CN112742362A

CN112742362A - Coke-oven gas hydrodesulfurization catalyst and preparation method and application thereof

Info

Publication number: CN112742362A
Application number: CN201911054638.2A
Authority: CN
Inventors: 孙霞; 吴玉; 侯朝鹏; 褚阳; 刘锋; 李学锋; 张荣俊; 夏国富; 阎振楠; 徐润; 王鹏飞; 邹亮
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-31
Filing date: 2019-10-31
Publication date: 2021-05-04
Anticipated expiration: 2039-10-31
Also published as: CN112742362B

Abstract

Discloses a coke oven gas hydrodesulfurization catalyst and a preparation method and application thereof. The catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component comprises molybdenum and VIII group metals, and the carrier is raspberry type oxide microspheres; the molybdenum content is 10-45 wt% calculated by oxide and based on the catalyst; the content of the VIII group metal is 1-16 wt%; the content of the support oxide is from 39 to 89% by weight. The raspberry type oxide microsphere has better mass transfer and heat transfer characteristics, the strength is obviously higher than that of the existing product with a similar structure, and meanwhile, the preparation method is simple, low in cost, high in efficiency and suitable for large-scale industrial application. The hydrodesulfurization of the coke oven gas provided by the invention adopts raspberry type carrier alumina as a carrier, so that the performance of the catalyst is improved.

Description

Coke-oven gas hydrodesulfurization catalyst and preparation method and application thereof

Technical Field

The application relates to a coke oven gas hydrodesulfurization catalyst and a preparation method and application thereof.

Background

The coke oven gas is a byproduct of coking in a coke-oven plant, and comprises the main components of methane, hydrogen, carbon monoxide, carbon dioxide and the like. The recycling of the coke oven gas plays an important role in the clean utilization of coal resources in China. The presence of sulfides in coke oven gas can cause subsequent industrial pipelinesAnd equipment is corroded, so that the activity of a pure oxygen conversion catalyst in the converter is reduced (the main active component of the conversion catalyst is Ni which can react with sulfide to generate NiS to reduce the activity), the content of residual methane in the outlet gas of the converter is increased, the energy consumption of the whole device is increased, and the methanol synthesis catalyst (the active component Cu simple substance reacts with the sulfide to generate CuS) is poisoned and inactivated. Therefore, during the purification of coke oven gas, the total sulfur volume fraction must be removed to less than or equal to 0.1X 10^-6Therefore, a series of desulfurization measures are required. In the existing coke oven gas desulfurization process, most of H₂S is removed in the wet desulphurization process, and the removal of organic sulfur such as carbonyl sulfide, mercaptan, thioether, thiophene and the like needs a hydroconversion method, i.e. the organic sulfur is converted into hydrogen sulfide under the action of a hydrodesulfurization catalyst, and then the desulfurizer absorbs H₂S。

Generally, the coke oven gas pre-hydrogenation and primary hydrogenation catalysts are Mo-based catalysts promoted by Fe, and the secondary hydrogenation is Mo-based catalysts promoted by Fe or Ni. Generally, in the operation process of the coke oven gas hydrogenation catalyst, the oxygen content is generally below 0.5 percent, and the use temperature is generally about 360-420 ℃. Some coke oven gases have a high oxygen content, usually > 0.5%, and the oxygen content can reach more than 1%. Every 1% of oxygen in the coke oven gas can bring about a temperature rise of about 150 ℃. Therefore, higher requirements are put on the high temperature resistance of the hydrogenation catalyst. The iron-molybdenum catalyst has side reactions: methanation reaction, combustion reaction and carbon precipitation reaction. The conversion reaction and the side reaction of the iron-molybdenum catalyst are exothermic reactions, and the temperature rise of the catalyst layer is well controlled in the operation.

In the organic sulfur hydrodesulfurization process, the selection of the hydrogenation catalyst has certain requirements on the contents of carbon monoxide and carbon dioxide in coke oven gas so as to prevent the generation of methanation side reaction to cause severe temperature rise of a catalyst bed layer. For high concentration of CO and CO₂During the hydrogenation purification of the coke-oven gas, the following problems need to be solved, namely, the methanation side reaction generated during the primary and secondary hydrogenation of the high-concentration oxycarbide is avoided; secondly, the decomposition and carbon precipitation of CO and olefin are avoided; thirdly, the generation of carbonyl compounds is avoided, so that the hydrogenation process is safely carried out(ii) a Fourthly, controlling the influence of trace oxygen and ammonia in the coke oven gas on the activity of the catalyst; controlling the temperature rise of bed hot spot in the second stage hydrogenation reaction process.

At present, the hydrodesulfurization of the coke oven gas generally uses Fe-Mo/gamma-Al developed in China₂O₃The catalyst has relatively less methanation reaction and CO disproportionation carbon deposition reaction in the using process, but the catalysis of Fe on Mo is weaker, and Fe-Mo/gamma-Al₂O₃The hydrodesulfurization rate of the catalyst is only about 60 percent, the use temperature is high and is 350-420 ℃, and the activity of the catalyst is unstable. Patent CN101797508A discloses a hydrodesulfurization catalyst of coke oven gas and a preparation method thereof, wherein the catalyst is gamma-Al₂O₃Is prepared by loading active components on a catalyst carrier by an impregnation method, wherein the active components comprise iron oxide, molybdenum oxide and cobalt oxide, the weight content of the iron oxide is 2-10 percent of the total amount of the catalyst, the weight content of the molybdenum oxide is 5-20 percent of the total amount of the catalyst, the weight content of the cobalt oxide is 0.1-5 percent of the total amount of the catalyst, and the balance is gamma-Al₂O₃。

The patent '200910273123.1' discloses a coke oven gas hydrodesulfurization catalyst, the active components of which include iron oxide, molybdenum oxide and cobalt oxide, and trace rare earth elements and alkali metal auxiliaries can be introduced, the prepared catalyst has the characteristics of high desulfurization activity, less methanation reaction and CO disproportionation reaction and good thermal stability. However, the alkali metal assistant is introduced by a stepwise impregnation method, which not only results in a complex preparation process, but also results in a poor acting force and uneven distribution of the alkali metal assistant and the active component molybdenum, so that the alkali metal assistant is helpful for reducing carbon deposition after introduction, but also results in reduction of catalyst activity.

