CN111085191A - Regular carrier catalyst with desulfurization effect and preparation and application thereof - Google Patents

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 layer attached on the surface of the regular carrier, the active coating layer includes a substrate containing IIA, IIB group metal oxide and a modified metal film attached on the outer surface of the substrate, the modified metal film includes modified metal, the modified metal is one or more of 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 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 is used for hydrodesulfurizing hydrocarbon, has high desulfurizing activity and high stability, and can reduce octane number loss of gasoline.

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 hydrocarbon 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 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 problem of providing a preparation and application method of the catalyst.

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 matrix containing IIA and IIB metal oxides and a modified metal film attached to the outer surface of the matrix, the modified metal film comprises modified metal, and the modified metal is one or more of 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 5-25 nm, preferably 5-20 nm or 5-15 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 structured carrier catalyst according to any one of claims 1 to 3, wherein the active component coating comprises 2 to 5 wt% of the modified metal, 90 to 98 wt%, for example, 95 to 98 wt% of the matrix, and 0 to 8 wt%, for example, 0 to 5 wt% of the second element selected from one or more of Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg, B, on a dry basis based on the total weight of the active component coating;

the substrate contains one or more of optional heat-resistant inorganic oxides such as alumina substrate, silica substrate, zirconia substrate, titania substrate and silica-alumina substrate, wherein the silica-alumina substrate such as kaolin and silica-alumina gel is preferably alumina;

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 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 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 or metal alloyAt least one of a honeycomb carrier.

The structured carrier catalyst according to any one of claims 1 to 5, wherein the modified metal film comprises one or more first metals selected from Cu, Ag, and Au, and optionally one or more second elements selected from Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg, and B, preferably, the weight ratio of the second element 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 one embodiment, the first metal is a plurality of metals selected from Cu, Ag, and Au, wherein the ratio of any two metals is 0.2-5: 1, for example, 0.5-2: 1.

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, preferably 10nm or less, more preferably 5nm or less, for example, 1 to 20nm, 4 to 10nm, 3 to 8nm, 1 to 10nm, or 2 to 5 nm.

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 Cu powder, Ag powder and Au powder; the alloy powder is an alloy formed by a plurality of Cu, Ag and Au, or an alloy formed by one or more of Cu, Ag and Au and one or more of second elements, and the second elements are one or more of Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg and B; in the alloy powder, the ratio of the second element: the weight ratio of the first metal is 0-1: 1 or 0-0.5: 1, such as 0-0.3: 1, and the first metal is one or more of Cu, Ag and Au.

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 the 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 is, for example, 5 to 50 minutes, such as 10 to 30 minutes or 15 to 20 minutes; the container used for centrifugal separation is 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 and a modified metal film, and the content of the substrate is 90-98 wt%, such as 95-98 wt%, the content of the modified metal is 2-5 wt%, and the content of the second element is 0-8 wt%, such as 0-5 wt%, based on the total weight of the active coating, on a dry basis.

Technical scheme 21. the method for preparing a structured carrier catalyst according to any one of technical schemes 7 to 20, 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 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 process for preparing a structured carrier catalyst according to any one of claims 7 to 21, wherein the matrix particles comprise one or more oxides of metals of groups IIA and IIB, and may further comprise one or more heat-resistant inorganic oxides selected from alumina, silica-alumina, zirconia and titania, preferably one or more oxides of metals of groups IIA and IIB, such as γ -alumina, β -alumina, α -alumina, η -alumina and κ -alumina, and the matrix particles may be obtained by mixing, molding or grinding the group IIA and IIB oxides of metals and/or the group IIA and IIB oxides of metals with a substance that can be converted into alumina under calcination conditions, such as hydrated alumina and/or alumina sol, and the matrix particles may be obtained by mixing, molding or grinding the group IIA and IIB oxides of metals with one or more oxides of metals of groups IIA and IIB, and IIB oxides of metals selected from hydrated alumina and/or alumina sol, such as hydrated alumina and/or alumina sol, and/or amorphous alumina, and the hydrated alumina is one or more oxides of metals selected from hydrotalcites, silica, one or more oxides of metals of groups IIA and/or attapulgite, sepiolite, and/or montmorillonite, preferably one or more of metals of groups IIA and montmorillonite.

