CN111085186A

CN111085186A - Regular carrier catalyst with desulfurization effect and preparation and application thereof

Info

Publication number: CN111085186A
Application number: CN201811239415.9A
Authority: CN
Inventors: 严加松; 王鹏; 孙言; 宋海涛; 姜秋桥; 林伟; 田辉平
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: 2018-10-23
Filing date: 2018-10-23
Publication date: 2020-05-01

Abstract

A regular carrier catalyst with desulfurization function and its preparation and application, the regular carrier catalyst includes a regular carrier and an active coating attached to the surface of the regular carrier, the active coating includes a heat-resistant inorganic oxide matrix and a modified metal film, the modified metal film includes a modified metal, the modified metal is one or more of Cr, Mo, W, Cu, Ag and Au. 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; and (3) contacting the suspension with the matrix particles, freezing and drying to obtain the matrix particles containing the modified metal membrane, and then coating the matrix particles containing the modified metal membrane on a regular carrier to obtain the regular carrier catalyst. The catalyst has high desulfurization activity, good stability and high product yield, is used for gasoline desulfurization, and has small octane value loss.

Description

Regular carrier catalyst with desulfurization effect and preparation and application thereof

Technical Field

The invention relates to a modified molecular sieve 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.

Therefore, the invention provides the following technical scheme:

technical scheme 1. a structured carrier catalyst with desulfurization, wherein the structured carrier catalyst comprises a structured carrier and an active coating (also called an active component coating) attached to the surface of the structured carrier, the active coating comprises a heat-resistant inorganic oxide matrix and a modified metal film, the modified metal film comprises a modified metal, and the modified metal is one or more of Cr, Mo, W, Cu, Ag and Au.

Technical scheme 2. the structured carrier catalyst according to the technical scheme 1, wherein the modified metal film is positioned on the outer surface of the matrix particles, and the thickness of the modified metal film 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.

The technical scheme 4. the structured carrier catalyst according to any one of the technical schemes 1 to 3, wherein the active component coating contains 5 to 15 weight percent of modified metal film and 85 to 95 weight percent of matrix in terms of dry basis based on the total weight of the active component coating; preferably, the modified metal film comprises 8-15 wt% of modified metal film and 85-92 wt% of matrix;

a refractory inorganic oxide matrix, such as one or more of an alumina matrix, a silica matrix, a zirconia matrix, a titania matrix, and a silica-alumina matrix, such as kaolin and/or silica-alumina gel; the preferred refractory inorganic oxide matrix is alumina.

Technical solution 5. the structured carrier catalyst according to any one of technical solutions 1 to 4, wherein the structured carrier is an integral carrier (honeycomb carrier) having a parallel pore structure with openings at both ends; 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 Cr, Mo, W, Cu, Ag and Au, and optionally one or more second metals selected from Ge, Sn, Pb, Sb and Bi, preferably, the weight ratio of the second metal to the first metal is 0-1: 1 or 0-0.8: 1 or 0-0.5: 1 or 0 to 0.3: typically, the reactive coating comprises 5 to 15 wt%, such as 8 to 15 wt%, of the first metal and 0 to 10 wt%, such as 0 to 5 or 0 to 3 wt%, of the second metal.

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 matrix particles, freeze-drying to obtain matrix particles containing the modified metal membrane, and coating the matrix particles containing the modified metal membrane on a structured carrier to obtain the structured carrier catalyst, wherein the matrix particles preferably have a particle diameter d₉₀Not 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, 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 contains a first metal, the first metal is one or more of Cr, Mo, W, Cu, Ag, or Au, and the metal powder can be one or more of pure metal powder or metal alloy powder; the metal powder may be one or more of pure metal powders of Cr, Mo, W, Cu, Ag or Au, or an alloy containing a plurality of Cr, Mo, W, Cu, Ag and Au, or an alloy of one or more of Cr, Mo, W, Cu, Ag and Au with other metals, such as one or more of V, Ge, Pb, Sn, Sb and Bi, preferably, the weight ratio of the other metals to the first metal is not more than 1, such as 0-0.9: 1, such as 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 solution 17. the preparation method of the structured carrier catalyst according to any one of technical solutions 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 may be, for example, 10 to 30 minutes, for example, 15 to 20 minutes. The container used for centrifugal separation may be cylindrical or prismatic, and the ratio of the diameter to the height thereof is, for example, 0.1 to 1:1, or 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 50000Pa to 1Pa 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 12, 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 and a modified metal film, and the content of the substrate is 85-95 wt% and the content of the modified metal is 5-15 wt% in terms of dry basis by taking the total weight of the active coating as a reference; preferably, the content of the matrix is 85 to 92 wt%, and the content of the modified metal is 8 to 15 wt%.

