CN112742391B

CN112742391B - Natural gas hydrodesulfurization catalyst and preparation and application thereof

Info

Publication number: CN112742391B
Application number: CN201911053542.4A
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: 2023-06-09
Anticipated expiration: 2039-10-31
Also published as: CN112742391A

Abstract

Discloses a natural 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 cobalt, and the carrier is a raspberry oxide microsphere. The raspberry oxide microsphere has better mass transfer and heat transfer characteristics, has strength obviously higher than that of the existing products with similar structures, and has the advantages of simple preparation method, low cost and high efficiency, and is suitable for large-scale industrial application. The natural gas hydrodesulfurization provided by the invention adopts the raspberry type carrier suitable for the micro-channel as a carrier, so that the performance of the catalyst is improved.

Description

Natural gas hydrodesulfurization catalyst and preparation and application thereof

Technical Field

The invention relates to a hydrodesulfurization catalyst for natural gas and oilfield gas, and a preparation method and application thereof.

Background

In the production processes of large and medium-sized synthetic ammonia, oil refining system hydrogen production, methanol synthesis and the like, hydrocarbon raw materials such as natural gas, oilfield associated gas, light oil and the like all contain a certain amount of sulfides. Natural gas mainly contains hydrogen sulfide and low-boiling organic compounds. These sulfides are detrimental to a range of catalysts for ammonia synthesis, hydrogen production, methanol synthesis, etc., particularly steam reforming, hypo-reforming, and methanation catalysts. Therefore, there is a strict limit to the sulfur content in the raw material, and it is usually not more than 0.1X10 ^-6 ～0.5×10 ^-6 . The hydrogen sulfide can be removed by a zinc oxide desulfurizing agent; organic sulfur, especially complex organic sulfur such as thiophenes, must be converted to hydrogen sulfide using a hydroconversion catalyst and then removed using a zinc oxide desulfurizing agent.

The hydrotreating catalyst is typically formed by supporting group VIB and group VIII metal components on an alumina support. In general, the hydrogenation active component of the catalyst is preferably Co-Mo combinations for the reaction processes mainly comprising hydrodesulfurization, and Ni-Mo or Ni-W combinations for the reaction processes mainly comprising hydrodeoxygenation, hydrodenitrogenation and aromatic hydrogenation.In order to combine the advantages of different catalysts, there are also catalysts using Ni-Co-Mo, ni-Mo-W as active components. For example, CN 1229835a discloses a light oil hydrotreating catalyst containing molybdenum and/or tungsten, which contains tungsten oxide and/or molybdenum oxide, nickel oxide and cobalt oxide supported on an alumina carrier, the content of the tungsten oxide and/or molybdenum oxide being 4% by weight to less than 10% by weight, the content of the nickel oxide being 1 to 5%, the content of the cobalt oxide being 0.01 to 1% by weight, and the ratio of the total atomic number of nickel and cobalt to the total atomic number of nickel, cobalt, tungsten and/or molybdenum being 0.3 to 0.9. Compared with the prior art, the catalyst has lower metal content and higher low-temperature activity. The catalyst is especially suitable for the hydrogenation and mercaptan removal process of light oil products. CN103182310a discloses a preparation method of a distillate hydrotreating catalyst. From gamma-Al ₂ O ₃ Or silicon-containing gamma-Al ₂ O ₃ The active components of Ni, co and W/Mo are loaded, and the active components also contain P element as a promoter component and can also contain any element in Mg, zn, fe, ca as the promoter component. The preparation method of the catalyst comprises the following steps: (1) Firstly preparing gamma-Al ₂ O ₃ Or silicon-containing gamma-Al ₂ O ₃ A carrier; (2) In gamma-Al ₂ O ₃ Or silicon-containing gamma-Al ₂ O ₃ Loading Ni metal components and P auxiliary components on a carrier, and then drying and roasting; (3) Impregnating the carrier obtained in the step (2) by adopting a solution containing a Co compound and a W and/or Mo compound, drying and roasting to obtain a catalyst finished product. The catalyst can be used for hydrotreating light distillate oil such as reforming raw materials, gasoline fractions, kerosene fractions and the like, and has high hydrodesulfurization activity.

Depending on the feedstock used or the type and amount of sulfur contained therein, different types of hydroconversion catalysts may be selected. Most of the foreign hydrogenation catalysts still use cobalt and molybdenum as active components, the appearance is mostly strip-shaped, but Topse is hollow strip-shaped, davison is spoke-shaped in the United states, and Polish is clover-shaped or clover-shaped in the four-leaf, so as to reduce resistance. The organic sulfur hydroconversion reaction belongs to the internal diffusion control under the factory use condition. If the space velocity is too large, the residence time of the hydrocarbon feedstock in the catalyst bed is short and the organosulfur does not enter the inner surface of the catalyst I.e., has passed through the catalyst bed, incomplete hydrogenolysis and reduced utilization of the catalyst inner surface. In practice, too low a space velocity will reduce the plant capacity and too high a space velocity will result in a reduced desulfurization rate. The general hydrogenation conversion catalyst has the operation application range of light oil of 1-6h ^-1 Natural gas 1000h ^-1 -3000h ^-1 As high a space velocity as possible is typically employed while ensuring the outlet sulfur content precursor.