Patent "CN 201310107002.6" discloses a novel organic sulfur hydrogenation catalyst and a preparation method thereof. The catalyst comprises Al2O3 carrier, ZnO, iron oxide and molybdenum oxide in specific weight parts; according to the invention, ZnO added in the hydrodesulfurization catalyst is used as an auxiliary agent, so that the ZnO has an excellent synergistic effect with the iron oxide and molybdenum oxide active components, and compared with the hydrodesulfurization catalyst in the prior art, the hydrodesulfurization catalyst has higher thiophene conversion and removal efficiency when used for removing organic sulfides such as thiophene in gas. However, when the catalyst is used for coke oven gas desulfurization, CO disproportionation and carbon deposition are easily caused, the service life of the catalyst is influenced, and the catalyst needs to be frequently replaced in actual production, so that the production cost is increased.

The above catalysts are all granular catalysts suitable for a conventional fixed bed. The catalyst which has simple process, strong raw material adaptability and low operation cost is sought, and the method has important significance for expanding the raw material supply of hydrogen production devices of oil refineries and large-scale fertilizer plants.

Disclosure of Invention

The inventor researches and discovers that when the carrier with the raspberry-type cavity structure is used for preparing the coke oven gas hydrodesulfurization catalyst, the reaction performance of the catalyst is obviously improved.

In a first aspect, the application relates to a coke oven gas hydrodesulfurization catalyst, which comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component comprises molybdenum and a group VIII metal, and the group VIII metal is one or two of iron and cobalt;

the carrier is a raspberry type oxide microsphere, the raspberry type oxide microsphere is a hollow microsphere with a large hole on the surface, a hollow structure is arranged in the hollow microsphere, and the large hole is communicated with the hollow structure to form a cavity with an opening at one end; wherein the carrier oxide in the raspberry type oxide microspheres is selected from one or more of alumina, silica, zirconia and titania;

the molybdenum content is 10-45 wt% calculated by oxide and based on the catalyst; the content of the VIII group metal is 1-16 wt%; the content of the support oxide is from 39 to 89% by weight.

In one embodiment, the catalyst further comprises one or more promoter metal components selected from Zn, Mg, Ca, K, Zr, Ce, La or Mn, the promoter metal component being present in an amount of 10 wt.% or less, preferably 7 wt.% or less, calculated as oxide, based on the catalyst.

In one embodiment, the molybdenum content is 15 to 43 wt.% in terms of oxide and the group VIII metal content in terms of oxide is preferably 1.5 to 13 wt.%, based on the catalyst.

In one embodiment, the raspberry type oxide microspheres have a sphericity of 0.50 to 0.99 and a diameter of 60 to 400 μm.

In one embodiment, the diameter of the hollow structure is 15-200 μm, and the wall thickness of the wall surrounding the hollow structure is 20-100 μm.

In one embodiment, the coke oven gas hydrodesulfurization catalyst is used in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.

In a second aspect, the present application provides a method of preparing a coke oven gas hydrodesulfurization catalyst as described herein comprising the steps of:

providing the vector;

and (3) impregnating the carrier with a solution containing a compound of an active metal component, drying and roasting to obtain the coke oven gas hydrodesulfurization catalyst.

In one embodiment, providing the carrier comprises the steps of:

adding nitrate, peptizing agent, pore-forming agent, oxide and/or precursor thereof into a dispersing agent and stirring to obtain dispersed slurry;

aging the dispersed slurry;

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

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

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

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

In one embodiment, the oxide and/or its precursor is selected from one or more of an aluminum source selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a zirconium source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a titanium source selected from one or more of titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminum chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetra-isopropyl titanate, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium hydroxycarbonate, and tetrabutoxy zirconium.

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

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

In one embodiment, the method further comprises adding a blasting agent to the dispersing agent, wherein the blasting agent is selected from one or more of picric acid, trinitrotoluene, nitroglycerin, nitrocotton, danesel explosive, hexogen, and C4 plastic explosive.

In one embodiment, the amount of the blasting agent added is 0 to 1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or precursor thereof.

In one embodiment, the drying device is a flash drying device or a spray drying device.

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

In another aspect, the present application provides the use of the coke oven gas hydrodesulfurization catalyst of the present application in catalyzing the hydrodesulfurization of coke oven gas.

In yet another aspect, the present application provides a method for hydrodesulfurization of coke oven gas, comprising contacting coke oven gas with a hydrodesulfurization catalyst of the present application under coke oven gas hydrodesulfurization reaction conditions.

In one embodiment, the hydrodesulfurization reaction of the coke oven gas is carried out in a microchannel reactor, which is a reactor having a reaction channel with at least one dimension less than 1000 μm.

The raspberry type oxide microsphere has better mass transfer and heat transfer characteristics, the strength is obviously higher than that of the existing product with a similar structure, and meanwhile, the preparation method is simple, low in cost, high in efficiency and suitable for large-scale industrial application. The hydrodesulfurization of the coke-oven gas provided by the invention adopts raspberry type carriers as carriers, so that the performance of the catalyst is improved.

