium oxide (product of Beijing chemical plant, particle diameter d) is used₉₀Is 200 nm; ) Replacing said zinc oxide powder;

(2) attaching a molecular sieve coating: referring to example 1, except that the catalyst support obtained in the foregoing step (1) was used in place of the catalyst support prepared in step (1) of example 1;

composition of desulfurization catalyst a5 with regular structure:

based on the dry weight of a5, the catalyst contained cordierite 70 wt%, calcium oxide 2.5 wt%, alumina 2.5 wt%, molecular sieve 22.5 wt%, and metallic nickel 2.5 wt%.

Example 6

(1) Preparation of the structured Carrier containing the matrix:

the preparation method of ZT1 in example 1 was the same.

(2) Attaching a modified metal film:

adding 450g of nickel-tungsten alloy fine powder (sourced from Tianjin Hainan alloy Co., Ltd., weight ratio of nickel to tungsten is 3: 2) and 500ml of water into a 1000ml wide-mouth bottle, uniformly mixing, and adding 2.8g of surfactant sodium glycocholate (sourced from Nanjing Paersi Biotech Co., Ltd., purity AR); then, placing the wide-mouth bottle in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at the power of 150W; centrifuging the liquid after ultrasonic treatment at 1500r/min for 20min, and taking out the suspension; the weight ratio of nickel to tungsten in the suspension is 3: 2;

14.5 grams of SAPO-11 molecular sieve powder (the same SAPO-11 molecular sieve powder used in example 1), with 10 grams of deionized waterMixing, wet ball milling to slurry with particle diameter D₉₀5 microns; adding 100g of the suspension into the molecular sieve slurry; stirring for 10 min; pre-freezing the mixed slurry of the molecular sieve and the suspension at-10 ℃, and drying at-5 ℃ under 50Pa (absolute pressure) for 24h to obtain a final product, namely the SAPO-11 molecular sieve wrapped with the nickel-tungsten bimetallic membrane, which is recorded as ZA 6; the thickness of the metal film is 10nm, and the total content of modified metal Ni and W is 20 wt%;

(3) preparation of regular Supported catalysts

Get

Coating the regular carrier ZT1 containing matrix with slurry (solid content is 35 wt%) prepared from ZA6 and water, drying at 120 deg.C for 2 hr, calcining at 350 deg.C for 3 hr, and repeating twice to obtain the final product, namely the regular carrier catalyst, which is marked as A6.

Composition of a6 dry basis: the catalyst contained 70 wt% of cordierite, 2.5 wt% of zinc oxide, 2.5 wt% of alumina, 20 wt% of molecular sieve, 3 wt% of metallic nickel and 2 wt% of metallic tungsten.

Example 7

Adding 50g of nickel-titanium alloy fine powder (purity 98%, nickel-titanium weight ratio 3:1, Luoyang Tongzhong information technology Co., Ltd.) and 300ml of water into a 500ml wide-mouth bottle, mixing uniformly, and adding 120mg of surfactant lauryl sodium sulfate (purity AR); then, the mixture is placed in an ultrasonic cleaning machine and is subjected to ultrasonic treatment for 4 hours at the power of 240W; centrifuging the liquid after ultrasonic treatment in a centrifuge at 3000r/min for 10min, and taking out the suspension; the concentration of metallic nickel and titanium in the suspension was 25g/Kg, D₉₀Is 4 nm;

42.5 g of SAPO-11 molecular sieve powder (the same SAPO-11 powder used in example 1) was mixed with 35g of deionized water and wet ball milled into a slurry having a particle diameter D₉₀5 microns); the slurry was added in its entirety to the above 300g of suspension; stirring for 10 min;

freezing the obtained slurry at-20 ℃, and then drying the slurry at-10 ℃ under the pressure of 30Pa for 24h to obtain the SAPO-11 molecular sieve which is coated with the nickel-titanium metal membrane and is marked as ZA 7. ZA7 metal film with a thickness of 9nm15 percent of total metal content of the metal, the weight ratio of Ni to Ti is 3:1, and the modified molecular sieve D₉₀Is 5 microns.