CN201710708936.3 discloses a process for preparing catalyst for hydrogenation conversion of organic sulfur, which comprises mixing TiCl ₄ And AlCl ₃ The mixed solution of (2) and ammonia water solution react in a reactor heated by microwaves, are aged and spray-dried, and are roasted by microwaves to obtain catalyst carrier powder; mixing the mixed solution of ammonium paramolybdate and soluble first active auxiliary agent salt with carrier powder, immersing in ultrasonic wave, drying, roasting in a microwave roasting oven to obtain semi-finished product catalyst powder, mixing the mixed solution of ammonium paramolybdate, soluble first active auxiliary agent salt and soluble second active auxiliary agent salt with semi-finished product catalyst powder, immersing in ultrasonic wave, roasting to obtain finished product catalyst powder, uniformly mixing the prepared finished product catalyst powder, binder, pore-forming agent and water, extruding, forming, drying and roasting to obtain the finished product organic sulfur hydrogenation catalyst. The invention has the advantages of high conversion rate and long service life.

The above catalysts are all particulate catalysts suitable for use in conventional fixed beds. The catalyst with simple process, strong raw material adaptability and low operation cost is sought, and has important significance for expanding the raw material supply of hydrogen production devices of refineries and large-scale chemical fertilizer plants.

Disclosure of Invention

The inventor researches find that when a carrier with a raspberry type cavity structure is adopted to prepare the natural gas hydrodesulfurization catalyst, the reaction performance of the catalyst is obviously improved.

In one aspect, the present application provides a natural gas hydrodesulfurization catalyst comprising a support and an active metal component supported on the support, wherein the active metal component comprises molybdenum and cobalt,

the carrier is a raspberry oxide microsphere, the raspberry 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 one end open; wherein the carrier oxide in the raspberry oxide microspheres is selected from one or more of aluminum oxide, silicon oxide, zirconium oxide and titanium oxide;

molybdenum content of 12-45 wt%, calculated as oxide and based on the catalyst; cobalt content of 1-8 wt%; the content of carrier oxide is 47-87 wt.%.

In one embodiment, the catalyst further contains one or more auxiliary components selected from P, B, si or F, and the content of the auxiliary components in element is below 5 wt%, preferably below 4 wt%, based on the catalyst.

In one embodiment, the molybdenum content, calculated as oxide, is 15 to 43 wt.%, based on the catalyst; cobalt content of 2-7 wt% calculated on oxide basis; the content of carrier oxide is 50-83 wt%.

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

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

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

In another aspect, the present application provides a process for the hydrodesulfurization of a natural gas of the present application comprising the steps of:

providing the carrier;

impregnating the carrier with a solution of a compound containing an active metal component, drying and roasting to obtain the natural 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 the dispersing agent, and stirring to obtain dispersed slurry;

aging the dispersion slurry;

feeding the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; and (3) drying and forming at the air outlet temperature of 50-300 ℃, preferably 120-200 ℃ to obtain the raspberry 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-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactant.

In one embodiment, the oxide and/or precursor thereof is selected from one or more of an aluminum source selected from one or more of pseudoboehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconium oxynitrate, zirconium nitrate, zirconium basic carbonate, and zirconium tetrabutoxide, and a titanium source 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 tetraisopropyl titanate.

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

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

In one embodiment, further comprising adding to the dispersant a blasting agent selected from one or more of picric acid, trinitrotoluene, nitroglycerin, nitrocotton, darner's explosive, nivalene, and C4 plastic explosive.

In one embodiment, the blasting agent is added in an amount of 0 to 1% by weight of the total dry basis of the nitrate salt, 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 yet another aspect, the present application provides the use of the natural gas hydrodesulfurization catalyst of the present application for catalyzing the hydrodesulfurization of natural gas.

In yet another aspect, the present application provides a process for hydrodesulfurizing natural gas comprising contacting natural gas with a natural gas hydrodesulfurization catalyst of the present application under natural gas hydrodesulfurization reaction conditions.

In one embodiment, the natural gas hydrodesulfurization reaction is carried out in a microchannel reactor, the microchannel reactor being one in which the reaction channels have at least one dimension and a size of less than 1000 μm.

The raspberry oxide microsphere has better mass transfer and heat transfer characteristics, has strength obviously higher than that of the existing products with similar structures, and has the advantages of simple preparation method, low cost and high efficiency, and is suitable for large-scale industrial application. The natural gas hydrodesulfurization provided by the invention adopts the raspberry type carrier suitable for the micro-channel as a carrier, 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 scheme of the invention is further described below according to specific embodiments. The scope of the invention is not limited to the following examples, which are given for illustrative purposes only and do not limit the invention in any way.

In one aspect, the present application provides a natural gas hydrodesulfurization catalyst comprising a support and an active metal component supported on the support, wherein the active metal component comprises molybdenum and cobalt.

The carrier is a raspberry oxide microsphere, the raspberry 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 one end open; wherein the carrier oxide in the raspberry oxide microspheres is selected from one or more of aluminum oxide, silicon oxide, zirconium oxide and titanium oxide.

In the catalyst, a catalyst carrier is raspberry oxide microspheres, wherein the raspberry oxide microspheres are hollow microspheres with a large hole on the surface, a hollow structure is arranged in the hollow microspheres, and the large hole and the hollow structure are communicated to form a cavity with one end open; wherein the carrier oxide in the raspberry oxide microspheres is selected from one or more of aluminum oxide, silicon oxide, zirconium oxide and titanium oxide.

The raspberry oxide microsphere has an appearance similar to a sphere, the sphericity is 0.50-0.99, and the diameter is 60-400 mu m. The hollow structure has a diameter of 15-200 μm and the wall thickness of the wall surrounding the hollow structure is 20-100 μm. The specific surface of the raspberry oxide microsphere is about 10-500m after roasting at 300-900 DEG C ² Per g, pore volume is about 0.1-2ml/g. The preparation method of the raspberry type oxide microsphere carrier is described in the following description of the specification. In one embodiment, the support oxide is present in an amount of 47 to 87 wt%, preferably 50 to 83 wt%, calculated as oxide and based on the catalyst.