Drawings

FIG. 1 shows a scanning electron micrograph of the support obtained in example 1.

Detailed Description

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

In one aspect, the present application provides a coke oven gas hydrodesulfurization catalyst comprising a carrier and an active metal component supported on the carrier, wherein the active metal component comprises molybdenum and a group VIII metal, iron and cobalt, and the group VIII metal is preferably one or both of iron and cobalt.

the molybdenum content is 10-45 wt% calculated by oxide and based on the catalyst; the content of the VIII group metal is 1-16 wt%.

In the catalyst, a catalyst carrier is a raspberry-type oxide microsphere, the raspberry-type oxide microsphere is a hollow microsphere with a large pore on the surface, a hollow structure is arranged in the hollow microsphere, and the large pore and the hollow structure are communicated to form a cavity with one open end; wherein the carrier oxide in the raspberry type oxide microspheres is selected from one or more of alumina, silica, zirconia and titania.

FIG. 1 shows a scanning electron micrograph of microspheres obtained in one example. The raspberry type oxide microspheres are approximately spherical in appearance, the sphericity of the raspberry type oxide microspheres is 0.50-0.99, and the diameter of the raspberry type oxide microspheres is 60-400 microns. The diameter of the hollow structure is 15-200 mu m, and the wall thickness of the wall surrounding the hollow structure is 20-100 mu m. After the raspberry type oxide microspheres are roasted at the temperature of 300-900 ℃, the specific surface area of the raspberry type oxide microspheres is about 10-500m²A pore volume of about 0.1 to 2 ml/g. The preparation method of the raspberry type oxide microsphere carrier is described in the specification of the application. In one embodiment, the content of support oxide is 39 to 89 wt.%, preferably 45 to 80 wt.%, calculated as oxide and based on the catalyst.

The sphericity of the microbead blank is calculated by the following formula:

σ＝4πA/L²

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

The active metal component in the catalysts of the present application includes molybdenum and a group VIII metal. These active metal components may be present in the form of metal oxides, also in the form of metal sulphides and even in the reduced state. These forms may be interconverted, for example, the metal oxide may be sulfided and converted to the metal sulfide form, or reduced and converted to the reduced form. The skilled person can select and transform accordingly according to the use requirement. For example, when desulfurization is performed, it may be activated to convert it into a sulfide form and then used for the catalytic reaction of desulfurization.

In one embodiment, the molybdenum content, calculated as oxide and based on the catalyst, is from 10 to 45% by weight, preferably from 15 to 43% by weight. In one embodiment, the group VIII metal content, calculated as oxide and based on the catalyst, is preferably from 1.5 to 13% by weight, calculated as oxide and based on the catalyst.

In one embodiment, the catalyst further comprises one or more promoter metal components selected from Zn, Mg, Ca, K, Zr, Ce, La or Mn, the promoter metal component being present in an amount of 10 wt.% or less, preferably 7 wt.% or less, calculated as oxide, based on the catalyst. These promoter metal components are present in the form of oxides.

The microchannel reactor is a reactor with reaction channels with at least one dimension of the dimension less than 1000 μm. The microchannel reactor has large specific surface area, and can shorten the residence time required by reaction; the heat transfer process is enhanced, so that chemical or chemical reactions can be carried out under almost isothermal conditions; strengthening the mass transfer process; the safety and the controllability are good; easy to be enlarged. By utilizing the microchannel reaction technology, the reaction of high-activity and particle catalysts under the isothermal condition can be realized, the defects of poor heat transfer of a fixed bed and incapability of applying small-granularity catalysts are overcome, and the problem of abrasion of fluidized bed catalysts is solved. Therefore, the method has important significance. The microchannel reactor is adopted, so that the process flow can be simplified, the device volume and equipment investment are reduced, unstable working conditions such as temperature runaway and the like are avoided, and the occupied area is reduced, but the development of the efficient microchannel catalyst suitable for the microreactor is necessary. The size and the shape of catalyst particles are optimized by optimizing the metal loading and the formula of the catalyst; the productivity of the reactor can be increased by increasing the space-time yield of the catalyst by increasing the space velocity, increasing the length of the reaction channel, etc. The coke oven gas hydrodesulfurization catalyst can be used for a microchannel reactor.

The raspberry type oxide microspheres are roasted at 400-1300 ℃, preferably 450-1100 ℃, and then preferably 500-700 ℃ to obtain oxides. The specific surface area is about 0.1 to 900m²Preferably 10 to 300 m/g²A pore volume of about 0.01 to 3.6ml/g, preferably 0.1 to 0.9 ml/g.

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

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

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

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

The strength of the microspheres can be evaluated by using the breakage rate; the strength of the microspheres is higher when the breakage rate is lower.

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

In a second aspect, the present application provides a method of preparing a coke oven gas hydrodesulfurization catalyst of the present application comprising the steps of:

providing the vector;

In one embodiment, the raspberry type oxide microsphere support of the present invention can be prepared by a method comprising:

adding nitrate, peptizing agent, pore-forming agent and oxide precursor into a dispersing agent and stirring to obtain dispersed slurry;

aging the dispersed slurry; and

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

In the preparation method of the invention, the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate and yttrium nitrate. Nitrate ions in the nitrate promote a self-propagating combustion reaction at high temperatures that can act as an oxidizer for the pore former, producing gases and vapors that form cavities in the oxide material.