Will be provided with

The regular carrier ZT2 containing the matrix is coated with slurry (solid content is 35 wt%) formed by ZA7 and water, dried for 2 hours at 120 ℃, roasted for 2 hours at 400 ℃, and the process is repeated for 2 times, so that the content of the modified molecular sieve in the product is 17 wt%, and the regular carrier catalyst is recorded as A7.

On a dry basis, a7 contained 80 wt% cordierite, 1 wt% zinc oxide, 2 wt% alumina, 15 wt% molecular sieve, 1.5 wt% metallic nickel, and 0.5 wt% metallic titanium.

Example 8

Adding 30g of nickel-aluminum alloy fine powder (nickel-aluminum weight ratio is 4:1, average particle size is 20 μm, sourced from Nanjing chemical reagent Co., Ltd.) and 150ml of water into a 250ml wide-mouth bottle, uniformly mixing, and adding 200mg of surfactant stearic acid (carbon chain length is 18, sourced from Aladdin chemical reagent Co., Ltd., purity is 99.5%); then, carrying out ultrasonic treatment for 10h in an ultrasonic cleaning machine at the power of 210W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 30min, and taking out the suspension; the total concentration of metallic nickel and aluminium in the suspension was 20g/Kg, D₉₀Is 6 nm.

17 g of SAPO-11 molecular sieve powder (D)₉₀14 micron, technical grade, product of the middle petrochemical catalyst, zilu division), mixed with 30 grams of deionized water, wet ball milled to a slurry with a particle diameter D₉₀5 microns; then 150g of the above suspension was added thereto; stirring for 10 min;

the slurry was frozen at-65 ℃ and dried at-60 ℃ under 20pa for 36h to give a modified molecular sieve designated ZA 8. ZA8 has a metal film thickness of 10nm, a total content of nickel and aluminum modified metal of 15 wt%, a weight ratio of nickel to aluminum in the modified metal of 4:1, D₉₀Is 5 microns.

Will be provided with

The regular carrier ZT3 containing the matrix is coated with slurry (solid content is 30 wt%) formed by ZA8 and water, dried for 2 hours at 120 ℃, roasted for 2 hours at 450 ℃, and coated twice repeatedly, so that the modified molecular sieve content in the final product is 15 wt%, and the final product, namely the regular carrier catalyst, is marked as A8.

Based on the dry weight of the desulfurization catalyst A8 with a regular structure, the desulfurization catalyst A contained 75 wt% of cordierite, 4 wt% of zinc oxide, 6 wt% of alumina, 12.75 wt% of a molecular sieve, 2.25 wt% of the total content of metallic nickel and aluminum, and a weight ratio of nickel to aluminum of 4: 1.

Example 9

Adding 10g of iron-nickel alloy fine powder (iron-nickel weight ratio 2:1, average particle size 15 μm, purity 98 wt% from south-palace Ruiteng alloy materials Co., Ltd.) and 100ml of glycerol (analytical grade) into a 200ml wide-mouth bottle, mixing uniformly, and adding 60mg of surfactant sodium glycocholate (purity AR from Nanjing Parls Biotech Co., Ltd.); then, putting the wide-mouth bottle into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at 160W power; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 20min, and taking out the suspension; the total concentration of metallic iron and nickel in the suspension is 25g/Kg, the weight ratio of iron to nickel is 2:1, D₉₀Is 5 nm;

mixing 11.3 g of SAPO-11 molecular sieve powder (also in example 1) with 10g of deionized water, and wet ball-milling to obtain slurry, wherein the particle diameter d90 is 5 microns; then adding the whole into 100g of the suspension; stirring for 10 min; obtaining slurry JY-7;

and freezing the slurry JY-7 at-20 ℃, and drying at-15 ℃ and 30Pa (absolute pressure) for 24h to obtain a final product, namely the SAPO-11 molecular sieve wrapped with the iron-nickel bimetallic membrane, which is recorded as ZA 9. The ZA9 metal film had a thickness of 12nm, a total iron and nickel modified metal content of 18 wt%, and a weight ratio of iron to nickel in the modified metal of 2: 1. D of modified molecular sieve ZA9₉₀Is 5 microns.

Will be provided with

The matrix-containing structured carrier ZT1 was coated with a slurry of ZA9 and water (35% by weight solids) ZT1, 1Drying at 20 ℃ for 2 hours, roasting at 450 ℃ for 2 hours, and repeatedly coating for 2 times to enable the weight of the modified molecular sieve in the product to account for 25 wt%, thereby obtaining the regular carrier catalyst, which is recorded as A9.