The sphericity of the bead body is calculated from the following formula:

σ＝4πA/L ²

wherein: sigma is sphericity; a is the projection area of the microsphere, and the unit is m ² The method comprises the steps of carrying out a first treatment on the surface of the L is the projected perimeter of the microsphere, and the unit is m; a and L were obtained from SEM pictures of microspheres, processed by the Image-Pro Plus picture processing software.

The raspberry oxide microspheres of the invention are calcined at 400-1300 ℃, preferably 450-1100 ℃, and further preferably 500-700 ℃ to obtain oxides. The specific surface is about 0.1-900 m ² Preferably 10 to 300m per gram ² The pore volume per gram is about 0.01 to 3.6ml/g, preferably 0.1 to 0.9ml/g.

The raspberry oxide microsphere has a crushing rate of 0-1%, and the crushing rate is measured according to a method provided by a similar strength standard number Q/SH3360 226-2010, and the specific method is as follows:

firstly, selecting sieves S1 and S2 with the mesh numbers of M1 and M2 respectively, wherein M1 is less than M2, enabling microspheres to be tested to pass through the sieve S1 with the mesh number of M1 firstly, enabling the microsphere powder after sieving to pass through the sieve S2 with the mesh number of M2, and finally enabling the microsphere powder trapped by the sieve S2 to serve as a sample to be tested.

Adding a certain mass of sample to be tested into a cylindrical steel container with the section diameter of 10mm, applying a certain pressure to the microspheres through a cylinder, continuously screening the pressed microsphere powder by using 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 added mass of the microspheres to obtain the breakage rate of the microspheres.

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

The strength of the microsphere can be evaluated by utilizing the crushing rate; the strength of the microspheres is higher as the crushing rate is smaller.

The raspberry-shaped oxide microsphere has low crushing rate and obviously higher strength than the prior known oxide microsphere, such as the apple-shaped hollow molecular sieve microsphere disclosed by CN108404970A under the condition of pressurization, which is determined by the different raw materials and preparation methods. The high strength makes the raspberry oxide microsphere have larger porosity, greatly reduced pressure drop, excellent processability and wear resistance, short reaction diffusion distance in the catalyst field as a carrier, and wide application prospect, and can be made into high-temperature heat insulation materials, biological materials and photochemical materials.

The active metal components in the catalysts of the present application include molybdenum and cobalt. These active metal components may be present in the form of metal oxides, also in the form of metal sulfides, and even in the reduced form. These existing forms may be converted to each other, for example, the metal oxide may be converted to a metal sulfide form after sulfidation, or may be converted to a reduced form after reduction. The person skilled in the art can make the corresponding selections and transformations according to the needs of the use. For example, in performing desulfurization, 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 is 12 to 45 wt.%, preferably 15 to 43 wt.%, calculated as oxide and based on the catalyst. In one embodiment the cobalt content is 1 to 8 wt.%, preferably 2 to 7 wt.%.

In one embodiment, the catalyst further contains one or more auxiliary components selected from P, B, si or F, and the content of the auxiliary components in terms of elements is below 5 wt%, preferably below 4 wt%, based on the catalyst.

A microchannel reactor is a reactor in which the reaction channels have at least one dimension and a size of less than 1000 μm. The specific surface area of the microchannel reactor is large, so that the residence time required by the reaction can be shortened; the heat transfer process is enhanced so that the chemical or chemical reaction can be carried out almost under isothermal conditions; strengthening the mass transfer process; the safety and the controllability are good; is easy to amplify. By utilizing the micro-channel reaction technology, the reaction of the high-activity and micro-particle catalyst under the isothermal condition can be realized, the defects that the heat transfer of a fixed bed is poor and the catalyst with small granularity cannot be applied are overcome, and the problem of catalyst abrasion of a fluidized bed is solved. Therefore, has very important significance. By adopting the micro-channel reactor, the process flow can be simplified, the device volume and equipment investment can be reduced, unstable working conditions such as temperature runaway and the like can be avoided, the occupied area can be reduced, but the development of the efficient micro-channel catalyst suitable for the micro-reactor is necessary. Optimizing the catalyst particle size and shape by optimizing the catalyst metal loading and formulation; the productivity of the reactor can be increased by increasing the space velocity, increasing the length of the reaction channel, etc. to increase the catalyst space time yield. The natural gas hydrodesulfurization catalyst can be used for a microchannel reactor.

In a second aspect, the present application provides a process for preparing a natural gas hydrodesulfurization catalyst of the present application comprising the steps of:

providing the carrier;

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

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

aging the dispersion slurry; feeding the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃, and preferably 450-700 ℃; and (3) drying and forming at the air outlet temperature of 50-300 ℃, preferably 120-200 ℃ to obtain the raspberry 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 can promote the oxidant which can be used as a pore-forming agent under the high temperature condition, and the oxidant can perform self-propagating combustion reaction at the high temperature to generate gas and steam so that the oxide material forms a cavity.

In the preparation method of the invention, the peptizing agent is selected from one or more of acids, alkalis and salts. The acid can be selected from: inorganic acid (such as hydrochloric acid, sulfuric acid, nitric acid, etc.), organic acid (formic acid, acetic acid, oxalic acid, etc.), inorganic acid or a combination of one or more of the organic acids; the alkali can be selected from: inorganic base (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, sodium carbonate (anhydrous sodium carbonate), sodium carbonate (monohydrate, heptahydrate, decahydrate), sodium bicarbonate (baking soda), potassium carbonate, potassium bicarbonate, etc.), organic base (such as amine compound, alkali metal salt of alcohol, alkaloid, alkyl metal lithium compound, etc.), inorganic acid or combination of several kinds of organic acid; the salts can be selected from: inorganic acid salts (e.g., hydrochloric acid, sulfate, nitrate, etc.), organic acid salts (formate, acetate, oxalate, etc.), and one or a combination of inorganic acid salts or organic acid salts.

