A catalyst for dehydrogenation of alkylaromatics and its preparation and use

Abstract

The application provides a catalyst for dehydrogenation of alkyl aromatic hydrocarbon, which comprises the following components in percentage by weight: 62-81% of Fe2O3, 8-13% of CeO2, 7-14% of alkali metal oxide, 0.1-5% of VIB group metal oxide, 0.1-6% of alkaline earth metal oxide, 0.005-4% of VIII group metal oxide except Fe, 0.001-3% of IB group metal oxide, and the weight content of carbon in the catalyst for dehydrogenation of alkyl aromatic hydrocarbon is 0.1-2%. The application adds a small amount of expandable organic resin template agent in the Fe-Ce-alkali metal-VIB group-alkaline earth metal-VIII group-IB group metal system, induces expansion and aging foaming under suitable conditions, adjusts the calcination atmosphere, controls partial carbonization and improves the mechanical strength, and thus the catalyst for dehydrogenation of alkyl aromatic hydrocarbon is prepared, the bulk density of which is 1150-1350 kg / m 3 , and the crushing strength is greater than 30 N / mm. In addition to maintaining high catalytic performance under low water ratio conditions, the catalyst has low bulk density and good crushing strength, and can be used in industrial production of dehydrogenation of alkyl aromatic hydrocarbon.

Description

Technical Field

[0001] This invention relates to the field of catalyst preparation technology, specifically to a catalyst for the dehydrogenation of alkyl aromatics and its preparation and application. Background Technology

[0002] Styrene is an important organic chemical raw material, mainly produced industrially by the dehydrogenation of ethylbenzene, with the main reaction being: This reaction is an endothermic reaction with an increase in volume. Vapor plays a crucial role in the reaction process:

[0003] (1) Provide heat to the reaction mixture;

[0004] (2) Reduce the partial pressure of the product and balance temperature and conversion rate;

[0005] (3) Remove coke through water-gas shift reaction;

[0006] (4) Minimize ethylbenzene cracking;

[0007] (5) Maintain the oxidized state of the Fe catalyst to prevent it from being reduced by H2;

[0008] (6) Inducing K redistribution on the catalyst during the reaction improves the catalytic lifetime.

[0009] The activation of the catalyst precursor to produce a metastable potassium ferrite phase, the high-temperature cracking of water, and the vaporization of carbon determine that this reaction is usually carried out at temperatures above 600°C. Most existing styrene catalysts are Fe-K based, with iron oxide as the main catalyst and potassium as the main promoter, while also containing structural stabilizers such as oxides of Ce, Mg, Mo, W, or Ca. In recent years, market demands for high-load operation, energy conservation and emission reduction, and larger-scale plants have urged catalysts to be continuously improved towards higher yields, tolerance to low water ratios, high stability, low bulk density, and high strength.

[0010] The intrinsic activity of the ethylbenzene dehydrogenation reaction is relatively high under the reaction conditions. The actual reaction rate is influenced by intraparticle diffusion, making it an internal diffusion-controlled reaction. Reducing the catalyst size is beneficial for improving catalytic activity, but it also increases the bed pressure drop. Increasing the macropore size reduces internal diffusion resistance, which helps to reduce side reactions and improve selectivity. The specific surface area of ​​existing catalysts is typically 1-10 m². 2The bulk density is typically between 1.30-1.70 kg / L. Higher bulk density does not necessarily improve catalyst strength and performance, but it does increase material consumption during catalyst production. Industrially, dehydrogenation catalysts are mostly formed into cylindrical particles of about 3 mm. Current technologies primarily reduce bulk density using traditional pore-forming agents and by altering the catalyst configuration. Pore formation is one of the main methods for preparing inorganic porous materials, and the method directly affects the pore structure and porosity of the material. CN101182235A describes several pore-forming methods, including pore-forming agent methods, foaming methods, sol-gel methods, partial sintering methods, reaction sintering methods, mechanical pore-forming methods, surfactant self-assembly methods, and template replication methods. Among these, the pore-forming agent method is one of the most widely used. This method not only facilitates the preparation of porous materials but also allows for adjustment of the pore structure and porosity by modifying the shape, size, and amount of the pore-forming agent, thus meeting different application requirements. However, the pore-forming agent method is often affected by the decrease in crushing strength, limiting the degree of density reduction. In addition, increasing particle size and changing catalyst configuration (trilobite, pentlobite, hollow, etc.) can reduce the packing density of the catalyst to some extent, but the catalytic activity decreases significantly due to the reduced exposed surface area.

[0011] Alloying, blending, and composite processes are the main development methods for functional synthetic materials. The preparation of high-strength, low-density materials has always been a research hotspot in science and industry. Foamed ceramic materials are a typical example, widely used in adsorbents, filters, sensors, catalytic materials, and building materials due to their high porosity, high specific surface area, high temperature resistance, and high mechanical strength. Domestic and international patents often use alumina, zirconium oxide, silicon carbide, silicon nitride, boron nitride, and graphene as the main research or production raw materials. For example, CN102850084A discloses a method for preparing porous ceramics using organic resin foamed microspheres as a pore-forming agent. It selects a core-shell structured microsphere with a very uniform particle size, and the outer shell is made of high-strength acrylic resin. By heating to 50–300℃, the gas inside the microsphere expands, increasing its volume several to tens of times, thus achieving a high porosity. Although significant progress has been made in its research and application, foamed ceramic materials are still relatively novel, and there are almost no reports on their application as catalytic materials in the field of alkyl aromatic hydrocarbon dehydrogenation. In the field of catalysts, the typical method for preparing high-strength, low-density catalytic materials is still through the introduction of pore-forming agents. US4977123A discloses a method of calcining a precursor of mixed metal oxides, crushing and sieving it to obtain mixed oxides of a certain particle size, adding an inorganic binder clay, and then extruding, molding, drying, and heat-treating to obtain a non-supported mixed metal oxide extrusion adsorbent and catalytic material with a catalyst pore size of 0.1–25 μm and a crushing strength ranging from 4.45–44.5 N / mm. However, the above patent does not mention the bulk density of the catalyst after molding.