The process for producing a structured carrier catalyst according to any one of claims 7 to 22, 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 0 to 75: 25 to 100, for example, 0 to 50:50 to 100 or 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.

The technical scheme 24 is a sulfur-containing hydrocarbon desulfurization method, 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 the technical schemes 1 to 6, wherein the reaction temperature is 150 to 350 ℃, the reaction pressure is 0.5 to 5MPa, and the sulfur-containing hydrocarbon feeding weight hourly space velocity 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 24, wherein the hydrogen donor is 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 26. according to the desulfurization method of the technical scheme 24 or 25, 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 at the same reaction temperature, can run for a long period, and can reduce the 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 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 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 coated on 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 2 to 5 wt% of the modifying metal and 90 to 98 wt% of the substrate, optionally containing 0 to 8 wt%, for example 0 to 5 wt% of the second element.

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 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, 50 to 400W, 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 D₉₀Measurement is carried out by a laser particle size instrumentThe method can be seen in the national standard GB/T19077-2016, particle size distribution laser diffraction method. D₉₀Also written as d₉₀D90 or D90, are particle diameters corresponding to a cumulative particle size distribution of 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, and the centrifugation time may be 5-50 minutes, for example 10-30 minutes or 15-20 minutes. 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 oxide containing at least one metal in the IIA and IIB groups and the heat-resistant inorganic oxide matrix particles, the outer surface of the oxide particles containing at least one metal in the IIA and IIB groups and the outer surface of the heat-resistant inorganic oxide particles, and then the particles are mixed or sequentially and respectively coated on the regular carrier.

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

s1, preparing an oxide source of at least one metal in the IIA and IIB groups and an optional heat-resistant inorganic oxide source into matrix particles, and optionally roasting, wherein the oxide source of at least one metal in the IIA and IIB groups is an oxide of at least one metal in the IIA and IIB groups and/or at least one metal oxide precursor in the IIA and IIB groups; the inorganic oxide source is preferably an alumina source;

s2, mixing the particle diameter D₉₀Mixing the substrate particles with the particle size of not more than 10 microns, such as 1-10 microns or 2-8 microns, preferably 2-5 microns, with the suspension, and freeze-drying to obtain a substrate containing the modified metal film;

s3, 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 first embodiment of the method for preparing a structured carrier catalyst, the preferred inorganic oxide source is an alumina source, wherein the alumina source is a substance capable of being converted into alumina under the calcination condition in the previous step S1, 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. The roasting temperature of the roasting in the step S1 is preferably 250-700 ℃, for example 300-600 ℃, and the roasting time is 1-5 hours, for example 2-4 hours.

In the first embodiment of the method for preparing a structured carrier catalyst according to the present invention, the weight ratio of the alumina source in terms of alumina to the oxide source of at least one metal in group IIA or IIB in terms of oxide is preferably 0 to 80:20 to 100, for example 0 to 70:30 to 100 or 0 to 60:40 to 100 or 0 to 50:50 to 100 or 25 to 60: 40-75 or 60-70: 30-40.

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 first embodiment of the preparation method of the regular supported catalyst, the solid content of the prepared coating slurry is not particularly required, 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 preparation method of the regular carrier catalyst provided by the invention is that the suspension and the matrix are uniformly mixed, and then the mixture is frozen and dried, usually, the mixture is frozen 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 particles wrapping the modified metal film.

According to the preparation method of the present invention, the suspension may be brought into contact with the matrix particles 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 particles with the suspension, after uniform dispersion, freeze-drying, and coating a 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: the amount of the solvent is 0.001 to 100mg, and 1mL is, for example, 0.01 to 10mg of the surfactant per mL of the hydroxyl group-containing solvent. 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 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 pore channels of the carrier is 2.5 times of the volume of the carrier, the applied vacuum pressure is-0.03 MPa (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.

Zinc oxide powder Zibo Haishun Zinc Ltd, model HHG-02, D₉₀8 microns, noted JZ 1.