In the preparation method of the invention, the pore-forming agent is one or more selected from starch, synthetic cellulose, polyalcohol and surfactant. The synthetic cellulose is preferably one or more of carboxymethyl cellulose, methyl cellulose, ethyl cellulose and hydroxy fiber fatty alcohol polyvinyl ether; the polyalcohol 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 its derivatives, and acrylic acid copolymer and maleic acid copolymer with molecular weight of 200-2000000.

In the preparation method of the invention, the oxide and/or the precursor thereof can be directly alumina, silica, zirconia and titanium oxide, or can be precursor for forming the oxide, and can be specifically 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, 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 zirconium tetrabutoxide, and the titanium source is selected from one or more of titanium dioxide, meta-titanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate and tetraisopropyl titanate.

When the above aluminum source, silicon source, zirconium source and titanium source are used, chemical agents for precipitating or gelling them, such as acids (e.g., inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc., or organic acids such as acetic acid, etc.), and/or bases (e.g., sodium carbonate, sodium hydroxide, etc.), are also included.

When it is desired 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, copper oxide, and the like may be added, and precursors capable of forming these oxides may be added.

In the preparation method of the invention, 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 like, and the acids can be formic acid, acetic acid, propionic acid and the like. Preferably, the dispersing agent is a mixture of water and a small amount of ethanol, the small amount of ethanol can achieve better dispersing effect in water and can serve as a boiling point regulator, and the water evaporation effect and the liquid drop shrinkage effect are matched and matched better through the adjustment of the dispersing agent, so that the microsphere appearance effect is more regular and smoother.

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

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

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

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

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

Then the dispersion slurry is aged at 0-90 ℃ for 0.1-24 hours, preferably 0.5-2 hours.

After aging treatment, the dispersion slurry is sent into a spray drying device, and is dried and molded 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 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 to material drying. After the wet material is dispersed in a drying tower, the moisture is quickly vaporized in contact with hot air, and a dried 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, crushing and the like.

The working principle of spray drying is that the materials to be dried are dispersed into very fine particles like fog through mechanical action (such as pressure, centrifugation and airflow spraying), the evaporation area of moisture is increased, the drying process is accelerated, and most of moisture is removed in a short time by contacting with hot air, so that solid matters in the materials are dried into powder.

The spray drying apparatus used in the present invention is a conventional apparatus in the existing flow, and the present invention is not particularly limited thereto. Spray drying apparatus generally comprises: the device comprises a feeding system, a hot air system, a drying tower system, a material 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 surface of the top end of the drying tower system, the material 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 basically necessary to provide a spray of the stock solution; drying tiny liquid drops in spraying; the separation and recovery of the fine powder products. In the spray drying apparatus, an atomizer, a drying chamber, and a fine powder recoverer are generally equipped corresponding to the above functions.

Because of the more control parameters and complex factors in the spray drying process, the particle size and particle shape after spray drying are very complex. It is a difficulty to selectively shape the product into a desired single shape, such as a cavity, typically in the size range of microns, and typically in a mixture of shapes including spheres, discs, apples, grapes, cavities, and meniscus.

One method in the prior art is to form spherical emulsion under the surface tension of surfactant, then spray forming at a lower temperature instantly, gasifying or pyrolyzing pore-forming agent in the spherical emulsion, and the gas generated by the vaporization and pyrolysis can cause the cavity in the microsphere emulsion; the slow release of the gas causes the formation of macropores on the surface to communicate with the hollow structure in the interior, and the molecular sieve particles form secondary stacking holes to become mesopores on the surface of the molecular sieve microspheres in the spray forming process, and the subsequent roasting process is combined to obtain the large-particle hollow molecular sieve microspheres.

The method is characterized in that under the high temperature of 400-1200 ℃ of air inlet temperature, the oxide and the reducing agent in the slurry undergo strong oxidation-reduction self-propagating combustion reaction, and a large amount of gas is instantaneously generated; at the same time, the spray of droplets enters a high temperature zone, where it evaporates strongly, and the surface tension of the thickened slurry results in a sharp contraction of the droplets. The internal strong explosion and the external strong shrinkage form a raspberry type hollow material with good strength. The prepared raspberry oxide microsphere has high strength, high sphericity and high yield.

The raspberry oxide microsphere can be used as a carrier after being roasted, and can be prepared into various catalysts after corresponding active components are loaded. The roasting temperature can be 400-1300 ℃, preferably 450-1100 ℃, and more preferably 500-700 ℃; the calcination time may be 1 to 12 hours, preferably 2 to 8 hours, and more preferably 3 to 4 hours.

The carrier obtained after calcination is prepared into corresponding solution containing active components according to the pore volume of the carrier, and then the catalyst is impregnated.

The method of supporting the active metal component on the support is not particularly limited in the present invention 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 the active metal component-containing compound under conditions sufficient to deposit an effective amount of the active metal component onto the support, such as by impregnation, co-precipitation, or the like, with impregnation being preferred. The method according to the present invention is not particularly limited as to the impregnation method, and may be a conventional choice in the art, for example: pore saturation impregnation and excess impregnation (i.e., supersaturation impregnation). According to the method of the invention, the impregnation is preferably an excess impregnation. The pore saturation impregnation and overdose impregnation methods are well known in the art and are not described in detail herein.