Technical scheme 21. the method for preparing a structured carrier catalyst according to any one of technical schemes 7 to 12, wherein the step of coating the structured carrier with the matrix particles containing the modified metal film comprises the steps of coating the structured carrier with the matrix slurry containing the modified metal film, drying and roasting, wherein the drying temperature is from room temperature to 150 ℃, for example, from 80 ℃ to 120 ℃, and the drying time can be more than 1 hour, for example, from 2 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 method for preparing a structured carrier catalyst according to any one of claims 7 to 12, wherein the matrix particles are one or more of alumina particles, silica-alumina particles, zirconia particles, titania particles, or particles selected from alumina, silica and a plurality of alumina, zirconia and titania, preferably the matrix is alumina, such as one or more of γ -alumina, β -alumina, α -alumina, η -alumina, and κ -alumina, the alumina matrix particles are commercially available or are obtained by molding or grinding a material that can be converted into alumina under calcination conditions, such as hydrated alumina and/or alumina sol, the hydrated alumina is selected from one or more of boehmite, pseudo-boehmite, alumina trihydrate, and amorphous alumina, the silica-alumina is selected from one or more of clay, silica alumina source, hydrotalcite, bentonite, attapulgite, montmorillonite, bentonite, attapulgite, or montmorillonite, and attapulgite.

The technical scheme 23 is a desulfurization method of sulfur-containing hydrocarbon, which comprises the step of carrying out contact reaction on a hydrocarbon material containing a sulfur compound, a hydrogen donor and the structured carrier catalyst according to any one of technical schemes 1 to 6 or the structured carrier catalyst obtained according to any one of technical schemes 7 to 23, 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. Preferably, the 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 material is 1-10 h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.05 to 500.

Technical solution 24 the desulfurization method according to the technical solution 23, wherein the hydrogen donor may be one or more of hydrogen gas, hydrogen-containing gas, and hydrogen donor; the hydrogen gas can be supplied using a hydrogen-containing gas raw material of various purities, and the hydrogen gas content in the hydrogen-containing gas raw material is usually 30 vol% or more; hydrogen-containing gas such as one or more of catalytic cracking (FCC) dry gas, coking dry gas and thermal cracking dry gas, wherein 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 25. according to the desulfurization method of the technical scheme 23 or 24, 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 has small octane number loss compared with the existing desulfurization 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 under the same reaction temperature, can be operated for a long period and has small octane number loss 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 active washcoat in the structured support catalyst. 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 function comprises a regular carrier and an active coating, wherein the active coating comprises a matrix and a modified metal film (metal film for short), and the metal film is positioned on the outer surface of matrix particles. The metal film is attached to the outer surface of the matrix particle, and may cover part or all of the outer surface of the matrix particle, for example, the metal film may be a whole block or may be dispersed into multiple blocks on the outer surface of the matrix, and the blocks are continuous or spaced. The thickness of the metal film on the substrate particles 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 5-15 wt% of the modified metal and 85-95 wt% of the substrate, for example 8-15 wt% of the modified metal and 85-92 wt% of the substrate.