[0012] Generally, low packing density is achieved by increasing the proportion of compounds containing light elements (such as H, Li, Be, B, C, N, O, etc.) or by increasing pore volume through methods such as pore formation, foaming, and sol-gel processes. Since the catalyst precursors for alkyl aromatic hydrocarbon dehydrogenation reaction systems require high-temperature calcination in air for induced formation, and light elements, especially non-metallic elements (H, B, C, N, etc.), exhibit poor thermal stability in high-temperature air, the latter method of increasing porosity is often chosen. Summary of the Invention

[0013] To address the issue of high catalyst packing density in existing technologies, this invention provides an alkyl aromatic hydrocarbon dehydrogenation catalyst and its preparation method. The catalyst of this invention maintains good catalytic activity and yield under reaction conditions while exhibiting low packing density and high strength.

[0014] In a first aspect, the present invention provides a composition for preparing a catalyst for the dehydrogenation of alkyl aromatics, the composition comprising a metal source and additives, wherein the metal source includes an Fe source, a Ce source, an alkali metal source, a Group VIB metal source, an alkaline earth metal source, a Group IB metal source, and a Group VIII metal source other than Fe; the additives include an organic resin foaming agent, a lubricant, and a thickener; the amount of the additives added is 0.5% to 5% of the total mass of the catalyst composition based on the oxide content, and the amount of the organic resin foaming agent added is 0.3% to 3.5% of the total mass of the catalyst composition based on the oxide content.

[0015] In a specific embodiment of the present invention, the amount of metal source added is calculated based on the amount of corresponding metal oxide added; the total amount of metal sources added, namely the total amount of Fe source, Ce source, alkali metal source, Group VIB metal source, alkaline earth metal source, Group IB metal source, and Group VIII metal source other than Fe, is calculated based on the amount of oxide added. The amount of Group IB metal source added is 0.001 to 3% of the total amount of metal sources added, and / or the amount of Group VIII metal source other than Fe added is 0.005 to 4% of the total amount of metal sources added.

[0016] As a specific embodiment of the present invention, the amount of the thickener added is 0.1 to 1% of the total mass of the catalyst composition based on the oxide content, and / or the amount of the lubricant added is 0.1 to 0.5% of the total mass of the catalyst composition based on the oxide content.

[0017] As a specific embodiment of the present invention, the catalyst for the dehydrogenation of alkyl aromatics is prepared by an organic resin foaming method and by calcination in a furnace with a calcination atmosphere of 5-50% O2 / N2.

[0018] As a specific embodiment of the present invention, the alkali metal source is selected from at least one of Li, Na, K, Rb, and Cs, preferably at least one of Li, Na, and K; and / or the group VIB metal source is selected from at least one of Cr, Mo, and W; and / or the alkaline earth metal source is selected from at least one of Be, Mg, Ca, Sr, and Ba, preferably at least one of Mg, Ca, and Sr; and / or the group VIII metal source other than Fe is selected from at least one of Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt; and / or the group IB metal source is selected from at least one of Cu, Ag, and Au.

[0019] As a specific embodiment of the present invention, the Fe source is at least selected from at least one of iron oxide red, iron oxide yellow, iron nitrate, iron citrate, and iron ammonium citrate; and / or the alkali metal source is selected from at least one of (Li, Na, K, Rb, Cs) carbonates, oxalates, bicarbonates, nitrates, citrates, and hydroxides; And / or the Ce source is selected from at least one of cerium oxide, cerium oxalate, cerium acetate, cerium carbonate, cerium hydroxide, cerium nitrate, and cerium ammonium nitrate; and / or the VIB metal source is selected from at least one of (Cr, W, Mo) ammonium salts, metaic acid ammonium salts, and metal oxides; and / or the alkaline earth metal source is selected from at least one of (Be, Mg, Ca, Sr, Ba) oxides, carbonates, and hydroxides; and / or the IB group metal source is selected from at least one of (Cu, Ag, Au) metal oxides, hydroxides, carbonates, oxalates, acetates, and nitrates; and / or the VIII group metal source other than Fe is selected from at least one of (Co, Ni, Ru, Rh, Pd, Os, Ir, Pt) VIII group metal compounds including nitrates, carbonates, hydroxides, chlorides, acetates, and metal complexes (taking palladium as an example, such as chloropalladium acid, ammonium chloropalladium, tetraamminepalladium nitrate, tetraamminepalladium hydroxide, tetraamminepalladium bicarbonate, tetraamminepalladium oxalate, etc.).

[0020] In a specific embodiment of the present invention, the thickener is selected from inorganic thickeners, such as fumed silica, sodium bentonite, organobentonite, diatomaceous earth, attapulgite, molecular sieves, silica gel, etc.; natural polymers and their derivatives, such as starch, gelatin, sodium alginate, casein, guar gum, chitosan, xanthan gum, soybean protein gum, natural rubber, lanolin, agar, etc.; and synthetic polymers, such as polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, carbomer resin, polyacrylic acid, sodium polyacrylate, polyacrylate copolymer emulsion, and cis-butadiene rubber. Styrene-butadiene rubber, polyurethane, modified polyurea, low molecular weight polyethylene wax, etc.; cellulose ethers and their derivatives, such as hydroxyethyl cellulose, ethyl cellulose, methyl hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, methyl hydroxypropyl cellulose, etc.; associative alkali-swellable thickeners, such as alkali-swellable polyacrylates, polyacrylate copolymer emulsions, etc.; polyurethane thickeners, such as at least one of nonionic hydrophobic modified ethoxy polyurethane copolymers, hydrophobic modified ethoxy polyurethane rheology-modified alkali-swellable emulsions, and modified polyurea thickeners.

[0021] As a specific embodiment of the present invention, the organic resin foaming agent is selected from at least one of expandable polystyrene EPS, expandable graphite polystyrene, expandable phenolic resin, expandable polyethylene EPE, expandable polypropylene EPP, expandable polyethylene-styrene EPO, expandable polystyrene-acrylonitrile copolymer, expandable polystyrene-methyl methacrylate, expandable polyvinyl chloride, expandable polyamide, expandable polyester, expandable epoxy resin, etc.