A9 contained cordierite 70 wt%, zinc oxide 2.5 wt%, alumina 2.5 wt%, molecular sieve 20.5 wt%, metallic iron 3 wt%, and metallic nickel 1.5 wt%, based on the dry weight.

Example 10

Adding 50g of iron-cobalt alloy fine powder (iron-cobalt weight ratio of 3:1, average particle size of 12 microns, purity of 99% from Kaixin alloy materials Co., Ltd., Danyang) and 300ml of glycerol (analytically pure) into a 500ml wide-mouth bottle, uniformly mixing, and adding 120mg of surfactant sodium dodecyl sulfate (analytically pure); then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 4h at the power of 180W; centrifuging the liquid subjected to ultrasonic treatment at 2000r/min for 10min, and taking out the suspension; the total concentration of metallic iron and cobalt in the suspension was 20g/Kg, the weight ratio of iron to cobalt was 3:1, D₉₀Is 4 nm;

a powder of SAPO-11 molecular sieve (same as the SAPO-11 molecular sieve used in example 1) 24 g was mixed with deionized water 10g, wet ball milled into a slurry having a particle diameter D₉₀5 microns; then 300g of the suspension is added into the solution and stirred for 10 min;

freezing the slurry at-20 deg.C, and vacuum drying at-15 deg.C under 20Pa for 30h to obtain final product, namely SAPO-11 molecular sieve coated with Fe-Co membrane, wherein the modified molecular sieve is ZA 10. The total content of the modified metal of iron and cobalt is 20 wt%, and the weight ratio of iron to cobalt in the modified metal is 2:1, ZA 10D₉₀Is 5 microns.

ZT2(

I.e., 30mm in diameter and 50mm in height) was coated with a slurry of ZA10 and water (35% by weight solids), dried at 120 ℃ for 2 hours, calcined at 450 ℃ for 2 hours, and coated repeatedly 2 times to make the modified molecular sieve 17% by weight, the final product being a structured support catalyst, designated a 10.

On a dry basis, a10 contained 80 wt% of cordierite, 1 wt% of zinc oxide, 2 wt% of alumina, 13.6 wt% of molecular sieve, 2.55 wt% of metallic iron, and 0.85 wt% of metallic cobalt. .

Example 11

Adding 30g of iron-magnesium alloy fine powder (iron-magnesium weight ratio is 4:1, average particle size is 16 microns, source Anyang, Jinding iron alloy Co., Ltd., purity is 99.5%) and 150ml of glycerol into a 250ml wide-mouth bottle, uniformly mixing, and adding 200mg of surfactant stearic acid; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 10 hours at the power of 280W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 30min, and taking out the suspension; the total concentration of metallic iron and cobalt in the suspension was 18g/Kg, the weight ratio of iron to magnesium was 4:1, D₉₀Is 5 nm;

22.3 g of SAPO-11 molecular sieve powder (the same SAPO-11 molecular sieve used in example 1) was mixed with 10g of deionized water and wet ball-milled into a slurry having a particle diameter D₉₀5 microns; then 150g of the suspension is added into the mixture and stirred for 10 min;

freeze-drying the above slurry for 24h at-25 deg.C under 50Pa (i.e. drying under-25 deg.C and 50Pa for 24 hr); the final product is SAPO-11 molecular sieve wrapping the iron-magnesium alloy membrane, the modified molecular sieve is marked as ZA11, wherein the total content of iron and magnesium modified metal is 10.8 wt%, and the weight ratio of iron to magnesium in the modified metal is 4:1, D of modified molecular sieves₉₀Is 5 microns.

Get

ZT3 (g), coated with a slurry of ZA11 and water, dried at 120 ℃ for 2 hours, calcined at 450 ℃ for 2 hours, and coated repeatedly such that the weight of modified molecular sieve in the coated product on a dry basis is 15 wt%, a structured supported catalyst, designated as a11, containing, by dry weight, 75 wt% cordierite, 4 wt% zinc oxide, 6 wt% alumina, 13.4 wt% molecular sieve, 1.3 wt% metallic iron, and 0.3 wt% metallic magnesium was obtained.