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

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

In the preparation method of the invention, the oxide and/or the precursor thereof can be directly alumina, silica, zirconia and titania, or the precursor forming the oxide can be used, and specifically can be one or more selected from an aluminum source, a silicon source, a zirconium source and a titanium source, wherein the aluminum source is one or more selected from pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, the silicon source is one or more selected from silicate, sodium silicate, water glass and silica sol, the zirconium source is one or more selected from zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconium oxynitrate, zirconium nitrate, zirconium hydroxycarbonate and tetrabutoxy zirconium, the titanium source is one or more selected from titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, titanium aluminum titanium chloride and tetraethyltitanate, one or more of tetrabutyl titanate, tetra-n-propyl titanate, and tetra-isopropyl titanate.

When the above aluminum source, silicon source, zirconium source and titanium source are used, they may further include a chemical agent for precipitating or gelling them, such as acids (e.g., inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid, or organic acids such as acetic acid), and/or alkalis (e.g., sodium carbonate and sodium hydroxide).

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

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

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

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

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

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

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

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

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

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

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

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

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

One method in the prior art is to form spherical emulsion under the action of surface tension of a surfactant, and then at the moment of spray forming at a lower temperature, a pore-forming agent is vaporized or pyrolyzed in the spherical emulsion, and gas generated by vaporization and pyrolysis can cause a cavity in the microsphere emulsion; and (3) slowly releasing gas to form macropores on the surface to be communicated with the internal hollow structure, forming secondary stacking holes on the molecular sieve particles in the spray forming process to form mesopores on the surface of the molecular sieve microspheres, and combining the subsequent roasting process to obtain the large-particle hollow molecular sieve microspheres.

In the method, under the high temperature of the inlet air temperature of 400-1200 ℃, the oxide and the reducing agent in the slurry generate strong oxidation-reduction self-propagating combustion reaction to instantly generate a large amount of gas; meanwhile, the liquid drops enter a high-temperature area for spraying, the liquid drops are strongly evaporated, and the surface tension formed by the thickened slurry causes the liquid drops to shrink rapidly. The strong explosion of the inside and the strong contraction of the outside form a raspberry type hollow material with good strength. The prepared raspberry type oxide microspheres have high strength, high sphericity and high yield.

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

Preparing corresponding solution containing active components according to the pore volume of the carrier obtained after roasting, and then impregnating the catalyst.

The method of supporting the active metal component on the support is not particularly limited, provided that it is sufficient to support the active metal component on the support.

For example, the support may be contacted with a solution containing an effective amount of an active metal component-containing compound, such as by impregnation, co-precipitation, and the like, preferably impregnation, under conditions sufficient to deposit an effective amount of the active metal component on the support. The method according to the invention is not particularly limited as regards the method of impregnation and can be chosen conventionally in the field, for example: pore saturation impregnation methods and excess impregnation methods (i.e., supersaturated impregnation methods). According to the method of the invention, the impregnation is preferably an excess impregnation. Such pore saturation impregnation and excess impregnation methods are well known in the art and will not be described in detail herein.

Followed by drying, firing or not firing. The drying method is a conventional method, for example, a heat drying method, and when the drying method is a heat drying, the operating conditions of the drying include: the temperature is 80-350 ℃, preferably 100-300 ℃, and the time is 1-24 hours, preferably 2-12 hours. When the catalyst needs to be calcined, the calcination temperature is for converting the compound containing the active metal component into the oxide thereof, the preferred calcination temperature is 300-900 ℃, the calcination time is 1-6 hours, the further preferred temperature is 400-800 ℃, and the calcination time is 2-4 hours. According to the invention, the roasting temperature can be 350-650 ℃, preferably 400-600 ℃; the calcination time may be 2 to 6 hours, preferably 3 to 5 hours.

The compound containing the active metal component is preferably selected from one or more of soluble compounds thereof, such as one or more of water-soluble salts and complexes of the active metal component.

The group VIB metal and the group VIII metal may be chosen as is conventional in the art according to the process of the present invention. When the catalyst prepared according to the process of the present invention is used for hydrodesulphurisation, the group VIB metal is preferably molybdenum and the group VIII metal is preferably one or more of iron and cobalt, preferably iron and cobalt.

According to the present invention, the aqueous solution may be prepared by dissolving a group VIB metal-containing compound and a group VIII metal-containing compound, which are commonly used in the art, in water.

The group VIB metal-containing compound may be a group VIB metal-containing water-soluble compound commonly used in the art, and the group VIII metal-containing compound may be a group VIII metal-containing water-soluble compound commonly used in the art. Specifically, the group VIB metal-containing compound may be one or more of ammonium molybdate, ammonium paramolybdate, and molybdenum oxide.

The group VIII metal-containing compound can be one or more of group VIII metal nitrate, group VIII metal chloride, group VIII metal sulfate, group VIII metal formate, group VIII metal acetate, group VIII metal phosphate, group VIII metal citrate, group VIII metal oxalate, group VIII metal carbonate, group VIII metal hydroxycarbonate, group VIII metal hydroxide, group VIII metal phosphate, group VIII metal phosphide, group VIII metal sulfide, group VIII metal aluminate, group VIII metal molybdate, group VIII metal tungstate and group VIII metal water-soluble oxide; preferably one or more of group VIII metal oxalates, group VIII metal nitrates, group VIII metal sulfates, group VIII metal acetates, group VIII metal chlorides, group VIII metal carbonates, group VIII metal hydroxycarbonates, group VIII metal hydroxides, group VIII metal phosphates, group VIII metal molybdates, group VIII metal tungstates, and group VIII metal water-soluble oxides.

Specifically, the group VIII metal-containing compound may be, but is not limited to: cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate and cobalt chloride. The group VIII metal-containing compound may be, but is not limited to: one or more of cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, cobalt chloride, ferric nitrate, ferric sulfate, ferric acetate, basic ferric carbonate and ferric chloride.