[0022] As a specific embodiment of the present invention, the lubricant comprises at least one of solid lubricant and liquid lubricant. The solid lubricant is selected from at least one of talc, graphite, fatty acid amide, erucamide, citric acid, molybdenum disulfide, stearic acid, stearate, ethylene bis-stearamide, polyethylene wax, solid paraffin, etc.; the liquid lubricant is selected from at least one of water, lubricating oil, glycerin, soluble oil, silicone oil (such as methyl silicone oil, benzyl silicone oil, ethyl silicone oil, etc.), liquid paraffin, n-butyl stearate, silicone resin, polyacrylamide solution, etc.

[0023] All of the above-mentioned raw materials used in this invention can be prepared in-house or purchased commercially; this invention does not impose any particular limitations on them.

[0024] Secondly, this invention provides a catalyst for the dehydrogenation of alkyl aromatics, wherein the carbon (C) content in the catalyst is 0.1-2% by weight, preferably controlled at 0.5-1.5%. The bulk density is 1150-1350 kg / m³. 3 The crushing strength is greater than 30 N / mm.

[0025] As a specific embodiment of the present invention, a catalyst for the dehydrogenation of alkyl aromatics comprises the following components by weight percentage: 62-81% Fe₂O₃, 8-13% CeO₂, 7-14% alkali metal oxides, 0.1-5% Group VIB metal oxides, 0.1-6% alkaline earth metal oxides, 0.005-4% selected from at least one Group VIII metal oxide other than Fe, and 0.001-3% selected from at least one Group IB metal oxide. Preferred contents are as follows: 64-78% Fe₂O₃; 8-12% alkali metal oxides; 9-13% CeO₂; 0.2-4% Group VIB metal oxides; 0.5-5% alkaline earth metal oxides; 0.02-3% selected from at least one Group VIII metal oxide other than Fe; and 0.01-2% selected from at least one Group IB metal oxide.

[0026] In a specific embodiment of the present invention, the weight ratio of the Group VIII metal oxide (excluding Fe) to the Group IB metal oxide is 0.01 to 70:1, preferably 0.5 to 3:1. The Group IB metal oxide and the Group VIII metal oxide (excluding Fe) work synergistically to give the alkyl aromatic hydrocarbon dehydrogenation catalyst of the present invention low bulk density and high strength, while maintaining good catalytic activity and yield under reaction conditions.

[0027] In the above technical solutions, alkaline earth metals (Be, Mg, Ca, Sr, Ba) are often used as structural aids to stabilize Fe. 3+ Simultaneously, adjusting surface alkalinity improves selectivity; Group IB elements (Cu, Ag, Au) possess good thermal and electrical conductivity, and their metallic forms and oxides also exhibit good chemical stability; Group VIII elements, including iron-group and platinum-group elements, are characterized by high melting and boiling points, high hardness, and high density, along with good ductility and high electrical and thermal conductivity. Iron-group elements have properties similar to Fe, readily forming alloys with iron, while platinum-group elements possess higher chemical stability, facilitating the adsorption, desorption, and dissociation of H2 on the surface, thus enhancing catalytic activity. Simultaneously, they inhibit coke formation during the reaction process, improving catalyst stability.

[0028] Thirdly, the present invention provides a method for preparing a catalyst for the dehydrogenation of alkyl aromatics, comprising uniformly mixing an Fe source, a Ce source, an alkali metal source, a Group VIB metal source, an alkaline earth metal source, a Group IB metal source, a Group VIII metal source, and organic resin particles or microspheres; adding a solvent to the mixture to prepare a thin slurry; adding a small amount of lubricant dropwise and mixing it with the slurry; after the solvent gradually evaporates and the slurry becomes a viscous paste, shaping it; extruding and granulating it into cylindrical particles with a diameter of 3 mm and a length of 5-10 mm; and finally, optionally drying and calcining the particles to obtain the finished catalyst.

[0029] Specifically, the following steps are included:

[0030] (1) The Fe source, Ce source, alkali metal source, group VIB metal source, alkaline earth metal source, group IB metal source, group VIII metal source and organic resin foaming agent are mixed by a mixer, ball mill or plow type mixer, preferably with a speed of 1~50 r / min and a time of 10~300 min to obtain the first mixed powder.

[0031] (2) Add solvent, thickener and lubricant to the first mixture and mix thoroughly to obtain the second mixture.

[0032] (3) Then, heat or negative pressure suction is used to remove part of the solvent to obtain the second mixed paste.

[0033] (4) The second mixed paste is shaped, dried, and calcined in a furnace with a 5-50% O2 / N2 atmosphere. The mixed material is shaped using one of the following: screw extruder, hydraulic extruder, mixer, or ply mill.

[0034] As a specific embodiment of the present invention, the drying conditions include: a temperature of 30 to 200°C and a time of 6 to 24 hours; preferably, the drying conditions include: drying at 40 to 100°C for 4 to 16 hours, and then raising the temperature to 120 to 180°C for 2 to 8 hours.

[0035] As a specific embodiment of the present invention, the roasting conditions include: a temperature of 200-1200°C and a time of 4-20 hours; preferably, the roasting conditions include: roasting at 300-700°C for 2-12 hours, and then raising the temperature to 800-1200°C and roasting for 2-8 hours.

[0036] As a specific embodiment of the present invention, the solvent is at least one of water, alcohol (methanol, ethanol, ethylene glycol), organic amine (such as dimethylformamide), ammonia, dimethyl sulfoxide, ether, and ester, and the amount of solvent added is 10 to 60% of the total mass of the catalyst for alkyl aromatic dehydrogenation based on oxide content, preferably 15 to 50%.

[0037] This invention uses organic resin particles or microspheres as foaming agents, and removes pores through a foaming process followed by high-temperature calcination. Calcination-induced pores reduce the catalyst density and provide channels for the diffusion of catalytic reactants and products, reducing diffusion resistance. Furthermore, by controlling the calcination atmosphere, the organic resin undergoes incomplete combustion and partial carbonization, remaining within the catalyst pores, which also contributes to improved catalyst strength.