Example 12

10g of cobalt molybdenum alloy was added to a 200ml jarMixing fine powder (weight ratio of cobalt to molybdenum 3:1, average particle diameter 10 μm, purity 99% from Tianjin kenna Metal materials Co., Ltd.) with 100ml of methanol-water mixture (methanol content 50 vol%), mixing, and adding 60mg of surfactant sodium glycocholate; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at the power of 320W; centrifuging the liquid after ultrasonic treatment at 1500r/min for 20min, and taking out the suspension; the total concentration of metallic cobalt and molybdenum in the suspension was 45g/Kg, the weight ratio of cobalt to molybdenum was 3: 2, D₉₀Is 6 nm;

18g of SAPO-11 molecular sieve powder (the same SAPO-11 molecular sieve used in example 1) was mixed with 20g of deionized water and wet ball milled into a slurry having a particle diameter D₉₀5 microns; then 100g of the above suspension was added thereto; stirring for 10 min; finally, freeze-drying the slurry for 24h, wherein the freeze-drying temperature is-30 ℃, and the absolute pressure is 50 Pa; the final product is SAPO-11 molecular sieve wrapped with cobalt-molybdenum bimetallic membrane, and is marked as ZA 12. ZA12 having a total cobalt and molybdenum modified metal content of 20 wt%, the weight ratio of cobalt to molybdenum in the modified metal being 3:1, D₉₀Is 5 microns.

Intercepting

ZT1 (g), coated with a slurry of ZA12 and water (35 wt% solids), dried at 120 ℃ for 2 hours, calcined at 450 ℃ for 2 hours, and coated 2 times so that the weight of the modified molecular sieve is 25 wt% of the final product, i.e., the structured supported catalyst, is designated as a 12. A12 contained, on a dry basis, cordierite 70 wt%, zinc oxide 2.5 wt%, alumina 2.5 wt%, molecular sieve 20 wt%, and metallic cobalt and molybdenum 5 wt%, combined, wherein the cobalt and molybdenum were present in a 3:1 weight ratio.

Example 13

A regular supported catalyst was prepared by the method of reference example 1 except that a suspension was prepared using cobalt titanium alloy powder (cobalt titanium weight ratio 1:1, average particle diameter 15 μm, available from Tianjin kenna metallic materials Co., Ltd., purity 99.5%).

To a 500ml jar was added 50g of cobalt-titanium alloy fine powder and 300ml of a mixture of methanol and water (methanol content 50 vol%)Mixing uniformly, and then adding 120mg of surfactant lauryl sodium sulfate; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 4h at the power of 450W; centrifuging the liquid subjected to ultrasonic treatment for 10min at 2000r/min, and taking out the suspension; the total concentration of metallic cobalt and titanium in the suspension was 30g/Kg, the weight ratio of cobalt to titanium was 1:1, D₉₀Is 5 nm;

36 g of SAPO-11 molecular sieve powder (the same SAPO-11 molecular sieve used in example 1) was mixed with 30g of deionized water, wet ball milled into a slurry having a particle diameter D₉₀5 microns; then 300g of the above suspension was added thereto; stirring for 10 min;

freeze-drying the slurry for 30h at-30 deg.C under 20 Pa; obtaining a final product, namely the modified molecular sieve, and recording the final product as ZA13, wherein the total content of the cobalt and titanium modified metals is 20 wt%, and the weight ratio of the cobalt to the titanium in the modified metals is 1:1, D₉₀Is 5 microns.

Intercepting

ZT2 of (1), coated with a slurry of ZA13 and water (30% by weight solids), dried at 110 ℃ for 2 hours, calcined at 350 ℃ for 2 hours, and coated repeatedly 2 times to give a structured supported catalyst, designated A13. On a dry basis, a13 contained 80 wt% of cordierite, 1 wt% of zinc oxide, 2 wt% of alumina, 13.6 wt% of molecular sieve, 1.7 wt% of metallic cobalt, and 1.7 wt% of metallic titanium.

Example 14

A structured supported catalyst was prepared by the method of reference example 1, except that cobalt-gallium alloy powder (cobalt-gallium weight ratio 4:1, average particle diameter 10 μm, available from Tianjin kenna metals Co., Ltd., purity 99%) was used, and the preparation process parameters are shown in Table 2, which is not described in reference example 1.