According to the process of the present invention, the aqueous solution may also contain various cosolvents commonly used in the art to increase the solubility of the group VIB metal-containing compound and the group VIII metal-containing compound in water; or stabilizing the aqueous solution against precipitation. The co-solvent may be any of various materials commonly used in the art to achieve the above-described functions, and is not particularly limited. For example, the co-solvent may be one or more of phosphoric acid, citric acid and ammonia. The concentration of the aqueous ammonia in the present invention is not particularly limited, and may be selected conventionally in the art. The amount of co-solvent may be selected as is conventional in the art, and typically the co-solvent may be present in the aqueous solution in an amount of from 1 to 10% by weight.

According to the process of the present invention, the catalyst may also contain an effective amount of an auxiliary metal component, such as Zn, Mg, Ca, K, Zr, Ce, La or Mn, etc., capable of further improving the properties of the finally prepared catalyst. These adjunct ingredients may be incorporated into the slurry during spray forming; the compound containing the adjuvant and the compound containing the active metal component with or without other adjuvant components can be contacted with the carrier after being prepared into a mixed solution; alternatively, the compound containing the auxiliary may be separately prepared as a solution, and then contacted with the carrier, followed by drying and calcination. When the adjuvant and the active metal component are introduced separately into the support, it is preferred to first contact the support with a solution containing the adjuvant compound, to dry and calcine it, and then to contact the support with a solution containing the compound of the active metal component (with or without the compound of the other adjuvant component), for example by ion exchange, impregnation, co-precipitation, etc., preferably by impregnation. In one embodiment, the calcination temperature is 200-700 ℃, preferably 250-500 ℃, and the calcination time is 2-8 hours, preferably 3-6 hours.

The coke oven gas hydrodesulfurization catalyst provided by the invention adopts raspberry type carriers as carriers, so that the performance of the catalyst is improved. Therefore, the application also relates to the application of the coke-oven gas hydrodesulfurization catalyst in the catalytic coke-oven gas hydrodesulfurization, and a method for the hydrodesulfurization reaction of the coke-oven gas.

The method for the hydrodesulfurization reaction of the coke-oven gas comprises the step of carrying out contact reaction on the coke-oven gas and the hydrodesulfurization catalyst under the condition of the hydrodesulfurization reaction of the coke-oven gas.

Specifically, the method for the hydrodesulfurization reaction of the coke oven gas comprises the following steps:

the sulfur-containing compound is used for activating the coke oven gas hydrodesulfurization catalyst,

and (3) introducing a raw material gas into the reactor to contact with the activated catalyst for hydrodesulfurization reaction, wherein the raw material gas comprises hydrogen and coke oven gas.

The conditions of the hydrodesulfurization reaction of the coke oven gas are as follows: the hydrogen content in the raw material gas is 38-50% (volume), and the sulfur content is 80-150mg/m³(ii) a The reaction temperature is 330-; the space velocity of the raw material gas is 5000-10000h^-1。

The following examples further illustrate the process of the present invention but are not intended to limit the invention in any way.

Examples 1-13 illustrate raspberry-type vectors and methods of making the same provided by the present invention. Comparative example 1 illustrates a conventional catalyst carrier and a method for preparing the same.

Pseudo-boehmite powder (Shandong) (produced by Shandong aluminum works, solid content 67.0 wt%; gamma-Al)₂O₃The content is not smallAt 98 wt%, the same applies below);

pseudo-boehmite powder (produced by Changling catalyst factory, solid content 69.5 wt%; gamma-Al)₂O₃The content is not less than 98 wt%, the same applies below);

alumina sol (produced by Zhou village catalyst works, containing 22 wt% Al)₂O₃)，

Hydrochloric acid, nitric acid, aluminum nitrate, aluminum sulfate, aluminum chloride (produced by Beijing reagent factory, industrial grade);

zirconium nitrate, yttrium nitrate (yutai qixin chemical limited, industrial grade);

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

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

deionized water

Example 1

Adding 20kg of deionized water into a reaction kettle, adding 4.0kg of pseudo-boehmite powder (Shandong), and stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, and grinding for about 10 min; adding 2.3kg of PEG4000, continuing pulping, stirring and aging at 25 ℃ for 1.5 hours, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5Mpa, the inlet temperature of the spray dryer is 580 ℃, the outlet temperature of the spray dryer is 130 ℃, and the slurry flows out of the outlet of the spray dryer for 2-5 seconds to obtain the microsphere particles. And roasting the obtained product at 600 ℃ to obtain a material ZT1 which can be used for a catalyst carrier, and performing scanning electron microscope characterization on the prepared microsphere, wherein the electron microscope result is shown in figure 1. The physical properties are shown in Table 1.

Comparative example 1:

adding 20kg of deionized water into a reaction kettle, adding 4.0kg of pseudo-boehmite powder (Shandong), and stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, mixing and grinding for about 10 min; adding 2.3kg of PEG4000, pulping, aging at 25 deg.C under stirring for 1 hr, and spray drying at inlet temperature of 580 deg.C and outlet temperature of 130 deg.C under atomizing pressure of 2.5 Mpa. The obtained product is roasted at 600 ℃ to obtain a material DBZT1 which can be used for a catalyst carrier, and the physical properties of the material are shown in Table 1. Compared with the embodiment 1, the aluminum nitrate is not added, the obtained powder has different shapes, is basically solid, and has a hollow structure which is rarely communicated with the outside at the central part.

Comparative example 2

5.5kg of HZSM-5 molecular sieve with the grain size of 300-350 nm, 3kg of kaolin, 1kg of cement and 0.5kg of ammonium carbonate are added into 20kg of deionized water, and shearing emulsification is carried out for 2 hours at 2000rpm by a homogenizing emulsifier to form uniform colloidal slurry, wherein the solid content of the colloidal slurry is 31.7%.