[0038] Fourthly, the present invention provides the application of the catalyst for the dehydrogenation of alkyl aromatics in the dehydrogenation reaction of alkyl aromatics; preferably in the dehydrogenation reaction of alkyl aromatics with low bulk density. It is particularly suitable for the industrial production of alkenyl aromatics under low water ratio conditions.

[0039] Fifthly, the present invention provides a method for the dehydrogenation of alkyl aromatics to produce alkenyl aromatics, comprising: reacting alkyl aromatics, water vapor, and the above-mentioned catalyst suitable for the dehydrogenation of low-bulk-density alkyl aromatics under alkyl aromatics dehydrogenation reaction conditions.

[0040] As a specific embodiment of the present invention, the dehydrogenation reaction conditions of the alkyl aromatic hydrocarbon include: a temperature of 580–650°C, more preferably 590–630°C; and a volume hourly space velocity of 0.5–1.5 h⁻¹. -1 More preferably 0.8 to 1.5 h -1 The weight ratio of water to alkyl aromatics is 0.5 to 1.3, preferably 0.9 to 1.3; the pressure is 20 kPaA to 0.10 MPaA, more preferably 40 kPaA to 0.10 MPaA.

[0041] The carbon content of the catalyst in this invention was measured using a Vario EL III elemental analyzer from Elementar GmbH, Germany. The measurement error C < 0.1% abs, and the measurement accuracy C < 0.04% abs.

[0042] In this invention, the tap density of the catalyst is measured using a tap density meter in accordance with the test methods and requirements specified in ASTM D4164-2003 Standard Test Method for Mechanical Tap Packing Density of Molded Catalysts and Catalyst Supports and SH-T 0958-2017 Determination of Mechanical Tap Packing Density of Molded Catalysts and Catalyst Supports.

[0043] In this invention, the crushing strength of the catalyst was measured according to the test methods and requirements specified in the current national chemical industry standard HG / T 2782-2011, using a DL-II intelligent particle strength tester. For each catalyst sample, 30 5mm long specimens were selected, and the arithmetic mean was taken as the crushing strength, in N / mm.

[0044] The catalyst prepared by the above method was evaluated for its performance in the dehydrogenation reaction of alkyl aromatics in an isothermal fixed bed. The process is briefly described below:

[0045] The reactor is a stainless steel tube with an inner diameter of 1”, filled with 50-150 ml of cylindrical catalyst with a diameter of 3 mm. Deionized water and ethylbenzene are separately fed into a preheating mixer via metering pumps, preheated and mixed into a gaseous state before entering the reactor. The reactor is heated by an electric heating wire to reach a predetermined temperature.

[0046] The reactants flowing out of the reactor were condensed in water and their composition was analyzed by gas chromatography.

[0047] Ethylbenzene conversion and styrene selectivity are calculated using the following formulas:

[0048]

[0049] .

[0050] Compared with existing technologies, this invention provides a method using a mixed metal oxide matrix of Fe-Ce-alkali metals (Li, Na, K, Rb, Cs)-Group VIB (Cr, Mo, W)-alkaline earth metals (Be, Mg, Ca, Sr, Ba)-Group IB (Cu, Ag, Au)-Group VIII (Co, Ni, Ru, Rh, Pd, Os, Ir, Pt). It utilizes the synergistic effect of Group IB metal sources and Group VIII metal sources other than Fe, adds a small amount of expandable organic resin template agent, and induces expansion, aging, and foaming under suitable conditions. This, combined with the high strength of the metal oxide matrix, the high porosity of the organic resin foaming agent, and atmosphere-induced partial carbonization to improve mechanical strength, is an effective solution for reducing the actual density and bulk density of catalysts. The resulting alkyl aromatic dehydrogenation catalyst has a bulk density of 1150–1350 kg / m³. 3 It exhibits a crushing strength greater than 30 N / mm. In addition to maintaining high catalytic performance under low water ratio conditions, it also has low bulk density and good crushing strength, making it suitable for industrial production of alkyl aromatics dehydrogenation. Detailed Implementation

[0051] The present invention will be further described below with reference to specific embodiments, but this does not constitute any limitation on the present invention.

[0052] The raw materials used in all embodiments of the present invention can be either self-made or commercially available.

[0053] Example 1

[0054] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0055] (1) Using a mixing mill, the following components were mixed evenly: iron oxide red equivalent to 44.60 parts Fe2O3, iron oxide yellow equivalent to 22.30 parts Fe2O3, cerium hydroxide equivalent to 12.78 parts CeO2, potassium carbonate equivalent to 9.84 parts K2O, ammonium molybdate equivalent to 2.13 parts MoO3, 1.82 parts WO3, magnesium carbonate equivalent to 3.06 parts MgO, 0.325 parts NiO, 0.325 parts Rh2O3, 0.325 parts PdO, 0.325 parts IrO2, 0.325 parts PtO2, 0.615 parts CuO, 0.615 parts Ag2O, 0.615 parts Au2O3, and expandable polystyrene equivalent to 1.67% of the total catalyst mass (based on oxides). The mixing speed was 48.5 r / min, and the stirring time was 50 min.

[0056] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 23.5% (wt) of the total catalyst mass (based on oxides), and add 0.41% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0057] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80°C for 4 hours and 160°C for 4 hours. Then place it in a tube furnace under an 8% O2 / N2 atmosphere and calcine at 400°C for 2 hours and 780°C for 2 hours to obtain the finished catalyst. The composition of the catalyst is listed in Table 1.

[0058] The catalyst was found to have a carbon content of 0.51% (wt) according to elemental analysis, a tap density of 127.1 g / 100 ml according to a tap density meter, and a crushing strength of 173.5 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0059] Example 2

[0060] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0061] (1) Using a mixing mill, the following components were mixed evenly: iron oxide red equivalent to 47.76 parts Fe2O3, iron oxide yellow equivalent to 23.89 parts Fe2O3, cerium hydroxide equivalent to 10.57 parts CeO2, potassium carbonate equivalent to 8.59 parts K2O, ammonium molybdate equivalent to 0.33 parts MoO3, calcium carbonate equivalent to 4.89 parts CaO, 0.424 parts CoO, 0.424 parts NiO, 0.424 parts RuO2, 0.424 parts Rh2O3, 0.424 parts PdO, 0.424 parts OsO2, 0.424 parts PtO2, 0.501 parts Ag2O, 0.501 parts Au2O3, and expandable polyurethane equivalent to 2.19% of the total catalyst mass (based on oxides). The mixing speed was 37.1 r / min, and the stirring time was 250 min.