The regular carrier catalyst (also called regular structure catalyst) with the desulfurization function comprises a regular carrier (regular structure carrier), and can be used for providing a catalyst bed layer in a fixed bed reactor. The regular structure carrier can be a whole carrier block, a hollow pore channel structure is formed inside the regular structure 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 pores per square inch, preferably 100-400 pores 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 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. The metal powder (the relative content of the hydroxyl-containing solvent) is not particularly required, and the hydroxyl-containing solvent can contain the modified metal element with the required content after ultrasonic treatment, so the use amount of the metal powder can be excessive (exceeding the metal content in the suspension), preferably, the weight ratio of the hydroxyl-containing solvent to the metal powder is 2-15: 1, for example, 3-12: 1 or 5-10:1, and the content of the modified metal element with the required concentration in the hydroxyl-containing solvent can be ensured by controlling the time and the power of ultrasonic treatment.

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 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 matrix particles 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 seen in national standard GB/T19077-2016, particle size distribution laser diffraction method. (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 centrifugal separation, the rotation speed of the slow centrifugal separation is 1200-3000 r/min, preferably 1500-2500 r/min, and the time of the centrifugal separation is 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 suspensionAnd D₉₀Analysis can be performed using a nanoparticle analyzer, such as the Zetasizer NanoZSP nanoparticle analyzer from Malvern.

According to the preparation method of the regular carrier catalyst provided by the invention, the suspension and the matrix are uniformly mixed, and then are frozen and dried, usually, the mixture is frozen and then is 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 process for preparing the structured support catalyst of the present invention, the suspension may be contacted with the matrix particles by any method suitable for contacting solids with liquids. Such as mixing, spraying, soaking.

For the convenience of freezing and drying, the hydroxyl-containing solvent (solvent for short) with a high freezing point (freezing point) is preferably selected in the invention, preferably, the temperature of the solvent is not lower than-25 ℃, more preferably, the freeze drying is 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 5-8 h at the specific ultrasonic power of 50-250W/(100 g of hydroxyl-containing solvent) and preferably 100-150W/(100 g of hydroxyl-containing solvent), then carrying out centrifugal separation on the mixed liquid after ultrasonic treatment at the rotation speed of 1200-3000 r/min and preferably 1500-2500 r/min, and obtaining 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.

The first embodiment of the preparation method of the regular carrier catalyst provided by the invention comprises the following steps:

s1, mixing the particle diameter D₉₀Mixing the substrate particles with the particle size of 1-10 microns, such as 2-8 microns, preferably 2-5 microns, with the suspension, and freeze-drying to obtain a substrate containing the modified metal film;

s2, preparing a slurry (called coating slurry) from the matrix containing the modified metal film, coating the slurry on a regular structure carrier (also called a regular carrier), drying and roasting.

According to the preparation method of the regular carrier catalyst, the coating is carried out, so that the content of the active coating in the product obtained by coating is 10-50 wt%, preferably 15-30 wt%, and more preferably 20-30 wt% on a dry basis. The coating is carried out one or more times, preferably, each time after coating, drying and optionally roasting, and the roasting is carried out after the last coating, so that the content of the active coating in the obtained product meets the requirement.

According to the process for the preparation of the structured carrier catalysts of the present invention, the matrix particles can be purchased commercially or manufactured in house. The matrix particles are preferably alumina particles; a method for preparing alumina particles includes the following steps:

pulping, spray drying, forming and roasting an alumina source, wherein the alumina source 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. Preferably, the method further comprises a step of pretreating the alumina source, wherein the step of pretreating the alumina source comprises the steps of adding water to the alumina source, mixing 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. Pretreating an alumina source, preferably selecting the added acid solution from one or more of 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. The roasting temperature is 400-800 ℃, for example 500-700 ℃; the roasting time is at least 0.5 hour, for example, 1 to 10 hours.

According to the preparation method of the regular supported catalyst, the first embodiment has no special requirement on the solid content of the prepared coating slurry, however, the difficulty of coating the slurry can be increased due to the fact that the solid content of the slurry is too high, and the adhesion amount of each coating can be reduced due to the fact that the solid content of the slurry is too low, so that the coating times are increased. Preferably, the solid content of the coating slurry is 10 to 45 wt%, preferably 20 to 40 wt%.

According to a first embodiment of the process for preparing a structured carrier catalyst of the present invention, the coating slurry may be distributed on the inner and/or outer surface of the structured carrier by various coating methods. 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.