Preparing matrix particles:

3.1kg of pseudoboehmite (produced by Shandong aluminum Co., Ltd., solid content 65% by weight, alumina 2kg, particle diameter d)₉₀35nm, the same below) was mixed with 7kg of deionized water (pH 7, the same below) and slurried, 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, aging was carried out at 60 ℃ for 1 hour to obtain a pretreated pseudo-boehmite, and 2.1kg of zinc oxide powder (product of beijing chemical plant, particle diameter d) was added to the pretreated pseudo-boehmite obtained above₉₀Is 75 nm; 0.2kg dry basis) were mixed and stirred, spray-dried, calcined at 450 ℃ for 2 hours to give alumina matrix particles having an average particle diameter of 60 μm, and ground to give D₉₀Is 5 micron substrate particle, noted as JZ 2.

Example 1

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

adding 50g of copper powder (with the average particle size of 15 microns and the content of more than 99 percent) and 400ml of glycol (analytically pure) into a 500ml wide-mouth bottle, uniformly mixing, and adding 120mg of surfactant sodium dodecyl sulfate (analytically pure, 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 copper in the suspension is 25g/Kg, and the granularity D of copper₉₀Is 10 nm;

47.5g of the above zinc oxide based particles JZ1 (toDry basis, the same applies hereinafter) and 40g of deionized water, and wet ball milling to obtain a slurry, D thereof₉₀5 microns, added to 100 grams of the above suspension; stirring for 10min to obtain a mixture, denoted as JY-1, pre-freezing the JY-1 at-40 ℃, and then drying for 24h under the vacuum condition of-30 ℃ and 50Pa to obtain a matrix containing a metal film, denoted as ZA1, wherein the thickness of the metal film ZA1 is 15nm, and the copper content is 5 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 regular carrier catalyst A1 contained, by dry weight, cordierite 70 wt%, zinc oxide 28.5 wt%, and metallic copper 1.5 wt%.

Comparative example 1

ZT1 was coated with a slurry of JZ1 to obtain a structured carrier containing a matrix, designated as ZTJ2, 10g of copper nitrate (calculated as copper) was dissolved in 100ml of ethylene glycol, then the reaction vessel was placed in an ultrasonic cleaner, subjected to ultrasonic treatment at 160W power for 6 hours, mixed and impregnated with ZTJ2 carrier, then dried at 120 ℃ and calcined at 450 ℃ for 2 hours to obtain a structured carrier catalyst product DB 1. The alloy contains cordierite 70 wt%, zinc oxide 28.5 wt%, and metallic copper 1.5 wt%.

Comparative example 1

A structured supported catalyst was prepared as in example 1 except that instead of the freeze drying described, it was dried by a drying procedure at 120 ℃ to give 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

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;

39 g of JZ2 and 40g of deionized water were mixed and wet ball milled to give D₉₀Slurry of 4 microns was added to 100g of the above suspension; stirring for 10 min; the slurry is pre-frozen at-40 ℃ and then dried at-30 ℃ and 20Pa for 24h, and the final product, namely the matrix coated with the silver metal film, is recorded as ZA2, the thickness of the metal film is 15nm, and the silver content accounts for 2.5 wt% of ZA2 in terms of dry basis.

(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 for many times 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 composition contained cordierite 80 wt%, zinc oxide 9.75 wt%, alumina 9.75 wt%, and metallic silver 0.5 wt%.

Example 3

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

30g of gold powder (average particle size 5 μm, purity 99%, national pharmaceutical group) and 150ml of ethylene glycol (same as used in example 1) were added to a 250ml jar, mixed well, and 200mg of sodium glycocholate surfactant (purity AR, source: Nanjing Pars Biotech Co., Ltd.) was added; then, putting the mixture into an ultrasonic cleaning machine, and carrying out ultrasonic treatment for 10 hours at the power of 220W; centrifuging the liquid subjected to ultrasonic treatment at 2500r/min for 10min, and taking out the suspension; the concentration of Au in the suspension is 8g/Kg, and the granularity D of gold₉₀Is 5 nm;

19.2 g of JZ1 were mixed with 30g of deionized water and wet ball milled to a slurry having a particle diameter D₉₀5 microns; then 100g 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 4 wt%. D₉₀Is 5 microns.

(2) Preparation of regular Supported catalysts

Will be provided with

ZT1 (E) was coated with a slurry of ZA3 and water (30% by weight solids), dried at 120 ℃ for 2 hours, calcined at 400 ℃ for 3 hours, and coated 3 times to give a structured supported catalyst, designated A3.