[0062] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 18.7% (wt) of the total catalyst mass (based on oxides), and add 0.75% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0063] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under an 11% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 820℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0064] The catalyst was found to have a carbon content of 0.73% (wt) according to elemental analysis, a tap density of 122.6 g / 100 ml according to a tap density meter, and a crushing strength of 174.7 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0065] Example 3

[0066] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0067] (1) Using a mixing mill, 51.723 parts of iron oxide red, 25.86 parts of iron oxide yellow, 9.13 parts of cerium carbonate, 10.72 parts of potassium carbonate, 1.17 parts of WO3, 0.74 parts of strontium carbonate, 0.09 parts of NiO, 0.09 parts of PdO, 0.09 parts of IrO2, 0.387 parts of Ag2O, and 2.98% of expandable graphite polystyrene (based on total catalyst mass as oxides) were mixed evenly at a speed of 37.1 r / min and a stirring time of 250 min.

[0068] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 30.2% (wt) of the total catalyst mass (based on oxides), and add 0.62% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0069] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 15% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 795℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0070] The catalyst was found to have a carbon content of 0.94% (wt) according to elemental analysis, a tap density of 119.4 g / 100 ml according to a tap density meter, and a crushing strength of 161.2 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0071] Example 4

[0072] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0073] (1) Using a mixing mill, the following components were mixed evenly: 49.10 parts of iron oxide red (Fe2O3), 24.549 parts of iron oxide yellow (Fe2O3), 8.32 parts of cerium carbonate (CeO2), 10.64 parts of potassium carbonate (K2O), 1.07 parts of ammonium molybdate (MoO3), 1.79 parts of magnesium hydroxide (MgO), 3.56 parts of calcium hydroxide (CaO), 0.59 parts of strontium hydroxide (SrO), 0.125 parts of CoO, 0.125 parts of Rh2O3, 0.125 parts of PtO2, 0.006 parts of Au2O3, and 1.43% of expandable phenolic resin (based on total catalyst mass as oxides). The mixing speed was 22.3 r / min and the stirring time was 100 min.

[0074] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 12.7% (wt) of the total catalyst mass (based on oxides), and add 0.13% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0075] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 9% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 950℃ for 2 hours to obtain the finished catalyst. The composition of the catalyst is listed in Table 1.

[0076] The catalyst was found to have a carbon content of 0.47% (wt) according to elemental analysis, a tap density of 128.3 g / 100 ml according to a tap density meter, and a crushing strength of 150.6 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0077] Example 5

[0078] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0079] (1) Using a mixing mill, the following components were mixed evenly: 49.90 parts of iron oxide red, 24.943 parts of iron oxide yellow, 11.05 parts of cerium hydroxide, 9.62 parts of potassium carbonate, 0.92 parts of WO3, 1.09 parts of MgO, 1.81 parts of CaO, 0.102 parts of NiO, 0.102 parts of Rh2O3, 0.102 parts of OsO2, 0.102 parts of PtO2, 0.259 parts of Ag2O, and 2.58% of expandable polystyrene (based on the total catalyst mass as oxides). The mixing speed was 39.5 r / min and the stirring time was 300 min.

[0080] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 43.5% (wt) of the total catalyst mass (based on oxides), and add 0.50% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0081] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 14% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 860℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0082] The catalyst was found to have a carbon content of 0.82% (wt) according to elemental analysis, a tap density of 120.8 g / 100 ml according to a tap density meter, and a crushing strength of 168.9 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0083] Example 6

[0084] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0085] (1) Using a mixing mill, the following components were mixed: iron oxide red (equivalent to 42.85 parts Fe2O3), iron oxide yellow (equivalent to 21.418 parts Fe2O3), cerium hydroxide (equivalent to 11.23 parts CeO2), potassium carbonate (equivalent to 13.81 parts K2O), ammonium molybdate (equivalent to 0.49 parts MoO3), ammonium tungstate (equivalent to 1.78 parts WO3), magnesium carbonate (equivalent to 3.78 parts MgO), 0.78 parts SrO, and 0.4... 13 parts CoO, 0.413 parts NiO, 0.413 parts RuO2, 0.413 parts Rh2O3, 0.413 parts PdO, 0.413 parts OsO2, 0.413 parts IrO2, 0.413 parts PtO2, 0.558 parts CuO, and 3.37% expandable polyurethane (based on total catalyst mass, in oxides) were mixed evenly at a speed of 47.6 r / min for 70 min.

[0086] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 27.1% (wt) of the total catalyst mass (based on oxides), and add 0.96% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0087] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 5% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 750℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0088] The catalyst was found to have a carbon content of 1.72% (wt) according to elemental analysis, a tap density of 117.2 g / 100 ml according to a tap density meter, and a crushing strength of 153 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0089] Example 7

[0090] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0091] (1) Using a mixing mill, 53.063 parts of iron oxide red, 26.533 parts of iron oxide yellow, 9.07 parts of cerium carbonate, 7.10 parts of potassium carbonate, 0.14 parts of WO3, 0.25 parts of magnesium hydroxide, 0.242 parts of CoO, 0.242 parts of NiO, 0.242 parts of RuO2, 0.242 parts of OsO2, 0.242 parts of PtO2, 1.317 parts of CuO, 1.317 parts of Au2O3, and 0.87% of expandable graphite polystyrene (based on oxides) of the total catalyst mass were mixed evenly at a speed of 29.3 r / min and a stirring time of 90 min.