The method and conditions for drying and calcining the structured carrier coated with the coating slurry according to the first embodiment of the method for preparing a structured carrier catalyst of the present invention 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, 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 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 250-330 ℃ or 250-300 ℃, the reaction pressure is 1-3.5 MPa, the hydrogen partial pressure is preferably 0.5-2 MPa, and the sulfur-containing hydrocarbon feed weight hourly space velocity 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, the pressures involved are all expressed in absolute pressure.

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; the catalyst does not need to be repeatedly subjected to oxidation regeneration-reduction, and the active metal is not easy to aggregate, thereby being 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 (megapascals, namely, the absolute pressure minus the standard atmospheric pressure is-0.03 MPa), the coating temperature is 35 ℃, and the coating time is 60-300 seconds.

The used structured vector, noted ZT 1: is a cellular cordierite regular carrier, produced by Jiangsu Yixing non-metal chemical mechanical plant Limited company and has 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 μm²And cutting the required size for coating when in use.

Preparation of alumina matrix particles:

3.1kg of pseudoboehmite (produced by Shandong aluminum Co., Ltd., solid content 65% by weight, alumina 2kg, particle diameter d)₉₀35nm, same below) was mixed with 7kg of deionized water (pH 7, same below) and slurried uniformly, 1000mL of hydrochloric acid having a concentration of 18% by weight was added, the pH of the slurry was adjusted to 1.8 to make the slurry in a gel state, aged at 60 ℃ for 1h to obtain a pretreated pseudoboehmite, spray-dried, and calcined at 450 ℃ for 2 hours to obtain alumina matrix particles having an average particle size of 61 μm, designated JZ 1.

Example 1

(1) Preparation of a substrate containing a metal film:

first, 10g of chromium powder (average particle size of 10 μm, source: Shanghai Aladdin Biotechnology Co., Ltd.) and 100ml of ethylene glycol (national drug group, purity AR) were added to a 200ml jar, mixed well, and 60mg of surfactant sodium glycocholate (purity AR, source: Nanjing Paersi Biotechnology Co., Ltd.) was 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 metal chromium in the suspension is 12g/Kg, and D₉₀Is 6 nm;

13.8g of the above-mentioned alumina matrix particles JZ1 (dry basis, the same applies hereinafter) and 13g of deionized water were mixed and ground to obtain D₉₀5 micron slurry, added to 100 grams of the above suspension; stirring for 10min to obtain a mixture, marked as JY-1, and mixing the JY-1Pre-freezing at-40 deg.C, and drying at-30 deg.C under 50Pa for 24 hr to obtain matrix containing metal film, ZA1, ZA1 metal film with thickness of 6nm and chromium content of 8 wt%.

(2) 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, repeatedly coating for 3 times, wherein the dry basis weight of the active coating accounts for 30 wt%, and the final product is the regular carrier catalyst, and is marked as A1.

The structured carrier catalyst A1 contained, by dry weight, 70% cordierite, 27.6% alumina, and 2.4% metallic chromium.

Comparative example 1

JZ1 (same as example 1, ground to D90 ═ 5 μm), mixed with ammonium chromate solution, impregnated, beaten and coated with structured carrier ZT1 to obtain structured carrier catalyst product DB 1. The active coating and chromium content were the same as in example 1.

Comparative example 2

10g of ammonium chromate (calculated as chromium) 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 and impregnated with JZ1 described in example 1, and then drying is carried out at 120 ℃, roasting is carried out at 450 ℃ for 2 hours, the structured carrier catalyst is coated, drying is carried out at 120 ℃ for 2 hours, and roasting is carried out at 450 ℃ for 2 hours, so that the product DB2 is obtained. Based on its dry weight, it contained 70 wt% cordierite, 27.6 wt% alumina, and 2.4 wt% chromium.

Comparative example 3

In the existing S-ZORB adsorbent, nickel is a hydrogenation active component, the composition of the S-ZORB adsorbent is that the content of zinc oxide is 44.3 wt%, the content of expanded perlite is 24.0 wt%, the content of alumina is 13.6 wt%, and the content of nickel is 18.1 wt%, and a structured carrier ZT1 is coated with the adsorbent slurry to obtain a structured carrier catalyst which is recorded as DB 3.