And then dried, calcined or not calcined. The drying method and the conventional method, for example, a method of heat drying, and when the drying method is heat drying, the operation conditions of the drying include: the temperature is 80 to 350 ℃, preferably 100 to 300 ℃, and the time is 1 to 24 hours, preferably 2 to 12 hours. When the catalyst is to be calcined, the calcination temperature is preferably 300 to 900 ℃ for 1 to 6 hours, more preferably 400 to 800 ℃ for 2 to 4 hours, for the purpose of effecting conversion of the active metal component-containing compound to its oxide. According to the invention, the temperature of the calcination may be 350-650 ℃, preferably 400-600 ℃; the calcination time may be 2 to 6 hours, preferably 3 to 5 hours.

The active metal component-containing compounds are preferably selected from one or more of their soluble compounds, such as one or more of water-soluble salts, complexes of active metal component-containing compounds. According to the present invention, the aqueous solution may be prepared by dissolving a molybdenum-containing compound and a cobalt-containing compound, which are commonly used in the art, in water.

The molybdenum-containing compound may be a molybdenum-containing water-soluble compound commonly used in the art, and the cobalt-containing compound may be a cobalt-containing water-soluble compound commonly used in the art. In particular, the molybdenum-containing compound may be one or more of ammonium molybdate, ammonium paramolybdate, molybdenum oxide.

The cobalt-containing compound may be one or more of a nitrate of cobalt, a chloride of cobalt, a sulfate of cobalt, a formate of cobalt, an acetate of cobalt, a phosphate of cobalt, a citrate of cobalt, an oxalate of cobalt, a carbonate of cobalt, a basic carbonate of cobalt, a hydroxide of cobalt, a phosphate of cobalt, a phosphide of cobalt, a sulfide of cobalt, an aluminate of cobalt, a molybdate of cobalt, a tungstate of cobalt, and a water-soluble oxide of cobalt; preferably one or more of cobalt oxalate, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt chloride, cobalt carbonate, cobalt hydroxycarbonate, cobalt hydroxide, cobalt phosphate, cobalt molybdate, cobalt tungstate and cobalt water-soluble oxide.

In particular, the cobalt-containing compound may be, but is not limited to: one or more of cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate and cobalt chloride. According to the method of the present invention, the aqueous solution may further contain various co-solvents commonly used in the art to enhance the solubility of the molybdenum-containing compound and the cobalt-containing compound in water; or stabilize the aqueous solution against precipitation. The cosolvent may be any of various solvents commonly used in the art that can achieve the above functions, and is not particularly limited. For example, the cosolvent may be one or more of phosphoric acid, citric acid, and aqueous ammonia. The concentration of the aqueous ammonia is not particularly limited in the present invention, and may be selected as usual in the art. The amount of the co-solvent may be selected as usual in the art, and in general, the co-solvent may be contained in the aqueous solution in an amount of 1 to 10% by weight.

The catalyst may also contain an effective amount of an adjunct component capable of further improving the performance of the final prepared catalyst according to the process of the present invention. The content of the auxiliary component in terms of elements is 5% by weight or less, preferably 4% by weight or less, based on the catalyst. The method of introducing these auxiliary components may be incorporated into the slurry at the time of spray forming; the compound containing the auxiliary agent may be contacted with the carrier after the compound containing the active metal component and the compound containing the active metal component with or without other auxiliary agent components are formulated into a mixed solution; it is also possible to formulate the solution of the auxiliary-containing compound separately and then contact it with the support, after which it is dried and calcined. When the auxiliary agent and the active metal component are introduced separately into the support, it is preferable to first contact the support with a solution containing the auxiliary agent compound, and then contact the support with a solution of the active metal component-containing compound (compound with or without other auxiliary agent component) after drying and firing, for example, by ion exchange, impregnation, co-precipitation, or the like, and impregnation is preferable. The calcination temperature is 200-700 ℃, preferably 250-500 ℃, and the calcination time is 2-8 hours, preferably 3-6 hours.

The natural gas hydrodesulfurization provided by the invention adopts raspberry type carrier as carrier, so that the performance of the catalyst is improved. Thus, the present application also relates to the use of the natural gas hydrodesulfurization catalyst of the present application for catalyzing the hydrodesulfurization of natural gas, and to a process for the hydrodesulfurization of natural gas.

The process of the present application for hydrodesulfurization of natural gas comprises contacting natural gas with a natural gas hydrodesulfurization catalyst of the present application under natural gas hydrodesulfurization reaction conditions.

Specifically, the method for hydrodesulfurization of natural gas comprises the following steps:

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

a feed gas comprising hydrogen and natural gas is passed into a reactor to contact the activated catalyst for hydrodesulfurization.

The conditions for the hydrodesulfurization of natural gas are: the hydrogen content in the raw material gas is 0-12%, and the sulfur content is 60-350ppm; the reaction temperature is 300-350 ℃, and the reaction pressure is 2.0-2.5MPa; the airspeed of the raw material gas is 5000-10000h ^-1 。

The following examples are provided to 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 provided by the invention and methods of making the same. Comparative example 1 illustrates a conventional catalyst support and a method for preparing the same.

Pseudo-boehmite powder (Shandong) (produced by Shandong aluminum factory, solid content 67.0 wt%, gamma-Al) ₂ O ₃ The content is not less than 98% by weight, the same applies below);

pseudo-boehmite powder (produced by Kaolin catalyst plant, solid content 69.5% by weight, gamma-Al) ₂ O ₃ The content is not less than 98% by weight, the same applies below);

aluminum sol (manufactured by Zhoucun catalyst plant, containing 22 wt% of Al ₂ O ₃ )，

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

zirconium nitrate, yttrium nitrate (fish table Ji Xin chemical industry limited, industrial grade);

polyethylene glycol PEG4000 powder (double howl rubber plastic materials Co., ltd.);

methylcellulose (Hubei Jiang Mintai chemical Co., ltd.);

deionized water

Example 1

Adding deionized water 20kg into a reaction kettle, adding pseudo-boehmite powder (Shandong) 4.0kg, and uniformly stirring and mixing for about 10min; 200g of nitric acid is added and grinded for about 10min; adding 2.3kg of PEG4000, adding 1.2kg of aluminum nitrate, pulping continuously, stirring at 25 ℃ for ageing 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 flowing out from the outlet of the spray dryer through 2-5 s to obtain microsphere particles. And roasting the obtained product at 600 ℃ to obtain a material ZT1 for the catalyst carrier, and carrying out 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.