[0092] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 51.9% (wt) of the total catalyst mass (based on oxides), and add 0.87% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0093] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 12% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 835℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0094] The catalyst was found to have a carbon content of 0.15% (wt) according to elemental analysis, a tap density of 133.5 g / 100 ml according to a tap density meter, and a crushing strength of 158.4 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0095] Example 8

[0096] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0097] (1) Using a mixing mill, 50.132 parts of iron oxide red, 25.07 parts of iron oxide yellow, 9.96 parts of cerium carbonate, 8.24 parts of potassium carbonate, 0.51 parts of ammonium molybdate, 0.46 parts of calcium carbonate, 2.68 parts of strontium hydroxide, 0.309 parts of CoO, 0.309 parts of RuO2, 0.309 parts of PdO, 0.309 parts of IrO2, 0.856 parts of CuO, 0.856 parts of Ag2O, and 1.76% of expandable phenolic resin (based on total catalyst mass, in oxides) were mixed evenly at a speed of 26.8 r / min for 120 min.

[0098] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 36.9% (wt) of the total catalyst mass (based on oxides), and add 0.27% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0099] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 10% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 905℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0100] The catalyst was found to have a carbon content of 0.56% (wt) according to elemental analysis, a tap density of 123.0 g / 100 ml according to a tap density meter, and a crushing strength of 166.1 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0101] Example 9

[0102] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0103] (1) Using a mixing mill, the following components were mixed evenly: 46.89 parts of iron oxide red, 23.44 parts of iron oxide yellow, 12.53 parts of cerium hydroxide, 12.61 parts of potassium carbonate, 1.14 parts of ammonium molybdate, 2.03 parts of ammonium tungstate, 1.20 parts of CaO, 0.061 parts of RuO2, 0.061 parts of OsO2, 0.038 parts of Au2O3, and 3.30% of expandable polystyrene (based on total catalyst mass as oxides). The mixing speed was 34.2 r / min and the stirring time was 210 min.

[0104] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 57.0% (wt) of the total catalyst mass (based on oxides), and add 0.27% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0105] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 6% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 880℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0106] The catalyst was found to have a carbon content of 1.65% (wt) according to elemental analysis, a tap density of 115.1 g / 100 ml according to a tap density meter, and a crushing strength of 151.3 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0107] Example 10

[0108] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0109] (1) Using a mixing mill, the following components were mixed evenly: 45.12 parts of iron oxide red (Fe2O3), 22.555 parts of iron oxide yellow (Fe2O3), 12.54 parts of cerium hydroxide (CeO2), 10.98 parts of potassium carbonate (K2O), 2.37 parts of ammonium molybdate (MoO3), 0.42 parts of ammonium tungstate (WO3), 0.96 parts of magnesium carbonate (MgO), 1.30 parts of calcium hydroxide (CaO), 0.460 parts of CoO, 0.460 parts of RuO2, 0.460 parts of Rh2O3, 0.460 parts of PdO, 0.460 parts of IrO2, 0.460 parts of PtO2, 0.995 parts of CuO, and 2.42% of expandable polyurethane (based on the total catalyst mass as oxides). The mixing speed was 42 r / min and the stirring time was 180 min.

[0110] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 48.0% (wt) of the total catalyst mass (based on oxides), and add 0.35% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0111] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 13% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 925℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0112] The catalyst was found to have a carbon content of 0.75% (wt) according to elemental analysis, a tap density of 118.9 g / 100 ml according to a tap density meter, and a crushing strength of 166.8 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0113] Example 11

[0114] A method for preparing a catalyst for the dehydrogenation of alkyl aromatics includes the following steps:

[0115] (1) Using a mixing mill, the following components were mixed evenly: 42.08 parts of iron oxide red (Fe2O3), 21.026 parts of iron oxide yellow (Fe2O3), 12.72 parts of cerium carbonate (CeO2), 11.73 parts of potassium carbonate (K2O), 2.45 parts of ammonium molybdate (MoO3), 2.45 parts of ammonium tungstate (WO3), 2.94 parts of MgO, 0.98 parts of calcium carbonate (CaO), 0.99 parts of SrO, 0.018 parts of NiO, 0.872 parts of CuO, 0.872 parts of Ag2O, 0.872 parts of Au2O3, and 3.05% of expandable graphite polystyrene (based on the total catalyst mass as oxides). The mixing speed was 40.4 r / min and the stirring time was 60 min.

[0116] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 17.8% (wt) of the total catalyst mass (based on oxides), and add 0.96% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0117] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80°C for 4 hours and 160°C for 4 hours. Then place it in a tube furnace under a 7% O2 / N2 atmosphere and calcine at 400°C for 2 hours and 800°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0118] The catalyst was found to have a carbon content of 1.42% (wt) according to elemental analysis, a tap density of 117.8 g / 100 ml according to a tap density meter, and a crushing strength of 152.5 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0119] Comparative Example 1

[0120] The catalyst was prepared according to Example 1, except that expandable organic resin was not added and the template agent was replaced with inorganic cement. The preparation method includes the following steps:

[0121] (1) Using a mixing mill, the following components were mixed evenly: iron oxide red equivalent to 43.855 parts Fe2O3, iron oxide yellow equivalent to 21.93 parts Fe2O3, cerium hydroxide equivalent to 12.57 parts CeO2, potassium carbonate equivalent to 9.67 parts K2O, ammonium molybdate equivalent to 2.09 parts MoO3, 1.79 parts WO3, magnesium carbonate equivalent to 3.01 parts MgO, 0.320 parts NiO, 0.320 parts Rh2O3, 0.320 parts PdO, 0.320 parts IrO2, 0.320 parts PtO2, 0.605 parts CuO, 0.605 parts Ag2O, 0.605 parts Au2O3, and silicate cement equivalent to 1.67% of the total catalyst mass (based on oxides). The mixing speed was 48.5 r / min, and the mixing time was 50 min.

[0122] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 23.5% (wt) of the total catalyst mass (based on oxides), and add 0.41% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C for thorough kneading.

[0123] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under an 8% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 780℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 2.