30g of cobalt-gallium alloy fine powder and 150ml of a mixture of methanol and water (methanol content: 50 vol%) were added to a 250ml jar, mixed uniformly, and 200mg of stearic acid as a surfactant was added; then, placing the reaction container in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 10 hours at the power of 240W; centrifuging the liquid at 1500r/min for 30min, taking out and suspendingFloating liquid; the total concentration of metallic cobalt and gallium in the suspension was 35g/Kg, the weight ratio of cobalt to gallium was 4:1, D₉₀Is 5 nm;

a powder of SAPO-11 molecular sieve 29.75 g (same as SAPO-11 molecular sieve of example 1) was mixed with deionized water 30g, wet ball milled to a slurry of particle diameter D₉₀5 microns; then 150g of the above suspension was added thereto; stirring for 10 min; freeze-drying for 24h at-35 deg.C under 30Pa (absolute pressure); obtaining a modified molecular sieve, which is recorded as ZA14, wherein the total content of the cobalt and gallium modified metal is 15 wt%, and the weight ratio of cobalt to gallium in the modified metal is 4: 1. particle diameter D of modified molecular sieves₉₀Is 5 microns.

Intercepting

Coating ZT3 with ZA14 and water to form slurry (solid content is 35 wt%), drying at 120 deg.C for 2 hours, calcining at 450 deg.C for 2 hours, and repeating coating for 2 times (the repeating coating means performing the coating, drying and calcining processes) to obtain the regular carrier catalyst of the invention, which is marked as A14; the catalyst contains 75 wt% of cordierite, 4 wt% of zinc oxide, 6 wt% of alumina, 10 wt% of molecular sieve, 4 wt% of metallic cobalt and 1 wt% of metallic gallium.

Example 15

A structured carrier catalyst was prepared as in example 1, except that a Sn-Sb alloy powder was used, wherein Sn: sb 2:1 weight ratio. The resulting catalyst was designated A15.

Example 16

A structured supported catalyst was prepared as in example 1, except that an alloy powder having a Ti-Zr-V ratio of 1:1:0.5 was used. The regular carrier catalyst A16 was obtained.

Example 17

A structured carrier catalyst was prepared as in example 1, except that a Sb-Bi-Cu alloy powder was used in a Sb-Bi-Cu weight ratio of 5:4: 1. The regular carrier catalyst A17 was obtained.

Application example

For examples 1 to 17 according to the present invention, comparative example1 and comparative example 1 modified sieves A1-A17, DB1 and BJ1 prepared by the method adopt a fixed bed micro-reaction experimental facility to carry out desulfurization evaluation experiments, and the specific method comprises the following steps: a regular carrier catalyst (may also be referred to as a desulfurization catalyst) was packed in a fixed bed reactor having an inner diameter of 30mm and a length of 1 m. Hydrogen is used as hydrogen supplying medium, the reaction temperature is 300 ℃, the reaction pressure is 1.38Mpa, the hydrogen-oil ratio is 100, and the weight space velocity of the raw material hydrocarbon oil is 4h^-1Under the reaction conditions of (1), a desulfurization reaction of the sulfur-containing hydrocarbon oil is carried out. The raw material hydrocarbon oil is gasoline, the composition is shown in table 1, and the reaction result is shown in tables 2-4.

TABLE 1

Item	Analyzing data	Item	Analyzing data
				Density (20 ℃ C.) (kg.m)^-3)	727.3	Induction phase (min)	922
Actual gum (mg/mL)	0.34	Distillation range (. degree.C.)
				Refractive index (20 ℃ C.)	1.4143	Initial boiling point	38.5
Sulfur content (ng./. mu.L)	960.48	5％	49.0
				Mercaptan sulfur content (ng/. mu.L)	10.2	10％	55.5
Hydrogen sulfide content (ng/. mu.L)	0	30％	74.7
				Octane number (RON/MON)	93.7/83.6	50％	97.2
Group composition volume (%)		70％	124.2
				Saturated hydrocarbons	44.0	90％	155.2
Olefins	41.2	95％	165.2
				Aromatic hydrocarbons	14.8	End point of distillation	185.0

TABLE 2

TABLE 3

TABLE 4

Note: in tables 2 to 4:

1. the feed gasoline had a sulfur content of 960ppm, a RON of 93.7 and a MON of 83.6.