Composition of a 3: on a dry basis, this contained 75 wt.% cordierite, 24 wt.% zinc oxide and 1 wt.% metallic tungsten.

Example 4

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

adding 10g of Cu-Ag alloy fine powder (from Tianjin Hainan alloy Co., Ltd., weight ratio of copper to silver of 2: 1) and 100ml of water (deionized water) into a 200ml wide-mouth bottle, uniformly mixing, and adding 60mg of surfactant sodium glycocholate (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; the total concentration of metallic copper and silver in the suspension is 15g/Kg, the weight ratio of copper to silver is 2:1, D₉₀Is 5 nm;

28.5 g of JZ1 powder was mixed with 25g 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 coated with metal film, and marking as ZA 4; the thickness of the metal film is 10nm, and the total content of the modified metal Cu and Ag is 5 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, and repeating the coating twice, the final product being a structured support catalyst, designated as a 4.

Composition of a4 dry basis: the alloy contains cordierite 70 wt%, zinc oxide 28.5 wt%, metallic copper 1 wt%, and metallic silver 0.5 wt%.

Example 5

Adding 30g of gold-magnesium alloy fine powder (gold-magnesium weight ratio is 4:1, average particle size is 20 μm, source Nanjing chemical reagent Co., Ltd.) and 150ml of ethanol (analytically pure) into a 250ml wide-mouth bottle, uniformly mixing, and adding 200mg of surfactant stearic acid (carbon chain length is 18, source 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 gold and magnesium in the suspension was 20g/Kg, D₉₀Is 6 nm.

38 g of JZ1 powder was mixed with 30g of deionized water and wet ball milled to a slurry (particle diameter D therein)₉₀5 microns); the slurry was added in its entirety to 100g of the above suspension; stirring for 10 min;

the slurry obtained above was frozen at-65 ℃ and dried at-60 ℃ under a pressure of 20pa for 36h to obtain a matrix coated with a metal film, designated ZA 5. ZA5 having a metal film thickness of 8nm, a total metal content of modified metal of 5 wt.%, a ratio of gold to magnesium of 4:1 by weight, and D₉₀Is 5 microns.

Get

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

On a dry basis, a5 contained 80 wt% cordierite, 19 wt% zinc oxide, 0.8 wt% metallic gold, and 0.2 wt% metallic antimony.

Example 6

(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; ) Replacing said zinc oxide 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 6:

the a6 contained, by dry weight, cordierite 70 wt%, magnesia 27 wt%, and metallic copper 3 wt%.

Example 7

Adding 10g of Ag-Sb alloy fine powder (silver/antimony weight ratio of 5:1, average particle diameter of 15 μm, purity 98 wt% from Nangong Ruiteng alloy 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 silver and antimony in the suspension was 25g/Kg, the weight ratio of silver to antimony was 5:1, D₉₀Is 5 nm;

39 g of JZ2 and 40g of deionized water were ball milled by a wet method to obtain D₉₀Particles of 4 microns are added to 100g of the suspension; stirring for 10 min; pre-freezing the slurry at-40 ℃, and then drying the slurry at-30 ℃ and 20Pa for 24h to obtain a final product, namely a matrix coated with a metal film, wherein the thickness of the metal film is 10nm, the total content of silver and antimony accounts for 6 wt% of ZA7 on a dry basis, and the weight ratio of the silver to the antimony is 5: 1.

(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 ZA7 and water, coating ZT1 with the slurry of ZA7, drying at 120 ℃ for 2 hours, roasting at 450 ℃ for 2 hours, and repeatedly coating for 2 times (the repeated coating refers to the coating, drying and roasting processes), so that the content of an active coating in the obtained structured carrier catalyst accounts for 20 weight percent, and the obtained structured carrier catalyst is marked as A7. Composition of the structured catalyst a 7: based on the dry weight of a7, the alloy contained 80 wt% of cordierite, 9.4 wt% of zinc oxide, 9.4 wt% of alumina, 1 wt% of metallic silver, and 0.2 wt% of metallic antimony.