[0124] The catalyst was found to have a carbon content of 0 by elemental analysis, a tap density of 154.6 g / 100 ml by a tap density meter, and a crushing strength of 142.7 N / 5 mm by a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was added to the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0125] Comparative Example 2

[0126] The catalyst was prepared according to Example 2, except that the expandable organic resin content of the template agent was excessive. The preparation method includes the following steps:

[0127] (1) Using a mixing mill, the following components were mixed evenly: iron oxide red equivalent to 47.76 parts Fe2O3, iron oxide yellow equivalent to 23.89 parts Fe2O3, cerium hydroxide equivalent to 10.57 parts CeO2, potassium carbonate equivalent to 8.59 parts K2O, ammonium molybdate equivalent to 0.33 parts MoO3, calcium carbonate equivalent to 4.89 parts CaO, 0.424 parts CoO, 0.424 parts NiO, 0.424 parts RuO2, 0.424 parts Rh2O3, 0.424 parts PdO, 0.424 parts OsO2, 0.325 parts PtO2, 0.501 parts Ag2O, 0.501 parts Au2O3, and expandable polyurethane equivalent to 5.93% of the total catalyst mass (based on oxides). The mixing speed was 37.1 r / min, and the stirring time was 250 min.

[0128] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 18.7% (wt) of the total catalyst mass (based on oxides), and add 0.75% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0129] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under an 11% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 820℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 2.

[0130] The catalyst was found to have a carbon content of 2.85% (wt) according to elemental analysis, a tap density of 97.3 g / 100 ml according to a tap density meter, and a crushing strength of 90.2 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was added to the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0131] Comparative Example 3

[0132] The catalyst was prepared according to Example 3, except that the formulation did not contain Group IB metal promoters (Cu, Ag, and Au). The preparation method includes the following steps:

[0133] (1) Use a mixing mill to mix 51.93 parts of iron oxide red, 25.96 parts of iron oxide yellow, 9.16 parts of cerium carbonate, 10.76 parts of potassium carbonate, 1.17 parts of WO3, 0.75 parts of strontium carbonate, 0.09 parts of NiO, 0.09 parts of PdO, 0.09 parts of IrO2, and 2.98% of expandable graphite polystyrene (based on total catalyst mass, in oxides) evenly, at a speed of 37.1 r / min and a stirring time of 250 min.

[0134] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 30.2% (wt) of the total catalyst mass (based on oxides), and add 0.62% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0135] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace under a 15% O2 / N2 atmosphere and calcine at 400℃ for 2 hours and 795℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 2.

[0136] The catalyst was found to have a carbon content of 1.26% (wt) according to elemental analysis, a tap density of 113.2 g / 100 ml according to a tap density meter, and a crushing strength of 136.7 N / 5 mm according to a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0137] Comparative Example 4

[0138] The catalyst was prepared according to Example 8, except that the calcination atmosphere in the tubular furnace used during the preparation process was air. The preparation method includes the following steps:

[0139] (1) Using a mixing mill, 50.13 parts of iron oxide red, 25.072 parts of iron oxide yellow, 9.96 parts of cerium carbonate, 8.24 parts of potassium carbonate, 0.51 parts of ammonium molybdate, 0.46 parts of calcium carbonate, 2.68 parts of strontium hydroxide, 0.309 parts of CoO, 0.309 parts of RuO2, 0.309 parts of PdO, 0.309 parts of IrO2, 0.856 parts of CuO, 0.856 parts of Ag2O, and 1.76% of expandable phenolic resin (based on total catalyst mass, in oxides) were mixed evenly at a speed of 26.8 r / min for 120 min.

[0140] (2) Next, transfer the mixed dry powder to a kneader, add solvent water equivalent to 36.9% (wt) of the total catalyst mass (based on oxides), and add 0.27% of hydroxyethyl cellulose and 0.2% of polyacrylamide lubricant equivalent to the total catalyst mass (based on oxides). At the same time, heat to 80°C to knead thoroughly, so that the expandable organic resin expands and ages.

[0141] (3) After taking it out, extrude it into strips and cut it into pellets with a diameter of 3 mm and a length of 5-10 mm. Place it in an oven and bake at 80℃ for 4 hours and 160℃ for 4 hours. Then place it in a tube furnace in an air (21% O2 / N2) atmosphere and calcine at 400℃ for 2 hours and 905℃ for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 2.

[0142] The catalyst was found to have a carbon content of 0 by elemental analysis, a tap density of 139.5 g / 100 ml by a tap density meter, and a crushing strength of 122.3 N / 5 mm by a DL-II intelligent particle strength meter. Simultaneously, 100 ml of the catalyst was loaded into the reactor and incubated at atmospheric pressure and a liquid hourly space velocity (LHSV) of 1.0 h⁻¹. －1 Performance was evaluated at a temperature of 630℃ and a water ratio of 1.10 (wt). The results of physical property tests and steady-state performance are listed in Table 3.

[0143] Table 1. Weight percentage composition of catalysts

[0144]

[0145] Table 2. Weight percentage composition of catalysts

[0146]

[0147] Table 3 Comparison of Catalyst Performance

[0148]

[0149] The above examples and comparative examples illustrate that by adding a small amount of expandable organic resin template agent to the Fe-Ce-alkali metal-VIB-alkaline earth metal-VIII-IB metal system and inducing it to expand, age, and foam under suitable conditions, while adjusting the calcination atmosphere to control partial carbonization and improve mechanical strength, the resulting catalyst not only maintains high catalytic performance under low water ratio reaction conditions, but also has low bulk density and good crushing strength, and can be used in the industrial production of alkyl aromatic dehydrogenation.

[0150] Any numerical value mentioned in this invention, if there is only a two-unit interval between any minimum and any maximum value, includes all values ​​that increase by one unit each time from the minimum to the maximum value. For example, if the amount of a component, or the value of a process variable such as temperature, pressure, or time, is stated as 50-90, in this specification it means specifically listing values ​​such as 51-89, 52-88… and 69-71 and 70-71, etc. For non-integer values, it may be appropriately considered that a unit is 0.1, 0.01, 0.001, or 0.0001. These are merely some specifically specified examples. In this application, in a similar manner, all possible combinations of numerical values ​​between the listed minimum and maximum values ​​are considered to have been disclosed.