And adding 300g P123 surfactant into the colloidal slurry, and continuing stirring for 1h to obtain the microsphere slurry.

And (3) conveying the microsphere slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.8MPa, the inlet temperature of the spray dryer is 280 ℃, the outlet temperature of the spray dryer is 120 ℃, and the microsphere slurry flows out from the outlet of the spray dryer for 2-5 seconds to obtain microsphere particles which are similar to apple-shaped particles. The obtained product is roasted at 600 ℃ to obtain a material DBZT2 which can be used for a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 2

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (Changling), and stirring and mixing uniformly for about 10 min; adding 175g of nitric acid, and grinding for about 10 min; adding 2.0kg of PEG4000, adding 0.5kg of zirconium nitrate, adding 5g of nitroglycerin, continuing pulping, stirring and aging at 25 ℃ for 0.5 hour, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5Mpa, the inlet temperature of the spray dryer is 560 ℃, the outlet temperature of the spray dryer is 140 ℃, and flowing out from the outlet of the spray dryer for 2-5 seconds to obtain the raspberry type microsphere particles. The obtained product is calcined at 500 ℃ to obtain a material ZT2 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 3

Adding 20kg of deionized water into a reaction kettle, adding 4.0kg of pseudo-boehmite powder (Changling), and stirring and mixing uniformly for about 10 min; adding 175g of nitric acid, and grinding for about 10 min; adding 2.0kg of PEG4000, adding 1.2kg of aluminum nitrate, adding 5g of nitroglycerin, continuing pulping, stirring and aging at 25 ℃ for 0.5 hour, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5MPa, the inlet temperature of the spray dryer is 580 ℃, the outlet temperature of the spray dryer is 130 ℃, and the slurry flows out from the outlet of the spray dryer for 2-5 seconds to obtain the raspberry type microsphere particles. The obtained product is calcined at 500 ℃ to obtain a material ZT3 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 4

Adding 20kg of deionized water into a reaction kettle, adding 4.0kg of pseudo-boehmite powder (Shandong), and stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, and grinding for about 10 min; adding 2.3kg of PEG4000, adding 1.2kg of aluminum nitrate, adding 0.4kg of potassium nitrate, continuously pulping, stirring and aging at 25 ℃ for 1.5 hours, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5Mpa, the inlet temperature of the spray dryer is 560 ℃, the outlet temperature of the spray dryer is 135 ℃, and allowing the slurry to flow out of the outlet of the spray dryer for 2-5 seconds to obtain the microsphere particles. The obtained product is calcined at 600 ℃ to obtain a material ZT4 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 5

Adding 20Kg of deionized water into a reaction kettle, adding 4.0Kg of pseudo-boehmite powder (Shandong) and 0.3Kg of white carbon black below 300 meshes, stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, and grinding for about 10 min; adding 2.3kg of PEG4000, adding 1.8kg of cobalt nitrate, continuing pulping, stirring and aging at 25 ℃ for 1.0 hour, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5MPa, the inlet temperature of the spray dryer is 560 ℃, the outlet temperature of the spray dryer is 120 ℃, and allowing the slurry to flow out of the outlet of the spray dryer for 2-5 seconds to obtain the microsphere particles. And roasting the obtained product at 700 ℃ to obtain the ZT5 material used for the catalyst carrier. The physical properties are shown in Table 1.

Example 6

Adding 20Kg of deionized water into a reaction kettle, adding 4.0Kg of pseudo-boehmite powder (Shandong) and 0.5Kg of alumina powder below 300 meshes, stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, and grinding for about 10 min; adding 2.3kg of PEG4000, adding 1.2kg of ferric nitrate, continuing pulping, stirring and aging at 25 ℃ for 1.5 hours, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5Mpa, the inlet temperature of the spray dryer is 600 ℃, the outlet temperature of the spray dryer is 180 ℃, and the slurry flows out from the outlet of the spray dryer for 2-5 seconds to obtain the raspberry type microsphere particles. The product obtained in example 4 was calcined at 700 ℃ to obtain ZT6, a material used as a catalyst carrier, the physical properties of which are shown in Table 1.

Example 7

Adding 20Kg of deionized water into a reaction kettle, adding 4.0Kg of pseudo-boehmite powder (Shandong) and 0.5Kg of white carbon black below 300 meshes, stirring and mixing uniformly for about 10 min; adding 200g of nitric acid, and grinding for about 10 min; adding 2.3kg of PEG4000, adding 1.2kg of aluminum nitrate, continuing pulping, stirring and aging at 25 ℃ for 1.5 hours, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5Mpa, the inlet temperature of the spray dryer is 700 ℃, the outlet temperature of the spray dryer is 160 ℃, and allowing the slurry to flow out of the outlet of the spray dryer for 2-5 seconds to obtain the microsphere particles. The obtained product is calcined at 600 ℃ to obtain a material ZT7 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 8

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (Changling), and stirring and mixing uniformly for about 10 min; adding 175g of nitric acid, and grinding for about 10 min; adding 2.0kg of PEG4000, adding 0.9kg of cobalt nitrate, adding 5g of urea, continuing pulping, stirring and aging at 25 ℃ for 0.5 hour, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5MPa, the inlet temperature of the spray dryer is 660 ℃, the outlet temperature of the spray dryer is 140 ℃, and flowing out from the outlet of the spray dryer for 2-5 seconds to obtain the raspberry type microsphere particles. The obtained product is calcined at 500 ℃ to obtain a material ZT8 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 9

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (Changling), and stirring and mixing uniformly for about 10 min; adding 175g of nitric acid, and grinding for about 10 min; 2.0Kg of PEG4000, 1.2Kg of zinc nitrate, 5g of urea and 0.14Kg of ethanol are added. And (3) continuing pulping, stirring and aging at 25 ℃ for 0.5 hour, conveying the slurry to a spray dryer, wherein the atomization pressure of the spray dryer is 2.5MPa, the inlet temperature of the spray dryer is 560 ℃, the outlet temperature of the spray dryer is 140 ℃, and the slurry flows out from the outlet of the spray dryer for 2-5 seconds to obtain the raspberry type microsphere particles. The obtained product is calcined at 500 ℃ to obtain a material ZT9 which can be used as a catalyst carrier, and the physical properties of the material are shown in Table 1.