2.△ MON indicates an increased value of product MON;

3.△ RON indicates an increased value of product RON;

4.△ (RON + MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.

5. The sulfur content of the samples at each time point is the sulfur content of the samples collected within one hour before the sampling time point, and the gasoline composition and octane number are the average values of the analysis results of each sample.

From the results data of tables 2 to 4, it can be seen that:

after the regular carrier catalysts A1-A17 prepared in examples 1-17 are used as catalysts for gasoline desulfurization treatment, the sulfur content in a gasoline product is lower than 0.5ppm (chromatographic detection limit) in the initial reaction stage, and the sulfur content in the product is increased along with the reaction time, but after the reaction of 240-960 h, the sulfur content in the gasoline product can still be lower than 10ppm, and in some cases, even lower than 5ppm, and the gasoline octane number is improved. The gasoline yield is higher.

Claims

1. The regular carrier catalyst with the desulfurization function is characterized by comprising a regular carrier and an active coating attached to the outer surface of the regular carrier, wherein the active coating comprises a IIA and IIB group metal oxide matrix, a molecular sieve and a modified metal film, the modified metal film comprises modified metal, and the modified metal is one or more of Fe, Co, Ni, Mn, Ti, Zr, V, Ge, Pb, Sn, Sb and Bi.

2. The structured support catalyst of claim 1 wherein the modified metal membrane is on the outer surface of the molecular sieve particles and/or the outer surface of the matrix particles and/or the outer surface of the particles comprising the molecular sieve and the matrix, and the modified metal membrane has a thickness of 5 to 30 nm.

3. The structured catalyst of claim 1 wherein the active coating comprises from 5 to 50 wt.% and the structured support comprises from 50 to 95 wt.% on a dry basis, based on the total weight of the structured catalyst.

4. The structured supported catalyst of claim 1 wherein the active component coating comprises, on a dry basis, 4 to 50 weight percent of the matrix, 30 to 95 weight percent of the molecular sieve, and 1 to 25 weight percent of the modified metal film, based on the total weight of the active component coating; preferably, the modified metal film is positioned on the outer surface of the molecular sieve particles, the thickness of the modified metal film on the outer surface of the molecular sieve particles is 5-30 nm, and the modified metal accounts for 8-21 wt% of the total weight of the molecular sieve and the modified metal on a dry basis;

on a dry basis, the total content of the oxides of the IIA and IIB metals in the matrix is 5-100 wt%, and other matrix components are contained or not contained, wherein the content of the other matrix components is 0-95 wt%; other matrix components are, for example, one or more of an alumina matrix, a silica matrix, a zirconia matrix, a titania matrix, a silica-alumina matrix; the oxides of the IIA and IIB metals are one or more of calcium oxide, magnesium oxide and zinc oxide;

the regular structure carrier is an integral carrier with a parallel pore channel structure with openings at two ends.

5. A structured carrier catalyst according to any of claims 1 to 4 wherein the modifying metal comprises a first metal selected from one or more of Fe, Co, Ni, Mn, Ti, Zr, Pb, Ge, Sn and optionally a second metal selected from one or more of V, Sb, Bi, preferably in a weight ratio of the second metal to the first metal of from 0 to 1: 1.

6. A structured support catalyst according to claim 5,

the first metal is one or more of Fe, Co, Ni and Mn, optionally contains one or more of Ti, Zr, Pb, Ge and Sn, and the ratio of one or more of Fe, Co, Ni and Mn to one or more of Pb, Ge and Sn is 0.5-2: 0-1; alternatively, the first and second electrodes may be,

the modified metal comprises a first metal and an optional second metal, wherein the first metal is one or more of Pb, Ge and Sn, the second metal is one or more of Sb and Bi, and the weight ratio of the second metal to the first metal is 0.2-1: 1; alternatively, the first and second electrodes may be,

in a third embodiment, the first metal is Ti and/or Zr and the optional second metal is preferably V, preferably, Ti: Zr: the weight ratio of V is (0.8-1.2): 0.4-0.6); alternatively, the first and second electrodes may be,

the modified metal film comprises a third element, and the third element is selected from one or more of Cr, Mo, W, Cu, Ag, Au, Al, Ga, Mg and B; the weight ratio of the second metal to the first metal is 0-1: 1, and the weight ratio of the third element to the first metal is 0-1: 1.