As can be seen from FIG. 1, the prepared microspheres are similar to raspberry type microspheres in which the particle size of the raspberry type microspheres is 70 to 200 μm; the thickness of the shell layer is 35-50 mu m. The microsphere has a large hole on its surface.

Comparative example 1:

adding deionized water 20kg into a reaction kettle, adding pseudo-boehmite powder (Shandong) 4.0kg, and uniformly stirring and mixing for about 10min; 200g of nitric acid is added, and mixed grinding is carried out for about 10min; adding 2.3kg of PEG4000, pulping, stirring at 25deg.C, aging for 1 hr, and drying and shaping with spray drying device, wherein the atomization pressure of spray dryer is 2.5Mpa, and the inlet temperature of spray dryer is 580 deg.C and outlet temperature is 130 deg.C. The resulting product was calcined at 600 ℃ to give material DBZT1 useful for catalyst support, the physical properties of which are shown in table 1. Compared with the embodiment 1, the aluminum nitrate is not added, the powder has different shapes, is basically solid, and has a hollow structure which is rarely communicated with the outside in the center.

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 and emulsifying at 2000rpm are carried out for 2 hours by using a homogenizing emulsifying machine to form uniform colloid slurry, wherein the solid content of the colloid slurry is 31.7%.

300g of P123 surfactant was added to the colloidal slurry, and stirring was continued for 1 hour to obtain a 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 s to obtain microsphere particles similar to apples. The resulting product was calcined at 600 ℃ to give material DBZT2 useful for catalyst support, the physical properties of which are shown in table 1.

Example 2

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (kaolin), and uniformly stirring and mixing for about 10min; adding 175g of nitric acid and grinding for about 10min; adding 2.0kg of PEG4000, adding 1.2kg of aluminum nitrate, adding 5g of nitroglycerin, pulping continuously, stirring and ageing for 0.5 hours at 25 ℃, 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 raspberry microsphere particles are obtained after flowing out from the outlet of the spray dryer through 2-5 s. The resulting product was calcined at 500 ℃ to give material ZT2 useful for catalyst support, the physical properties of which are shown in table 1.

Example 3

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, and uniformly stirring and mixing for about 10min; 200g of nitric acid is added and grinded for about 10min; adding 2.3kg of PEG4000, adding 1.2kg of aluminum nitrate, pulping continuously, stirring at 25 ℃ for ageing 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 flowing out from the outlet of the spray dryer through 2-5 s to obtain microsphere particles. The obtained product is roasted at 600 ℃ to obtain the material ZT3 which can be used for the catalyst carrier. The physical properties 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 uniformly stirring and mixing 0.3Kg of white carbon black below 300 meshes for about 10min; 200g of nitric acid is added and grinded for about 10min; adding 2.3kg of PEG4000, adding 1.2kg of aluminum nitrate, pulping continuously, stirring at 25 ℃ for ageing 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 flowing out from the outlet of the spray dryer through 2-5 s to obtain microsphere particles. The obtained product is roasted at 600 ℃ to obtain the material ZT4 which can be used for the catalyst carrier. The physical properties are shown in Table 1.

Example 5

36kg of 40% silica sol (manufacturer) is added with 2.0kg of PEG4000, 1.8kg of cobalt nitrate, stirred for 1 hour at 50 ℃, evenly mixed, 15g of nitrocotton is added, pulping is continued, stirring and ageing are carried out at 50 ℃ for 1.5 hours, the mixture is conveyed to a spray dryer, 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 100 ℃, and the mixture flows out from the outlet of the spray dryer for 2-5 seconds, so that raspberry microsphere particles are obtained. The product obtained in example 4 was calcined at 700℃to give ZT5, a material useful for catalyst supports, the physical properties of which are shown in Table 1.

Example 6

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (kaolin), and uniformly stirring and mixing for about 10min; adding 175g of nitric acid and grinding for about 10min; adding 2.0kg of PEG4000, adding 1.2kg of cobalt nitrate, adding 5g of citric acid, pulping continuously, stirring and ageing for 0.5 hours at 25 ℃, 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 product flows out from the outlet of the spray dryer through 2-5 s, and roasting the obtained product at 500 ℃ to obtain a material ZT6 for a catalyst carrier, and the physical properties of the material are shown in Table 1.

Example 7

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (kaolin), and uniformly stirring and mixing for about 10min; adding 175g of nitric acid and grinding for about 10min; adding 2.0kg of PEG4000, adding 1.2kg of cobalt nitrate, adding 5g of urea, continuously pulping, stirring and ageing for 0.5 hours at 25 ℃, 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 140 ℃, and the raspberry microsphere particles are obtained after flowing out from the outlet of the spray dryer through 2-5 s. The resulting product was calcined at 500 ℃ to give ZT7, a material useful for catalyst supports, whose physical properties are shown in table 1.

Example 8

Adding 20kg of deionized water into a reaction kettle, adding 4.6kg of pseudo-boehmite powder (kaolin), and uniformly stirring and mixing for about 10min; adding 175g of nitric acid and grinding for about 10min; adding 2.0kg of PEG4000, adding 1.2kg of basic cobalt carbonate, adding 5g of nitroglycerin, pulping continuously, stirring and ageing for 0.5 hours at 25 ℃, 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 the raspberry microsphere particles are obtained after flowing out from the outlet of the spray dryer through 2-5 s. The resulting product was calcined at 500 ℃ to give ZT8, a material useful for catalyst supports, whose physical properties are shown in table 1.