[0151] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. An alkyl aromatic hydrocarbon dehydrogenation catalyst prepared from a composition, characterized in that, The composition comprises a metal source and additives. The metal source includes Fe, Ce, alkali metals, Group VIB metals, alkaline earth metals, Group IB metals, and Group VIII metals other than Fe. The additives include an organic resin foaming agent, a lubricant, and a thickener. The amount of additives added is 0.5-5% of the total mass of the catalyst composition based on its oxide content. The amount of organic resin foaming agent added is 0.3-3.5% of the total mass of the catalyst composition based on its oxide content. The catalyst is prepared from the composition using an organic resin foaming method and calcined in a furnace with a calcination atmosphere of 5-15% O2 / N2.

2. The catalyst according to claim 1, characterized in that, The amount of metal source added is calculated based on the amount of the corresponding metal oxide added. The amount of the Group IB metal source added is 0.001 to 3% of the total mass of the catalyst composition based on the oxide content, and / or the amount of the Group VIII metal source other than Fe added is 0.005 to 4% of the total mass of the catalyst composition based on the oxide content.

3. The catalyst according to claim 1, characterized in that, The amount of the thickener added is 0.1 to 1% of the total mass of the catalyst composition based on the oxide content, and / or the amount of the lubricant added is 0.1 to 0.5% of the total mass of the catalyst composition based on the oxide content.

4. The catalyst according to any one of claims 1-3, characterized in that, The alkali metal source is selected from at least one of Li, Na, and K; and / or The VIB group metal source is selected from at least one of Cr, Mo, and W; and / or The alkaline earth metal source is selected from at least one of Mg, Ca, and Sr; and / or The Group IB metal source is selected from at least one of Cu, Ag, and Au; and / or The group VIII metal source other than Fe is selected from at least one of Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt.

5. The catalyst according to any one of claims 1-3, characterized in that, The Fe source is selected from at least one of iron oxide red, iron oxide yellow, ferric nitrate, ferric citrate, and ferric ammonium citrate; and / or The alkali metal source is selected from at least one of alkali metal carbonates, oxalates, bicarbonates, nitrates, citrates, and hydroxides; and / or The Ce source is selected from at least one of cerium oxide, cerium oxalate, cerium acetate, cerium carbonate, cerium hydroxide, cerium nitrate, and cerium ammonium nitrate; and / or The VIB metal source is selected from at least one of the following: ammonium salts, metaammonium salts, and oxides of VIB metal; and / or The alkaline earth metal source is selected from at least one of the following: oxides, carbonates, and hydroxides of alkaline earth metals; and / or The Group IB metal source is selected from at least one of the following: oxides, hydroxides, carbonates, oxalates, acetates, and nitrates of Group IB metals; and / or The Group VIII metal source other than Fe is selected from at least one of the following: nitrates, carbonates, hydroxides, chlorides, acetates, and metal complexes of Group VIII metals other than Fe; and / or The organic resin foaming agent is selected from at least one of expandable polystyrene, expandable graphitic polystyrene, expandable phenolic resin, expandable polyethylene, expandable polypropylene, expandable polyethylene-styrene, expandable polystyrene-acrylonitrile copolymer, expandable polystyrene-methyl methacrylate, expandable polyvinyl chloride, expandable polyamide, expandable polyester, and expandable epoxy resin; and / or The lubricant is selected from at least one of talc, graphite, fatty acid amide, erucamide, citric acid, molybdenum disulfide, stearic acid, stearate, ethylene distearate, polyethylene wax, solid paraffin, water, lubricating oil, glycerin, soluble oil, silicone oil, liquid paraffin, n-butyl stearate, silicone resin, and polyacrylamide solution; and / or The thickener is selected from at least one of inorganic thickeners, natural polymers and their derivatives, synthetic polymers, associative alkali-swellable thickeners, and polyurethane thickeners.

6. The catalyst according to claim 5, characterized in that, The thickener is selected from cellulose ethers and their derivatives.

7. The catalyst according to any one of claims 1-3, characterized in that, The catalyst contains 0.1-2% carbon by weight, comprising the following components by weight percentage: 62-81% Fe2O3, 8-13% CeO2, 7-14% alkali metal oxides, 0.1-5% Group VIB metal oxides, 0.1-6% alkaline earth metal oxides, 0.005-4% selected from at least one Group VIII metal oxide other than Fe, and 0.001-3% selected from at least one Group IB metal oxide.

8. The catalyst according to claim 7, characterized in that, The weight ratio of the group VIII metal oxide (excluding Fe) to the group IB metal oxide is 0.01 to 70:

1.

9. The catalyst according to claim 8, characterized in that, The weight ratio of the group VIII metal oxide (excluding Fe) to the group IB metal oxide is 0.5 to 3:

1.

10. A method for preparing the catalyst according to any one of claims 1-9, comprising the following steps: (1) Fe source, Ce source, alkali metal source, group VIB metal source, alkaline earth metal source, group IB metal source, group VIII metal source and organic resin foaming agent are mixed to obtain the first mixed powder; (2) Add solvent, thickener and lubricant to the first mixture and mix to obtain the second mixture slurry; (3) Remove the solvent to obtain the second mixed paste; (4) The second mixed paste is dried and calcined in a furnace with a calcination atmosphere of 5-15% O2 / N2.

11. The preparation method according to claim 10, characterized in that, The drying conditions include: a temperature of 30–200°C and a time of 6–24 h; and / or the calcination conditions include: a temperature of 200–1200°C and a time of 4–20 h; and / or the solvent is at least one of water, alcohol, organic amine, ammonia, dimethyl sulfoxide, ether, and ester, and the amount of solvent added is 10–60% of the total mass of the catalyst based on its oxide content.

12. The use of the catalyst according to any one of claims 1-9 in alkyl aromatic hydrocarbon reactions.

13. A method for dehydrogenating alkyl aromatics to produce alkenyl aromatics, comprising: Under the conditions of alkyl aromatic hydrocarbon dehydrogenation reaction, alkyl aromatic hydrocarbons, water vapor, and the catalyst described in any one of claims 1-9 are contacted to react.

14. The method according to claim 13, characterized in that, The dehydrogenation reaction conditions for the alkyl aromatics include: a temperature of 580–650 °C and a volume hourly space velocity (VHSV) of 0.5–1.5 h⁻¹. -1 The weight ratio of water to alkyl aromatics is 0.5 to 1.3, and the pressure is 20 kPaA to 0.10 MPaA.

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