7. A method for preparing a structured carrier catalyst comprises the following steps: forming a mixture of metal powder, a hydroxyl-containing solvent and a surfactant, and then treating under ultrasonic waves to obtain an ultrasonic mixed solution; separating the mixed solution after ultrasonic treatment to obtain a suspension; and then coating the substrate containing the modified metal membrane and/or the molecular sieve containing the modified metal membrane or the particles containing the substrate and the molecular sieve containing the modified metal membrane on a regular carrier to obtain the regular carrier catalyst.

8. A process for preparing a structured carrier catalyst as claimed in claim 7, wherein the concentration of the modifying metal in the suspension is 5 to 45 g/Kg.

9. Process for the preparation of a modified structured support catalyst according to claim 7 or 8, wherein the particles in the suspension have a size D₉₀Is 20nm or less.

10. A process for preparing a structured carrier catalyst as claimed in claim 7, wherein the weight ratio of the hydroxyl-containing solvent to the metal powder is from 2 to 15: 1.

11. the process for preparing a structured carrier catalyst according to claim 7 or 10, wherein the ratio of the surfactant to the hydroxyl group-containing solvent is 0.001 to 100 mg/mL.

12. The preparation method of the structured carrier catalyst according to claim 7, wherein the ultrasonic treatment is carried out under the condition that the power of ultrasonic waves is 10-500W relative to 100ml of solvent, and the frequency of the ultrasonic waves is 20-100 KHz; the time of ultrasonic treatment is 3-15 hours.

13. A process for preparing a structured support catalyst according to claim 7, wherein the metal powder has an average diameter of less than 20 μm.

14. A process for preparing a structured support catalyst as defined in claim 7 or 13 wherein the metal powder is one or more of a pure metal powder or a metal alloy powder; the metal powder is metal alloy powder, pure metal powder or a mixture of a plurality of the metal alloy powder and the pure metal powder; the pure metal powder is one or more of Fe powder, Co powder, Ni powder, Mn powder, Ti powder, Zr powder, V powder, Sn powder, Sb powder and Bi powder; the alloy powder is an alloy formed by a plurality of Fe, Co, Ni, Mn, Ti, Zr, V, Sn, Sb and Bi, or an alloy formed by one or more of Fe, Co, Ni, Mn, Ti, Zr, V, Sn, Sb and Bi and one or more of third elements.

15. A process for preparing a structured carrier catalyst as claimed in claim 7 wherein the surfactant is an anionic, cationic or amphoteric surfactant; for example, one of sodium glycocholate, sodium dioctyl sulfosuccinate, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, sodium lauryl sulfate, stearic acid, oleic acid, lauric acid, fatty acid amine, cetyl trimethyl ammonium bromide, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, fatty acid methyl ester, and polyoxyethylene ether.

16. A process for preparing a structured support catalyst according to claim 7 wherein the hydroxyl-containing solvent is water and/or a hydroxyl-containing organic solvent; preferably, the hydroxyl-containing organic solvent is monohydric alcohol, dihydric alcohol, trihydric alcohol or their derivatives, the monohydric alcohol is one or more of methanol and ethanol, the dihydric alcohol is ethylene glycol, the dihydric alcohol derivatives are ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether and ethylene glycol ether, the trihydric alcohol is glycerol, and the trihydric alcohol derivatives are triethanolamine.

17. A process for preparing a structured carrier catalyst according to claim 7, wherein the separation is carried out by centrifugation at a rotational speed of 1200 to 3000 r/min.

18. A process for preparing a structured carrier catalyst as claimed in claim 7, wherein the freeze-drying is carried out by sublimation drying at low temperature and under high vacuum, the drying temperature being below the freezing point of the hydroxyl-containing solvent.

19. A process for preparing a structured support catalyst according to claim 7,

on the basis of the total weight of the structured carrier catalyst, the structured carrier catalyst comprises 10-50 wt% of an active coating and 50-90 wt% of a structured carrier on a dry basis;

the active coating comprises a substrate coating, a molecular sieve and a modified metal film, wherein the content of the molecular sieve is 30-95 wt%, the content of the substrate is 4-50 wt%, and the content of the modified metal film is 1-25 wt% on a dry basis based on the total weight of the active coating.