TABLE 1 physical Properties of the catalyst support

The following examples illustrate coke oven gas hydrodesulfurization catalysts made from the alumina shaped supports provided by the present invention.

Example 10

30.0g Fe (NO) are weighed out₃)₃·9H₂O，4.0g KNO₃Dissolved in 80g of water, 30.0g of citric acid was added, and 25.0g of ammonium heptamolybdate was added and dissolved at 60 ℃ with stirring. 100g of the alumina carrier prepared in example 1 is added into a rotary evaporation container, the solution is added, the catalyst is prepared by rotary evaporation and impregnation at 60 ℃, then a sample is dried for 2h at 120 ℃, calcined for 4h at 450 ℃, and the calcined sample is repeated for 4 times according to the steps to prepare the catalyst C1. Wherein the content of each component is shown in table 2.

Example 11

30.0g Fe (NO) are weighed out₃)₃·9H₂O，4.0g KNO₃Dissolved in 80g of water, 30.0g of citric acid was added, and 25.0g of ammonium heptamolybdate was added and dissolved at 60 ℃ with stirring. 100g of the alumina carrier prepared in example 1 is added into a rotary evaporation container, the solution is added, the catalyst is prepared by rotary evaporation and impregnation at 60 ℃, then a sample is dried for 2h at 120 ℃, calcined for 4h at 450 ℃, and the calcined sample is repeated for 6 times according to the steps to prepare the catalyst C2. Wherein the content of each component is shown in table 2.

Example 12

Adding 30 g of ammonium molybdate into 70 ml of water, dropwise adding ammonia water with the concentration of 25 weight percent while heating and stirring until the ammonium molybdate is dissolved, then adding 10 g of ferric citrate, stirring and dissolving, and adding water to a constant volume of 85 ml. 100 grams of support ZT8 was impregnated with the above solution using a saturation impregnation method. The immersion time was 0.5 hour. The resulting solid was dried at 120 ℃ for 2 hours, then calcined at 450 ℃ for 3 hours, and the calcined sample was repeated 4 times according to the above procedure to obtain catalyst C3. Wherein the content of each component is shown in table 2.

Example 13

Weighing 90 ml of aqueous solution of 2.8 g of basic cobalt carbonate, 24.0 g of molybdenum trioxide and 16 g of citric acid, adding the alumina carrier ZT 6100 g prepared in the embodiment 6 into a rotary evaporation container, adding the solution, carrying out rotary evaporation and impregnation at 60 ℃ to prepare a catalyst, drying a sample at 120 ℃ for 2h, roasting at 450 ℃ for 4h, and repeating the steps for 3 times on the roasted sample to prepare the catalyst C4. Wherein the content of each component is shown in table 2.

Example 14

Weighing 90 ml of aqueous solution of 2.8 g of basic cobalt carbonate, 24.0 g of molybdenum trioxide and 16 g of citric acid, adding the alumina carrier ZT 9100 g prepared in example 9 into a rotary evaporation container, adding the solution, carrying out rotary evaporation and impregnation at 60 ℃ to prepare a catalyst, drying a sample at 120 ℃ for 2h, roasting the sample at 450 ℃ for 4h, and repeating the steps for 3 times on the roasted sample to prepare the catalyst C5. Wherein the content of each component is shown in table 2.

Comparative example 3

The carrier obtained in comparative example 1 was used to prepare a catalyst by the method of example 10 to obtain catalyst D2.

TABLE 2 catalyst component content

Examples	Catalyst numbering	CoO,％	Fe₂O₃,％	Mo₂O₃，％	K₂O，％	ZnO，％
							10	C1		12.8	29.1	4.0
11	C2		15.7	35.4	4.9
							12	C3	3.79	7.34	36.3
13	C4	1.91	3.82	41.06
							14	C5	1.91		41.06		5.27
Comparative example 3	D2		12.8	29.1	4.0

Examples 15-17 illustrate the use of the catalysts provided by the present invention and their effectiveness.

The organosulfur hydrogenation catalyst prepared in this example was pre-sulfided and tested for desulfurization performance under the following procedures and conditions:

according to the invention, the catalyst is provided, vulcanization is carried out before the catalyst is used, after the catalyst is filled, nitrogen is firstly used as circulating gas to heat the catalyst to 130 ℃ at the speed of 30 ℃/h, and the temperature is kept for 1 h; then the temperature is increased to 250 ℃ at the speed of 30 ℃/h, and then the mixture is put into nitrogenHydrogen with a volume concentration of 10% and 1.0% H are added₂S; and (3) vulcanization reaction conditions: the reaction temperature is 360 ℃, and the space velocity of the raw material gas is 1000h^-1. After the vulcanization is completed, the coke oven gas is switched to carry out the experiment.