TABLE 1 physical Properties of catalyst support

The following examples illustrate natural gas hydrodesulfurization catalysts prepared from the shaped support provided by the present invention.

Example 9

30g of Co (NO) was weighed out ₃ ) ₂ ·6H ₂ O was dissolved in 80g of water, 30.0g of citric acid was added, and 48g of ammonium molybdate was added under stirring at 60℃to dissolve. 100g of the alumina carrier prepared in example 1 was put into a rotary evaporation vessel, the above solution was added, the catalyst was prepared by impregnation by rotary evaporation at 60℃and then the sample was dried at 120℃for 2 hours and calcined at 450℃for 4 hoursRepeating the above steps for 3 times to obtain catalyst C1. Wherein the content of each component is shown in Table 2.

Example 10

30g of Co (NO) was weighed out ₃ ) ₂ ·6H ₂ O was dissolved in 80g of water, 30.0g of citric acid was added, and 48.0g of ammonium molybdate was added under stirring at 60℃to dissolve. 100g of the alumina carrier (ZT 1) prepared in example 1 is added into a rotary steaming vessel, the solution is added, the catalyst is prepared by rotary steaming and dipping at 60 ℃, then the sample is dried at 120 ℃ for 2 hours and baked at 450 ℃ for 4 hours, and the baked sample is repeated for 5 times according to the steps to prepare the catalyst C2. Wherein the content of each component is shown in Table 2.

Example 11

40 g of ammonium molybdate was added to 70 ml of water, and aqueous ammonia having a concentration of 25% by weight was added dropwise with heating and stirring until the ammonium molybdate was dissolved, then 10 g of basic cobalt carbonate was added, and after stirring and dissolution, water was added to a constant volume of 85 ml. 100g of the carrier ZT1 were impregnated with the above solution by means of saturation impregnation. The impregnation time was 0.5 hours. The resulting solid was dried at 120℃for 2 hours, then calcined at 450℃for 3 hours, and the calcined sample was repeated 5 times in accordance with the above procedure to prepare catalyst C3. Wherein the content of each component is shown in Table 2.

Example 12

An aqueous solution of 6.8 g of basic cobalt carbonate, 24.0 g of molybdenum trioxide, 5.9 g of phosphoric acid and 10.3 g of citric acid (90 ml) was weighed, 100g of the alumina carrier (ZT 1) prepared in example 1 was added to a rotary evaporation vessel, the above solution was added, a catalyst was prepared by rotary evaporation impregnation at 60 ℃, then a sample was dried at 120℃for 2 hours and calcined at 450℃for 4 hours, and the calcined sample was repeated 4 times according to the above steps to prepare a catalyst C4. Wherein the content of each component is shown in Table 2.

Example 13

100.0 g of ZT6 carrier is weighed, 84 ml of aqueous solution containing 15.0 g of cobalt nitrate, 32.7 g of ammonium molybdate and 5.6 g of phosphoric acid is used for soaking for 4 hours, drying is carried out at 120 ℃ for 5 hours, roasting is carried out at 430 ℃ for 4 hours, and the roasted sample is repeated for 5 times according to the steps, so that the catalyst C5 is obtained. Wherein the content of each component is shown in Table 2.

Comparative example 3

Catalyst D1 was obtained by preparing a catalyst from the support obtained in comparative example 1 in the same manner as in example 10.

TABLE 2 content of the components in the catalyst

Examples	Catalyst numbering	CoO，％	Mo ₂ O ₃ ，％	P ₂ O ₅ ，％
					9	C1	9.9	33.0
10	C2	12.8	42.8
					11	C3	9.8	41.5
12	C4	5.12	35.0	6.2
					13	C5	6.1	42.1	6.4
Comparative example 3	D1	12.8	42.8

Examples 14-18 illustrate the use of the present invention to provide catalysts and their effects.

The organosulfur hydrogenation catalyst prepared in this example was subjected to presulfiding and desulfurization performance testing under the following steps and conditions:

According to the catalyst provided by the invention, the catalyst is required to be vulcanized before being used, and after the catalyst is filled, nitrogen is used as circulating gas to heat the catalyst to 130 ℃ at a speed of 30 ℃/h, and the temperature is kept for 1h; then, after the temperature was raised to 250℃at a rate of 30℃per hour, hydrogen gas having a volume concentration of 10% and H of 1.0% were added to nitrogen gas ₂ S, S; vulcanization reaction conditions: the reaction temperature is 360 ℃, and the space velocity of the raw material gas is 1000h ^-1 . And after the vulcanization is finished, the natural gas is switched for experiments.

The sulfur content of the natural gas is different according to the different gas sources in all places of the country, and in the national standard, the total sulfur content of the natural gas is as follows: class 1 is less than or equal to 60mg/m ³ The method comprises the steps of carrying out a first treatment on the surface of the Class 2 is less than or equal to 200mg/m ³ The method comprises the steps of carrying out a first treatment on the surface of the Class 3 is less than or equal to 350mg/m ³ . If used as civil fuel, the total sulfur content of the natural gas meets the standards of class 1 gas or class 2 gas. The composition of civil natural gas from Beijing gas company is shown in Table 3. The sulfide composition in natural gas is shown in table 4.