Comparative example 1

A structured supported catalyst was prepared as in example 1 except that the metal-containing membrane substrate was dried by a drying process at 120 ℃ without freeze-drying as described to provide a structured supported catalyst designated BJ 1.

Example 2

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

(1) Preparation of substrates containing Metal films

Adding 50g of tungsten powder (average particle size 12 μm, purity AR, manufacturing company: Shanghai Arlatin Biotechnology Co., Ltd.) and 400ml of ethylene glycol (analytical grade) into a 500ml wide-mouth bottle, mixing uniformly, and adding 120mg of surfactant sodium dodecyl sulfate (analytical grade, national drug group); 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, wherein the concentration of tungsten in the suspension is 25g/Kg, and the particle size D of tungsten₉₀10nm, mixing 45g of α -Al₂O₃(product of Shandong aluminum industries, D)₉₀6 microns) and 40g of deionized water are added into 200g of the suspension, the mixture is stirred for 10min, the slurry is pre-frozen at the temperature of minus 40 ℃, and then is dried for 24h at the temperature of minus 30 ℃ and the pressure of 20Pa, and the final product is α -Al coated with the tungsten metal film₂O₃Designated ZA2, having a metal film thickness of 10nm and a tungsten content of 10% by weight, calculated on a dry basis, of ZA 2.

(2) Preparation of regular Supported catalysts

Intercepting a structured carrier ZT1 with the diameter of 30mm and the length of 50mm, preparing slurry with the solid content of 30 weight percent by ZA2 and water, coating ZT1 with the slurry of ZA2, drying at 120 ℃ for 2 hours, roasting at 450 ℃ for 2 hours, and repeatedly coating to ensure that the content of an active coating in the obtained structured carrier catalyst accounts for 20 weight percent to obtain the structured carrier catalyst, which is marked as A2. Composition of the structured catalyst a 2: based on the dry weight of A2, the catalyst contained 80 wt% of cordierite, 18 wt% of alumina, and 2 wt% of metallic tungsten.

Example 3

(1) Preparation of a substrate containing a metal film:

30g of silver powder (Ag powder having an average particle size of 1 μm and a purity of 99.9%, Shanghai Arlatin Biotech Co., Ltd.) and 150ml of ethylene glycol (same as that used in example 1) were added to a 250ml jar, mixed well, and 200mg of stearic acid (purchased from the national pharmaceutical group, 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; the concentration of Ag in the suspension is 10g/Kg, the particle size D₉₀Is 4 nm;

17 g of β -Al₂O₃Powder (D90 ═ 20 microns, technical grade, product of the well petrochemical catalyst, Qilu division), mixed with 30 grams of deionized water, wet ball milled into a slurry with a particle diameter D₉₀5 microns; then 300g of the above suspension was added thereto; stirring for 10 min; the slurry was pre-frozen at-40 ℃ and then dried at-30 ℃ under 50Pa pressure (absolute) for 48h to give the final product, the matrix surrounding the metal film, designated ZA 3. The thickness of the metal film was 10nm, and the modified metal content was 15 wt%. D₉₀Is 5 microns.

(2) Preparation of regular Supported catalysts

Will be provided with

ZT1 of (1) was coated with a slurry of ZA3 and water (35% by weight solids), dried at 120 ℃ for 2 hours, calcined at 400 ℃ for 3 hours, and coated twice to give a structured supported catalyst, designated A3.

Composition of a 3: on a dry basis, this contained 75 wt.% cordierite, 21.25 wt.% alumina, and 3.75 wt.% metallic silver.