20. A method for preparing a structured carrier catalyst according to claim 7, 8, 9 or 20, wherein the modified metal content of the matrix particles containing the modified metal film is 10 to 20 wt%; in the molecular sieve particles containing the modified metal film, the content of modified metal is 10-20 wt%; the content of the modified metal in the particles containing the matrix and the molecular sieve and containing the modified metal film is 10-20 wt%.

21. The preparation method of the structured carrier catalyst according to claim 7, 18 or 20, wherein the modified metal film covers the outer surface of the molecular sieve particles, the thickness of the modified metal film on the outer surface of the molecular sieve particles is 5-30 nm, and the content of the modified metal accounts for 10-20 wt% of the total weight of the molecular sieve and the modified metal.

22. A process for the preparation of a structured support catalyst according to any of claims 7 to 22, wherein the process is a first or second or third or fourth embodiment as follows:

a first embodiment, comprising the steps of:

s1, contacting the suspension with a molecular sieve, and freeze-drying to obtain the modified molecular sieve; wherein the particle diameter d90 of the molecular sieve is 1-10 microns;

the second embodiment comprises the following steps:

s1, contacting the suspension with the molecular sieve, and freeze-drying to obtain the modified molecular sieve; wherein the particle diameter d90 of the molecular sieve is 1-10 microns;

the third embodiment comprises the following steps:

s1, mixing the matrix source and the molecular sieve, drying, optionally roasting, and preparing D₉₀Particles containing a matrix and a molecular sieve and having a particle size of not more than 1-10 μm; the substrate source comprises an oxide of at least one metal of groups IIA and IIB and/or an oxide precursor of at least one metal of groups IIA and IIB and optionally a source of a refractory inorganic oxide;

a fourth embodiment, comprising the steps of:

s1, forming the matrix source into slurry, drying, molding, roasting, and grinding to obtain D₉₀Substrate particles of no more than 1-10 microns; the substrate source comprises an oxide of at least one metal of groups IIA and IIB and/or an oxide precursor of at least one metal of groups IIA and IIB and optionally a source of a refractory inorganic oxide;

optionally S3, contacting the molecular sieve with the suspension, and freeze-drying to obtain molecular sieve particles containing the modified metal film; molecular sieve D₉₀No more than 1-10 microns;

s4, respectively forming slurry or mixing the matrix particles containing the modified metal film and the molecular sieve particles or the matrix particles containing the modified metal film and the molecular sieve particles containing the modified metal film to form slurry to coat the regular carrier, and optionally drying and optionally roasting to obtain the regular carrier catalyst.

23. A process for preparing a structured support catalyst according to claim 22,

in the steps of the first embodiment, the second embodiment, the third embodiment and the fourth embodiment, the baking temperature is 200 to 600 ℃ and the baking time is 1 hour or more.

24. A method for preparing a structured carrier catalyst as claimed in any one of claims 22 to 23 wherein the source of heat resistant inorganic oxide is an alumina source and the weight ratio of the alumina source, expressed as alumina, to the oxide of at least one metal from groups IIA or IIB, expressed as oxide is 40 to 75: 25-60.

25. A method for preparing a structured carrier catalyst according to any of claims 7 to 24, wherein the molecular sieve is one or more of a large pore zeolite, a medium pore zeolite and a non-zeolite molecular sieve; the large-pore zeolite is selected from one or more of L zeolite, Beta zeolite, mordenite and ZSM-18 zeolite; the medium pore zeolite is selected from one or more of ZSM-5 zeolite, ZSM-22 zeolite, ZSM-23 zeolite, ZSM-35 zeolite, ZSM-50 zeolite, ZSM-57 zeolite, MCM-22 zeolite, MCM-49 zeolite and MCM-56 zeolite, and is one or more of SAPO-11, SAPO-34 and SAPO-31.

26. A desulfurization method of sulfur-containing hydrocarbon comprises the step of carrying out contact reaction on a hydrocarbon material containing sulfur compounds, a hydrogen donor and the structured carrier catalyst as described in any one of claims 1 to 6, wherein the reaction temperature is 150-350 ℃, the reaction pressure is 0.5-5 MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon is 0.1-100 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01 to 1000.