Example 8

Adding 50g of Ag-Sn alloy fine powder (silver/tin weight ratio is 2:1, average particle size is 12 microns, purity is 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 silver and tin in the suspension is 20g/Kg, the weight ratio of silver to tin is 2:1, D₉₀Is 4 nm;

a structured carrier catalyst, A8, having the composition: the alloy contains 70 wt% of cordierite, 28.5 wt% of zinc oxide, and 1.5 wt% of total silver and tin, wherein the weight ratio of silver to tin is 2: 1.

example 9

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.

A structured carrier catalyst, A9, having the composition: the alloy contains 70 wt% of cordierite, 28.5 wt% of zinc oxide, 1.5 wt% of total content of gold and bismuth, and weight ratio of gold to bismuth is 2: 1.

application example

The modified sub-sieves A1-A9, DB1 and BJ1 prepared according to examples 1-9, comparative example 1 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 (gasoline) is 4h^-1Under the reaction conditions of (1), a desulfurization reaction of the sulfur-containing hydrocarbon oil is carried out. The gasoline composition is shown in Table 1, and the reaction results are 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 ℃ 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

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.

As can be seen from the data in tables 2 to 3:

after the regular carrier catalysts A1-A14 prepared in the embodiments 1-9 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 5ppm, the octane number loss of gasoline is small, and the gasoline yield is high.

Claims (16)

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 substrate containing IIA and IIB metal oxides and a modified metal film attached to the outer surface of the substrate, the modified metal film comprises modified metal, and the modified metal is one or more of Cu, Ag and Au.

2. The structured support catalyst of 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 25 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 2-5 wt% of modified metal and 90-98 wt% of matrix, such as 95-98 wt% and 0-8 wt% of second element, wherein the second element is one or more selected from Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg and B;

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

the oxide of the IIA or IIB metal is preferably 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.

4. A structured support catalyst according to any of claims 1 to 3 wherein the modified metal film comprises a first metal of one or more of Cu, Ag, Au and optionally a second element selected from one or more of Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg, B, preferably wherein the weight ratio of the second element to the first metal is from 0 to 1: 1; in one embodiment, the first metal is a plurality of metals selected from Cu, Ag and Au, and the ratio of any two metals is 0.2-5: 1.

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; and 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.

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-containing solvent is 0.001-100 mg/mL;

the ultrasonic treatment is carried out, wherein the power of ultrasonic waves is 10-500W relative to 100ml of solvent;

the average diameter of the metal powder is less than 20 mu m.

9. A process for the preparation of a structured carrier catalyst as claimed in claim 5 or 8, wherein the metal powder is a metal alloy powder, a pure metal powder or a mixture of a plurality of the above powders; the pure metal powder is one or more of Cu powder, Ag powder and Au powder; the alloy powder is an alloy formed by a plurality of Cu, Ag and Au, or an alloy formed by one or more of Cu, Ag and Au and one or more of second elements, and the second elements are one or more of Fe, Co, Ni, Mn, Al, Ti, Zr, Ga, V, Cr, Mo, W, Sn, Sb, Bi, Mg and B; in the alloy powder, the ratio of the second element: the weight ratio of the first metal is 0-1: 1, and the first metal is one or more of Cu, Ag and Au.

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

11. 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 preferably 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 derivative is one or more of 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 derivative is triethanolamine.

12. 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 from 1200r/min to 3000 r/min.

13. 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.

14. Process for the preparation of a structured support catalyst according to claim 5 or 9,

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 and a modified metal film, wherein the modified metal film comprises a modified metal and a second element, and the content of the substrate is 90-98 wt%, the content of the modified metal is 2-5 wt%, and the content of the second element is 0-8 wt% in terms of dry basis based on the total weight of the active coating.

15. A method of preparing a structured support catalyst as recited in claim 5 in which the step of coating the structured support with matrix particles comprising the modified metal film comprises the steps of coating the structured support with a matrix slurry comprising the modified metal film, drying, and calcining; the roasting temperature is 200-600 ℃, and the roasting time is more than 1 h.

16. A process for desulfurizing sulfur-containing hydrocarbon, comprising the step of contacting 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 15%0 to 350 ℃, the reaction pressure is 0.5 to 5MPa, and the weight hourly space velocity of the sulfur-containing hydrocarbon feeding is 0.1 to 100h^-1The volume ratio of the hydrogen donor to the sulfur-containing hydrocarbon is 0.01 to 1000.