Example 4

(1) Preparation of a substrate containing a metal film: adding 10g of molybdenum-tungsten alloy fine powder (sourced from Tianjin Hainan alloy Co., Ltd., weight ratio of molybdenum to tungsten of 3: 1) and 100ml of water (deionized water) into a 200ml wide-mouth bottle, uniformly mixing, and adding 60mg of surfactant sodium glycocholate (sourced from Nanjing Paersi Biotech Co., Ltd., purity AR); then, placing the jar in an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at 160W power; centrifuging the liquid after ultrasonic treatment at 1500r/min for 20min, and taking out the suspension; suspended in waterThe total concentration of metal molybdenum and tungsten in the liquid is 15g/Kg, and the weight ratio of molybdenum to tungsten is 3:1, D₉₀Is 5 nm;

14.5 g of JZ1 powder was mixed with 10g of deionized water and wet ball milled to a slurry with a particle diameter D₉₀5 microns; 100g of the above suspension was added thereto; stirring for 10 min; pre-freezing at-10 deg.C, drying at-5 deg.C under 50Pa (absolute pressure) for 24 hr to obtain final product, namely matrix wrapped with molybdenum-tungsten bimetallic membrane, and marking as ZA 4; the thickness of the metal film is 8nm, and the total content of the modified metal Mo and W is 9.4 wt%;

(2) preparation of regular Supported catalysts

Get

ZT1, coating the support with a slurry of ZA4 and water (35 wt% solids), drying at 120 ℃ for 2 hours, calcining at 350 ℃ for 3 hours, repeating the above process twice, and the final product is a structured supported catalyst, designated as a 4.

Composition of a4 dry basis: the alloy contained 70 wt% of cordierite, 27.2 wt% of alumina, 2.1 wt% of molybdenum metal and 0.7 wt% of tungsten metal.

Example 5

50g of Cu-Sn alloy fine powder (copper-tin weight ratio 3:1, average particle diameter 18 μm, Lei Gong alloy materials Co., Ltd., Qinghey county) and 300ml of a mixture of methanol and water (methanol content 50 vol%) were added to a 500ml jar, mixed uniformly, and then 120mg of sodium lauryl sulfate (purity AR) as a surfactant was added; then, the mixture is placed in an ultrasonic cleaning machine and is subjected to ultrasonic treatment for 5 hours at the power of 200W; centrifuging the liquid after ultrasonic treatment in a centrifuge at 3000r/min for 10min, and taking out the suspension; the total concentration of metallic copper and tin in the suspension was 25g/Kg, D₉₀Is 4 nm;

34 grams of JZ1 powder was mixed with 21 grams of deionized water and wet ball milled to a slurry (with particle diameter D)₉₀5 microns); the slurry was added in its entirety to 240g of the above suspension; stirring for 10 min;

freezing the obtained slurry at-20 deg.C, drying at-10 deg.C under 30Pa for 24 hr to obtain matrix for wrapping copper-tin metal film,denoted ZA 5. ZA5 having a metal film thickness of 9nm, a total modified metal content of 15 wt.%, a copper-tin weight ratio of 3:1, D₉₀Is 5 microns.

Get

The regular carrier ZT1 was coated with a slurry (solid content 30 wt%) of ZA5 and water, dried at 120 ℃ for 2 hours, and the above coating process was repeated 2 times, and calcined at 400 ℃ for 2 hours to give a product with an active coating content of 20 wt%, and a regular carrier catalyst was obtained, which was designated A5.

On a dry basis, a5 contained 80 wt% cordierite, 17 wt% alumina, 2.25 wt% metallic copper, and 0.75 wt% metallic tin.

Example 6

Adding 30gAu-Bi alloy fine powder (gold and bismuth weight ratio is 4:1, average particle size is 20 μm, sourced from Nanjing chemical reagent Co., Ltd.) and 150ml ethanol into a 250ml wide-mouth bottle, mixing uniformly, 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 9h in an ultrasonic cleaning machine at the power of 200W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 30min, and taking out the suspension; the total concentration of gold and bismuth in the suspension was 20g/Kg, D₉₀Is 6 nm.

18 g of JZ1 powder was mixed with 20g of deionized water and wet ball milled to a slurry with a particle diameter D₉₀5 microns; then 100g 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, and the resulting product, a metal film-containing matrix, designated ZA 6. ZA6, the thickness of the metal film was 8nm, the total content of gold and bismuth modified metal was 10 wt%, the weight ratio of gold and bismuth in the modified metal was 4:1, D₉₀Is 5 microns.

Will be provided with

The structured carrier ZT1 was coated with a slurry of ZA6 and water (35% by weight solids content), dried at 120 ℃ for 2 hours, calcined at 450 ℃ for 2 hours, and coated repeatedlyNext, the final product, the structured support catalyst, designated A6, was made to have an active coating content of 25 wt.%.

Based on the dry weight of the regular structure desulfurization catalyst a6, the catalyst contained 75 wt% cordierite, 22.5 wt% alumina, and 2.5 wt% total metallic nickel and aluminum, wherein the weight ratio of gold to bismuth was 4: 1.

Example 7

Adding 10g of Cr-Cu-Sb alloy fine powder (Cr-Cu-Sb weight ratio is 4: 5:1, average particle size is 15 μm, self-made) and 100ml of glycerol (analytical grade) into a 200ml wide-mouth bottle, uniformly mixing, and adding 60mg of surfactant sodium glycocholate (purity AR source Nanjing Palse Biotech limited); then, putting the wide-mouth bottle into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 6h at the power of 180W; centrifuging the liquid subjected to ultrasonic treatment at 1500r/min for 20min, and taking out the suspension; the total concentration of metal Cr-Cu-Sb in the suspension is 25g/Kg, the weight ratio of Cr-Cu-Sb is 5:4:1, D₉₀Is 5 nm;

mixing 11.3 g of JZ1 with 10g of deionized water, and wet ball-milling into 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;

the slurry JY-7 is frozen at the temperature of minus 20 ℃, and is dried for 24 hours at the temperature of minus 15 ℃ and under the absolute pressure of 30Pa, and the final product, namely the matrix wrapping the metal film, is recorded as ZA 7. The thickness of the ZA7 metal film is 12nm, the total content of Cr, Cu and Sb in the modified metal is 18 wt%, the weight ratio of Cr-Cu-Sb in the modified metal is 4: 5:1, ZA 7D₉₀Is 5 microns.

Will be provided with

Coating ZT1 with slurry (solid content 35 wt%) formed by ZA7 and water, drying at 120 deg.C for 2 hours, calcining at 450 deg.C for 2 hours, and repeatedly coating for 2 times (the repeated coating means the coating, drying and calcining processes are carried out again), wherein the active coating in the product accounts for 30 wt%, and the regular carrier catalyst is obtained and is marked as A7.

On a dry basis, a7 contained cordierite 70 wt% alumina 24.6 wt%, the total content of metals Cr, Cu and Sb was 5.4 wt%, the Cr-Cu-Sb weight ratio was 4: 5: 1.

application example

The modified sub-sieves A1-A14, DB1 and BJ1 prepared according to examples 1-7, comparative examples 1-3 and comparative example 1 of the invention are subjected to desulfurization evaluation experiments by using a fixed bed micro-reaction experimental device, 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 2-3. 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℃)	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

Note: in tables 2 to 3:

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 3, it can be seen that:

after the regular carrier catalysts A1-A7 prepared in examples 1-7 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 gradually increases 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, the octane number loss of gasoline is small, and the octane number can even be improved in example 7.

Claims

1. A regular carrier catalyst with desulfurization function is characterized by comprising a regular carrier and an active coating attached to the surface of the regular carrier, wherein the active coating comprises a heat-resistant inorganic oxide matrix and a modified metal film, the modified metal film comprises a modified metal, and the modified metal is one or more of Cr, Mo, W, Cu, Ag and Au.

2. The structured carrier catalyst as recited in claim 1, wherein the modified metal film is on the outer surface of the matrix particles, and the modified metal film has a thickness of 5 to 30 nm.

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

the active component coating comprises 5-15 wt% of modified metal film and 85-95 wt% of matrix on a dry basis based on the total weight of the active component coating;

the heat-resistant inorganic oxide matrix is one or more of an alumina matrix, a silica matrix, a zirconia matrix, a titania matrix and a silica-alumina matrix;

the regular structure carrier is an integral carrier with a parallel pore channel structure with openings at two ends, and the pore density of the cross section of the regular structure carrier is 40-800 pores/square inch, for example.

4. A structured support catalyst according to any of claims 1 to 4 wherein the modifying metal comprises a first metal selected from one or more of Cr, Mo, W, Cu, Ag, Au and optionally a second metal selected from one or more of Ge, Sn, Pb, Sb, Bi.

5. 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; contacting the suspension with matrix particles, freeze-drying to obtain matrix particles containing the modified metal membrane, and coating the matrix particles containing the modified metal membrane on a structured carrier to obtain the structured carrier catalyst, wherein the matrix particles preferably have a particle diameter d₉₀Not exceeding 10 microns.

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

7. Process for the preparation of a modified structured support catalyst according to claim 5 or 6, wherein the particles in the suspension have a size D₉₀Is 20nm or less.

8. A process for preparing a structured carrier catalyst as claimed in claim 5, wherein the weight ratio of the hydroxyl-containing solvent to the metal powder is from 2 to 15: 1;

the ratio of the surfactant to the hydroxyl group-containing solvent is 0.001 to 100 mg/mL.

9. The method for preparing a structured carrier catalyst according to claim 5, wherein the ultrasonic treatment is carried out under ultrasonic waves, the power of the ultrasonic waves is 10 to 500W relative to 100ml of the solvent, and the average diameter of the metal powder is less than 20 μm.

10. A process for preparing a structured carrier catalyst as claimed in claim 5 or 9 wherein the metal powder comprises a first metal, the first metal being one or more of Cr, Mo, W, Cu, Ag or Au, the metal powder being one or more of a pure metal powder or a metal alloy powder; may be one or more of pure metal powders of Cr, Mo, W, Cu, Ag, or Au, or an alloy containing a plurality of Cr, Mo, W, Cu, Ag, Au, or an alloy of one or more of Cr, Mo, W, Cu, Ag, Au with other metals, such as one or more of V, Ge, Pb, Sn, Sb, Bi.

11. The method for preparing a structured carrier catalyst as defined in claim 5 wherein the surfactant is 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, polyoxyethylene ether; the fatty acid amine carbon chain length is preferably between C8-C10; the fatty acid methyl ester carbon chain length is preferably between C8-C10.

12. A method for preparing a structured carrier catalyst as claimed in claim 5 wherein the hydroxyl containing solvent is water and/or a hydroxyl containing organic solvent, the hydroxyl containing organic solvent is an organic solvent containing one or more hydroxyl groups in the molecule, the hydroxyl containing organic solvent is for example a monohydric alcohol, a dihydric alcohol, a 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, ethylene glycol ether, the trihydric alcohol is glycerol, and the trihydric alcohol derivative is triethanolamine.

13. A process for preparing a structured carrier catalyst according to claim 5, wherein the separation is carried out by centrifugation at a rotational speed of 1200 to 3000 r/min.

14. A process for preparing a structured carrier catalyst as claimed in claim 5, 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.

15. A process for preparing a structured support catalyst according to claim 5,

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

the active coating comprises a substrate and a modified metal film, and the content of the substrate in the active coating is 85-95 wt% and the content of the modified metal is 5-15 wt% in terms of dry basis based on the total weight of the active coating.

16. A process for preparing a structured support catalyst according to claim 5,

coating the regular carrier with the matrix particles containing the modified metal film comprises the steps of coating the regular carrier with matrix slurry containing the modified metal film, drying and roasting, wherein the roasting temperature is 200-600 ℃, and the roasting time is more than 1 h.

17. A method for preparing a structured support catalyst as claimed in claim 5 wherein the matrix particles are one or more of alumina particles, silica-alumina particles, zirconia particles, titania particles or particles selected from the group consisting of alumina, silica and alumina, zirconia and titania.

18. 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 of any one of claims 1 to 4, 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. The hydrogen donor can be one or more of hydrogen, hydrogen-containing gas and hydrogen donorThe hydrocarbon material is selected from one or more of natural gas, dry gas, liquefied gas, gasoline, kerosene, diesel oil and gas oil.