TABLE 3 Natural gas composition

Methane	Ethane (ethane)	Propane	N-butane	Nitrogen gas
					98.56	0.21	0.13	0.13	0.95

TABLE 4 sulfide component and content (unit mg/m) in Natural gas for desulfurization experiments ³ )

Desulfurization experiments were performed using the above natural gas as a feed gas. The natural gas desulfurization experimental conditions are as follows: a mini-micro-channel reactor, the mini-reactor module has 64 reaction channels and 144 cooling channels, the reaction channels are 200mm long. Catalyst loading was 25mL. H in the raw material gas ₂ :1% by volume. Reaction pressure: 2.5MPa, reaction temperature: 320 ℃ and space velocity of 10000h ^-1 . Catalysts C1-C5 and comparative agent D1 were evaluated. The reactivity of the catalyst is shown in Table 4.

TABLE 5 reactivity of catalysts

It can be seen from the table that the raspberry type carrier provided by the invention is used as a catalyst carrier, and then the raspberry type carrier is prepared into the natural gas hydrodesulfurization catalyst, and the raspberry type carrier has better performance under the same other conditions.

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

It will be appreciated by persons skilled in the art that the embodiments described herein are merely exemplary and that various other alternatives, modifications and improvements may be made within the scope of the invention. Thus, the present invention is not limited to the above-described embodiments, but only by the claims.

Claims

1. A natural gas hydrodesulfurization catalyst comprises a carrier and an active metal component supported on the carrier, wherein the active metal component comprises molybdenum and cobalt,

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;

the preparation method of the carrier comprises the following steps:

aging the dispersion slurry;

sending the aged dispersion slurry into a drying device, wherein the air inlet temperature is 400-1200 ℃; drying and forming at the air outlet temperature of 50-300 ℃ to obtain the raspberry oxide microspheres;

the method further comprises the step of adding a blasting agent to the dispersing agent, wherein the blasting agent is one or more selected from picric acid, trinitrotoluene, nitroglycerin, nitrocotton, dana explosive, hemsleya amabilis and C4 plastic explosive;

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; the content of the blasting agent is not 0;

2. The catalyst according to claim 1, wherein the catalyst further comprises one or more auxiliary components selected from P, B, si and F, and the content of the auxiliary components in element is less than 5% by weight based on the catalyst.

3. The natural gas hydrodesulfurization catalyst according to claim 2, wherein the content of the auxiliary component in terms of elements is 4 wt% or less.

4. The natural gas hydrodesulfurization catalyst according to claim 1, wherein the molybdenum content in terms of oxide is 15-43 wt.% based on the catalyst; cobalt content of 2-7 wt% calculated on oxide basis; the content of carrier oxide is 50-83 wt%.

5. The natural gas hydrodesulfurization catalyst according to claim 1, wherein the sphericity of the raspberry oxide microspheres is 0.50 to 0.99 and the diameter is 60 to 400 μm.

6. The natural gas hydrodesulfurization catalyst according to claim 1 for use in a microchannel reactor having reaction channels with at least one dimension less than 1000 μm in size.

7. A process for preparing a natural gas hydrodesulfurization catalyst according to any one of claims 1 to 6 comprising the steps of:

Providing the carrier;

8. The method of claim 7, wherein the inlet air temperature is 450-700 ℃; the temperature of the air outlet is 120-200 ℃.

9. The method of claim 7, wherein the nitrate is selected from one or more of aluminum nitrate, zirconium nitrate, lanthanum nitrate, and yttrium nitrate.

10. The method of claim 7, wherein the peptizing agent is selected from one or more of acids, bases, and salts.

11. The method of claim 7, wherein the pore-forming agent is selected from one or more of starch, synthetic cellulose, polymeric alcohol, and surfactant.

12. The method of claim 7, wherein the oxide and/or precursor thereof is selected from one or more of an aluminum source selected from one or more of pseudoboehmite, aluminum alkoxide, aluminum nitrate, aluminum sulfate, aluminum chloride, and sodium metaaluminate, a silicon source selected from one or more of silicate, sodium silicate, water glass, and silica sol, a zirconium source selected from one or more of zirconium dioxide, zirconium tetrachloride, zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium phosphate, zirconyl nitrate, zirconium basic carbonate, and zirconium tetrabutoxide, and a titanium source selected from one or more of titanium dioxide, meta-titanic acid, titanium nitrate, titanyl sulfate, titanium dichloride, titanium trichloride, titanium tetrachloride, aluminum titanium chloride, tetraethyl titanate, tetrabutyl titanate, tetra-n-propyl titanate, and tetraisopropyl titanate.

13. The method of claim 7, wherein the dispersant is selected from one or more of water, alcohols, ketones, and acids.

14. The method according to claim 7, wherein the mass ratio of the nitrate, the peptizing agent, the pore-forming agent, and the oxide and/or its precursor is (10-500): (1-10): (10-500): (10-1000).

15. The method according to any one of claims 7 to 14, wherein the drying device is a flash drying device or a spray drying device.

16. The method according to any one of claims 7 to 14, wherein the temperature of the ageing treatment is 0-90 ℃.

17. The method of claim 16, wherein the temperature of the aging process is 20-60 ℃.

18. Use of a natural gas hydrodesulfurization catalyst according to any one of claims 1 to 6 or a catalyst obtainable by a process according to any one of claims 7 to 17 for catalyzing the hydrodesulfurization of natural gas.

19. A process for the hydrodesulfurization of natural gas comprising contacting natural gas under natural gas hydrodesulfurization reaction conditions with a natural gas hydrodesulfurization catalyst according to any one of claims 1 to 6 or a catalyst obtained by the process according to any one of claims 7 to 17.

20. The process of claim 19 wherein the natural gas hydrodesulfurization reaction is carried out in a microchannel reactor, the microchannel reactor being one in which the reaction channels have at least one dimension less than 1000 μm in size.