The coke oven gas desulfurization experimental conditions are as follows: a mini-microchannel reactor, the mini-reactor module having 64 reaction channels and 144 cooling channels, the reaction channels being 200mm long. The catalyst loading was 25 mL. Reaction pressure: 4.0MPa, reaction temperature: 350 ℃ and the space velocity of 10000h^-1. Catalysts C1-C3 and comparative D2 were evaluated. The activity evaluation, the side reaction evaluation and the stability test are carried out by simulating the coke oven gas, and the low-temperature activity of the catalyst is investigated at 300 ℃. The simulated coke oven gas has the component H₂：48v％、CO：10v％、CO₂：2v％、CH₄：19v％、N₂: 11 v%, total sulfur: 100mg/m³，H₂S：55mg/m³、COS：25mg/m³、CS₂：18mg/m³Thiophene: 18mg/m³The reactivity of the catalyst is shown in Table 3.

TABLE 3 reactivity of the catalysts

Examples	Catalyst and process for preparing same	Organic sulfur in tail gas of mgs/m³	500h carbon deposition amount%
				15	C1	0.08	0.25
16	C2	0.07	0.22
				17	C3	0.06	0.21
Comparative example 4	D2	0.2	1.0

As can be seen from Table 3, the raspberry-type carrier provided by the invention is used as a catalyst carrier and then is prepared into a coke oven gas hydrodesulfurization catalyst, the catalyst has better performance under the same other conditions, the desulfurization efficiency is higher, and the catalyst basically does not deposit carbon after long-time operation.

The results show that the catalyst obtained by the raspberry type microspherical particle carrier in the embodiment of the invention has obviously better comprehensive performance in sphericity, strength and catalytic performance than the comparative example.

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

Claims

1. A coke oven gas hydrodesulfurization catalyst comprises a carrier and an active metal component loaded on the carrier, wherein the active metal component comprises molybdenum and a VIII group metal, and the VIII group metal is one or two of iron and cobalt;

the molybdenum content is 10-45 wt% calculated by oxide and based on the catalyst; the content of the VIII group metal is 1-16 wt%; the content of the support oxide is 39 to 89.5% by weight.

2. The coke oven gas hydrodesulfurization catalyst of claim 1 further comprising one or more promoter metal components selected from the group consisting of Zn, Mg, Ca, K, Zr, Ce, La and Mn, wherein the promoter metal component is present in an amount of 10 wt.% or less, preferably 7 wt.% or less, based on the catalyst, calculated as the oxide.

3. The coke oven gas hydrodesulfurization catalyst of claim 1 wherein the molybdenum content, calculated as oxide, is from 15 to 40% by weight, based on the catalyst, and the group VIII metal content, calculated as oxide, is preferably from 1.5 to 8% by weight.

4. The coke oven gas hydrodesulfurization catalyst of claim 1 wherein the raspberry type oxide microspheres have a sphericity of 0.50-0.99 and a diameter of 60-400 μm.

5. The coke oven gas hydrodesulfurization catalyst of claim 1 wherein the hollow structure has a diameter of 15 to 200 μm and a wall thickness around the wall of the hollow structure of 20 to 100 μm.

6. The coke oven gas hydrodesulfurization catalyst of claim 1 used in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.

7. A process for preparing a catalyst for the hydrodesulfurization of coke oven gas as claimed in any of claims 1 to 6, comprising the following steps:

providing the vector;

8. The method of claim 7, wherein providing the carrier comprises the steps of:

aging the dispersed slurry;

9. The method according to claim 8, wherein the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

10. The method according to claim 8, wherein the peptizing agent is selected from one or more of acids, bases and salts.

11. The method of claim 8, wherein the pore former is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and a surfactant.

12. The production method according to claim 8, wherein the oxide and/or the precursor thereof is selected from one or more of an aluminum source, a silicon source, a zirconium source and a titanium source, wherein the aluminum source is selected from one or more of pseudo-boehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride and sodium metaaluminate, the silicon source is selected from one or more of silicate ester, sodium silicate, water glass and silica sol, the zirconium source is selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium basic carbonate and tetrabutoxy zirconium, the titanium source is selected from one or more of titanium dioxide, metatitanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate and tetra-isopropyl titanate.

13. The method according to claim 8, wherein the dispersant is one or more selected from the group consisting of water, alcohols, ketones, and acids.

14. The preparation method according to claim 8, characterized in that the mass ratio of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or precursor thereof is (10-500): (1-10): (10-500): (10-1000).

15. The method of claim 8, further comprising adding a blasting agent to the dispersion, the blasting agent selected from one or more of picric acid, trinitrotoluene, nitroglycerin, nitrocotton, dana explosives, hexogen, and C4 plastic explosives.

16. The preparation method according to claim 15, wherein the amount of the blasting agent added is 0 to 1% of the total dry basis weight of the nitrate, the peptizing agent, the pore-forming agent and the oxide and/or the precursor thereof.

17. The production method according to any one of claims 8 to 16, wherein the drying apparatus is a flash drying apparatus or a spray drying apparatus.

18. The method according to any one of claims 8 to 16, wherein the temperature of the aging treatment is 0 to 90 ℃, preferably 20 to 60 ℃.

19. Use of a catalyst for the hydrodesulfurization of coke oven gas as claimed in any of claims 1 to 6 or obtained by a process as claimed in any of claims 7 to 18 for the hydrodesulfurization of catalytic coke oven gas.

20. A method for hydrodesulfurizing coke-oven gas, comprising contacting coke-oven gas with the catalyst for hydrodesulfurizing coke-oven gas according to any one of claims 1 to 6 or the catalyst obtained by the method according to any one of claims 7 to 18 under the reaction conditions for hydrodesulfurizing coke-oven gas.

21. The process of claim 20, wherein the hydrodesulfurization of the coke oven gas is carried out in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm.