Dehydrogenation catalyst, preparation method and application thereof, and method for dehydrogenating alkyl aromatics to prepare alkenyl aromatics

Abstract

The present invention provides a dehydrogenation catalyst, a preparation method and application thereof, and a method for dehydrogenating alkyl aromatics to produce alkenyl aromatics. The catalyst comprises the following active components, measured by weight percentage: (a) 63-81% of Fe2O3; (b) 7-14% of K2O; (c) 6-13% of CeO2; (d) 0.1-4% of WO3; (e) 0.1-5% of an alkaline earth metal oxide; (f) 0.05-6% of at least one metal oxide selected from Group VB; and (g) 0.01-2% of at least one Group IIIB metal oxide other than Ce. The weight ratio of the Group VB metal oxide to the Group IIIB metal oxide other than Ce is 0.1-30. The catalyst of the present invention is used in dehydrogenation under low water ratio conditions, such as in the dehydrogenation reaction of ethylbenzene, and has good technical effects in promoting catalytic activity and single yield.

Description

Technical Field

[0001] The present invention relates to a dehydrogenation catalyst, a preparation method and application thereof, and a method for preparing alkenyl aromatic hydrocarbons by dehydrogenating alkyl aromatic hydrocarbons. Background Art

[0002] Styrene is an important basic organic chemical raw material. Currently, more than 85% of the world's industrial production uses direct dehydrogenation of ethylbenzene. The main reaction is C6H5-C2H5→C6H5CH=CH2+H2ΔH f298 = +123kJ / mol. This reaction is an endothermic reaction with increased volume, requiring a large amount of water vapor to provide energy, act as a diluent to promote chemical equilibrium, induce the formation of the catalyst's active phase, inhibit carbon deposition, and maintain the system's oxidation state. The activation of the catalyst precursor to produce a metastable potassium ferrite phase, the high-temperature cracking of water, and the vaporization of carbon dictate that the reaction typically proceeds at temperatures exceeding 600°C. Existing styrene catalysts are mostly Fe-K-based, with iron oxide as the primary catalyst and K as the primary additive. They also contain structural stabilizers such as oxides of Ce, Mg, Mo, W, or Ca. In recent years, market pressures for larger-scale equipment, high-load operation, and energy conservation and consumption reduction have driven continuous improvements in catalysts toward higher yields, greater mechanical strength, improved tolerance to low water ratios, and greater stability.

[0003] Cerium oxide is widely used in industry due to its unique cubic fluorite crystal structure, abundant surface defects, and excellent oxygen storage and release capabilities. Previous studies have shown that higher Ce content improves catalyst selectivity and yield, while the CeO2 crystal structure provides considerable mechanical strength and wear resistance. Existing techniques for improving catalytic performance primarily rely on manipulating the Ce content, the type and ratio of the cerium source, and the preparation method.

[0004] CN101992092B uses cerium oxalate and cerium carbonate as cerium sources, and simultaneously regulates the ratio of the two cerium sources; CN105562025B uses cerium salts and cerium oxide as cerium sources. CN104096568B reports a Fe-K-Ce-Mg-Mo ethylbenzene dehydrogenation to styrene catalyst and preparation method. The cerium source uses a certain ratio of cerium nitrate and homemade nano-cerium trioxide. The prepared catalyst has high crushing resistance and high catalytic activity under low water ratio conditions, but does not mention stability under low water ratio conditions. CN101992092B reports a catalyst in the Fe-K-Ce-Mo-Mg system. By adding a certain ratio of cerium oxalate and cerium carbonate, the mechanical strength and stability of the low-potassium catalyst are improved, but the applicable water ratio of 2.0 (by weight) is still relatively high.

[0005] Recently, US20170121241A1 disclosed a Fe-K-Ce-Mg-Ca-Mo hydrocarbon dehydrogenation catalyst. By adjusting the auxiliary agent composition and catalyst preparation method, the weight ratio of the Fe-K mixed oxide phase is controlled to be greater than 20% and the grain size of cerium oxide is controlled to be 10-30nm. At a water ratio of 1.25 (weight), the styrene yield can reach 69.2%. However, the catalyst grain size range is relatively limited, and the stability effect at low water ratio is not mentioned. Summary of the Invention

[0006] Based on the problem of low activity of dehydrogenation catalysts in the prior art, the purpose of the present invention is to provide a high-activity low-water-ratio-tolerant dehydrogenation catalyst and a preparation method thereof, wherein the dehydrogenation catalyst can maintain good catalytic activity and alkenyl aromatic hydrocarbon yield under low water-ratio conditions.

[0007] According to a first aspect of the present invention, the present invention provides a dehydrogenation catalyst comprising the following active components by weight percentage:

[0008] (a) 63-81% Fe2O3; (b) 7-14% K2O; (c) 6-13% CeO2;

[0009] (d) 0.1-4% WO3; (e) 0.1-5% alkaline earth metal oxide;

[0010] (f) 0.05-6% of at least one metal oxide selected from Group VB; (g) 0.01-2% of at least one metal oxide selected from Group IIIB except Ce;

[0011] The weight ratio of the VB group metal oxide to the IIIB group metal oxide excluding Ce is 0.1 to 30.

[0012] According to a second aspect of the present invention, the present invention provides a method for preparing the dehydrogenation catalyst of the present invention, the method comprising:

[0013] The K source, Ce source and Group IIIB metal source are pre-ground, mixed with the Fe source, W source, alkaline earth metal source, Group VB metal source, pore former, optional binder and solvent, optionally shaped, optionally dried and then calcined.

[0014] According to the third aspect of the present invention, the present invention provides the use of the dehydrogenation catalyst of the present invention in the dehydrogenation reaction of alkyl aromatics, preferably the alkyl aromatics are one or more of ethylbenzene, diethylbenzene, methylethylbenzene, isopropylbenzene, and tert-butylethylbenzene.

[0015] According to a fourth aspect of the present invention, a method for preparing alkenyl aromatics by dehydrogenating alkyl aromatics is provided, comprising: contacting alkyl aromatics with the dehydrogenation catalyst of the present invention under alkyl aromatic dehydrogenation reaction conditions for reaction; preferably, the alkyl aromatic dehydrogenation reaction conditions include: a temperature of 590-630°C, a volume space velocity of 0.8-1.5h -1 , the weight ratio of water to alkyl aromatic hydrocarbon is 0.9-1.3, and the pressure is -40kPa to 1.01MPa; preferably, the alkyl aromatic hydrocarbon is ethylbenzene.

[0016] The present invention adds at least one VB group metal (preferably V, Nb, Ta) oxide additive and at least one IIIB group metal oxide (preferably Sc, Y, La, Pr, Nd, Sm) additive to the iron-potassium-cerium-tungsten-alkaline earth metal system, preferably controlling the weight ratio of the VB group and the IIIB group metal oxides to be 0.1 to 30; in addition, in the preparation method, preferably, the particle size distribution of the raw materials K source and Ce source is screened by grinding, and the particle size matching degree (D 50K / D 50IIIB金属 =0.01 to 500) and calcination conditions, the final catalyst has a median pore size range of 0.1 to 0.6 μm. On the one hand, the present invention optimizes the promotion of oxygen storage and release of cerium oxide by controlling the ratio of VB group and IIIB group metal oxides, thereby improving the catalytic activity and yield of the catalyst at low water ratios; at the same time, the pore size distribution and pore volume of the catalyst are optimized by preferably regulating the matching degree of the raw material K and Ce source particle size, as well as the calcination conditions, further improving the catalyst's resistance to carbon deposition and structural stability. The catalyst of the present invention is used in dehydrogenation reactions under low water ratio conditions, such as the dehydrogenation of ethylbenzene, and has good technical effects in promoting catalytic activity and single yield. DETAILED DESCRIPTION

[0017] The endpoints of the ranges and any values ​​disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0018] The present invention provides a dehydrogenation catalyst, which comprises the following active components in weight percentage: (a) 63-81% Fe2O3; (b) 7-14% K2O; (c) 6-13% CeO2;

[0019] (d) 0.1-4% WO3; (e) 0.1-5% alkaline earth metal oxide;

[0020] (f) 0.05-6% of at least one metal oxide selected from Group VB; (g) 0.01-2% of at least one metal oxide selected from Group IIIB other than Ce; the weight ratio of the Group VB metal oxide to the Group IIIB metal oxide other than Ce is 0.1-30. The present invention adds at least one Group VB metal (preferably V, Nb, Ta) oxide promoter and at least one Group IIIB metal oxide (preferably Sc, Y, La, Pr, Nd, Sm) promoter to the iron-potassium-cerium-tungsten-alkaline earth metal system, preferably controlling the weight ratio of the Group VB to Group IIIB metal oxides to be 0.1-30, thereby optimizing the promotion of oxygen storage and release of cerium oxide and improving the catalytic activity and yield of the catalyst at low water ratios. The reason is speculated to be that VB group metals (V, Nb, Ta) have extremely high melting points, hardness, and corrosion resistance. In addition, doping with VB group elements such as V, Nb, and Ta can form solid solutions with Ce to stabilize Ce, increase the oxygen vacancy concentration on the CeO2 surface, improve the oxygen storage capacity of cerium oxide, and also improve the thermal stability of CeO2 at high temperatures. Group IIIB metals can enter the cerium oxide crystal structure, replace Ce, form more oxygen vacancies, and increase the stability of CeO2. These two types of metal oxides have a synergistic effect on improving the catalytic activity of the catalyst at low water ratios.

[0021] According to a preferred embodiment of the present invention, the catalyst comprises the following components by weight percentage:

[0022] (a) 64-78% Fe2O3; (b) 8-13% K2O; (c) 7-12% CeO2;

[0023] (d) 0.2-3% WO3; (e) 0.5-4% alkaline earth metal oxide;

[0024] (f) 0.1-5% of at least one metal oxide selected from Group VB; and (g) 0.05-1.5% of at least one metal oxide selected from Group IIIB other than Ce. This can further optimize the catalytic effect of promoting oxygen storage and release in cerium oxide, thereby improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0025] According to a preferred embodiment of the present invention, the weight ratio of the VB group metal oxide to the IIIB group metal oxide is 0.2 to 15. This can further optimize the promotion of oxygen storage and release of cerium oxide, and improve the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0026] According to a preferred embodiment of the present invention, the median pore size of the catalyst is 0.1-0.6 μm, preferably 0.2-0.5 μm, thereby further optimizing the promotion of oxygen storage and release of cerium oxide and improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0027] According to a preferred embodiment of the present invention, the pore volume of the catalyst is 0.05-0.2 cm 3 / g. This can further optimize the promotion of oxygen storage and release of cerium oxide, and improve the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0028] According to a preferred embodiment of the present invention, the VB group metal oxide is selected from at least one of V2O5, Nb2O5, and Ta2O5, preferably one or more of a mixture of V2O5 and Nb2O5, a mixture of V2O5 and Ta2O5, and a mixture of Nb2O5 and Ta2O5, and more preferably a mixture of V2O5, Nb2O5, and Ta2O5. This can further optimize the effect of promoting oxygen storage and release in ceria, thereby improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0029] According to a preferred embodiment of the present invention, the Group IIIB metal oxide other than Ce is selected from at least one of Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3, and Sm2O3, and preferably at least four of Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3, and Sm2O3. This can further optimize the effect of promoting oxygen storage and release in cerium oxide, thereby improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0030] According to a preferred embodiment of the present invention, the alkaline earth metal oxide is at least one of MgO, CaO, SrO, and BaO. This can further optimize the promotion of oxygen storage and release of cerium oxide, thereby improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratios.

[0031] According to the present invention, preferably, the catalyst contains an inorganic binder and / or an organic binder.

[0032] According to the present invention, preferably, the selected inorganic binder is derived from one or more of kaolin, diatomaceous earth, cement, silica sol, pseudo-boehmite, potassium silicate, montmorillonite, halloysite, pseudo-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite.

[0033] According to the present invention, preferably, the organic binder is derived from at least one of polyacrylamide, sodium polyacrylate, starch and povidone.

[0034] According to the present invention, preferably, the binder content is 0.1-3% based on the total weight of the catalyst.

[0035] According to the present invention, preferably, the catalyst does not contain molybdenum oxide.

[0036] The catalysts having the aforementioned characteristics of the present invention can achieve the purpose of the present invention. The present invention has no special requirements for its preparation method. According to the present invention, a preparation method of a dehydrogenation catalyst is provided, which comprises: pre-grinding a K source, a Ce source and a Group IIIB metal source, and then mixing them with an Fe source, a W source, an alkaline earth metal source, a Group VB metal source, a pore-forming agent, and optionally a binder and a solvent, optionally forming them, optionally drying them, and then calcining them.

[0037] According to the present invention, preferably, the catalyst comprises the following raw materials: Fe source, K source, Ce source, W source, alkaline earth metal oxide, at least one VB group metal oxide, at least one IIIB group metal oxide, a binder and a pore-forming agent weighed in a certain ratio, which are fully stirred and mixed in a mixer, and then a solvent is added dropwise in a kneader to form a uniform viscous paste, which is then extruded and granulated into cylindrical particles with a diameter of 3 mm and a length of 5 to 10 mm, and finally the catalyst is obtained through a drying and calcination process.

[0038] According to the present invention, preferably, the solvent in the kneading process is selected from at least one of water, alcohols, or esters, preferably deionized water. The solvent is added dropwise during the kneading process, and the amount of solvent added is adjusted according to the kneading time and the wetness of the material. Preferably, the amount of solvent added is 15-35% by weight, preferably 18-30% by weight, of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, Group VB metal source, and Group IIIB metal source added; the amounts of the Fe source, K source, Ce source, W source, alkaline earth metal source, Group VB metal source, and Group IIIB metal source added are all calculated as oxides.

[0039] According to a preferred embodiment of the present invention, the method comprises:

[0040] (1) grinding one or more K source dry powders in a ball mill or a sand mill to perform a first mixing; preferably, the grinding speed is controlled to be 100-1000 r / min, preferably 200-900 r / min; the grinding time is 1 min-5 h, preferably 15 min-3 h; and the ground K source powder is obtained by screening;

[0041] (2) grinding one or more Ce sources and dry powders of Group IIIB metal sources other than Ce in a ball mill or a sand mill, and performing a second mixing process, preferably controlling the grinding speed to be 50-1000 r / min, preferably 200-800 r / min; and the grinding time to be 1 min-3 h, preferably 10 min-2 h; and obtaining a ground mixed powder of Ce source and Group IIIB metal source through screening;

[0042] (3) performing a third mixing of the K source powder, the Ce source and the Group IIIB metal source mixed powder, the Fe source, the W source, the alkaline earth metal source, the Group VB metal source, the pore-forming agent and optionally the binder;

[0043] (4) The dry powder obtained by the third mixing is mixed with the solvent for the fourth time. The above preferred preparation method can further optimize the promoting effect on oxygen storage and release of cerium oxide, and improve the catalytic activity and yield of the dehydrogenation catalyst at low water ratio.

[0044] According to the method of the present invention, preferably, the particle size distribution of the dry powder K source powder obtained by the first mixing is: 50K The particle size is 1-500 μm, preferably 5-350 μm, and more preferably 10-200 μm. This can further optimize the promoting effect on oxygen storage and release of cerium oxide, and improve the catalytic activity and yield of the dehydrogenation catalyst at low water ratio.

[0045] According to the method of the present invention, preferably, in the particle size distribution of the dry powder Ce source and the IIIB group metal mixed powder obtained by the second mixing, D 50IIIB 金属 The particle size is 0.1-1000 μm, preferably 0.5-750 μm, and more preferably 1-500 μm; thereby further optimizing the promoting effect on oxygen storage and release of cerium oxide, and improving the catalytic activity and yield of the dehydrogenation catalyst at low water ratio.

[0046] According to the method of the present invention, preferably, D 50K / D 50IIIB金属 =0.005-200, preferably D 50K / D 50IIIB金属 = 0.02-50. This can further optimize the promoting effect on oxygen storage and release of cerium oxide, and improve the catalytic activity and yield of the dehydrogenation catalyst at low water ratio.

[0047] The present invention discovered that, because some raw materials decompose or react with other raw materials during the catalyst calcination process, under certain other composition conditions, by controlling the particle size of the raw materials K and Ce sources, optimizing the particle size matching, and combining other control conditions, it is possible to regulate the pore structure of the catalyst after calcination. Large pore diameters and small pore volumes result in an excessively low specific surface area within the pores, while small pore diameters and large pore volumes increase the mass transfer resistance between reactants and products. Therefore, only moderate pore diameters and pore volumes promote catalytic activity.

[0048] The raw materials used for the catalyst component of the present invention are as follows:

[0049] According to the present invention, the iron oxide is preferably selected from iron oxide red and / or iron oxide yellow. Preferably, the Fe source is iron oxide red and iron oxide yellow.

[0050] According to the present invention, the K source used is preferably selected from at least one of potassium carbonate, potassium bicarbonate and potassium hydroxide.

[0051] According to the present invention, the Ce source used is at least one selected from cerium oxide, cerium oxalate, cerium acetate, cerium carbonate, cerium hydroxide and basic cerium carbonate.

[0052] According to the present invention, the W source used is at least one selected from ammonium tungstate, ammonium metatungstate and tungsten trioxide.

[0053] According to the present invention, the alkaline earth metal (Mg, Ca, Sr, Ba) source is selected from at least one of oxides, hydroxides or carbonates.

[0054] According to the present invention, the VB group metal source (V, Nb, Ta) is selected from at least one of VB group metal oxides, VB group metal hydroxides, VB group metal nitrates, VB group metal acetates, metal acid salts of VB group metals, and VB group metal oxynitrates, and is preferably at least one of VB group metal oxides, VB group metal hydroxides, metal acid salts of VB group metals, and VB group metal nitrates.

[0055] According to the present invention, the source of the Group IIIB metal (Sc, Y, La, Pr, Nd, Sm) used is selected from at least one of Group IIIB metal oxides, hydroxides, nitrates, acetates, oxalates, carbonates, and basic carbonates.

[0056] According to the present invention, the Fe source is selected from red iron oxide and / or yellow iron oxide; preferably, the Fe source is red iron oxide and yellow iron oxide; and / or the K source is selected from at least one of potassium carbonate, potassium bicarbonate and potassium hydroxide; and / or the Ce source is selected from at least one of cerium oxide, cerium oxalate, cerium acetate, cerium carbonate, cerium hydroxide and basic cerium carbonate; and / or the W source is selected from at least one of ammonium tungstate, ammonium metatungstate and tungsten trioxide; and / or the alkaline earth metal source is selected from at least one of oxides, carbonates and hydroxides; and / or the VB group metal source is selected from VB At least one of Group IIIB metal oxides, Group VB metal hydroxides, Group VB metal nitrates, Group VB metal oxynitrates and Group VB metal acetates, preferably at least one of Group VB metal oxides, Group VB metal hydroxides and Group VB metal nitrates; and / or the Group IIIB metal source other than Ce is selected from at least one of Group IIIB metal oxides, Group IIIB metal hydroxides, Group IIIB metal oxalates, Group IIIB metal acetates, Group IIIB metal nitrates, Group IIIB metal carbonates and Group IIIB metal basic carbonates.

[0057] According to the present invention, in addition to the main catalyst components, a binder, pore-forming agent, etc. may also be added during the preparation process. The binder in the catalyst comprises an inorganic binder and / or an organic binder. Preferably, the binder is selected from at least one of the inorganic binders kaolin, diatomaceous earth, cement, silica sol, pseudo-boehmite, potassium silicate, montmorillonite, halloysite, pseudo-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite, and bentonite; and the organic binders polyacrylamide, sodium polyacrylate, starch, and povidone. Preferably, the binder content is 0.1-3%, based on the total weight of the catalyst.

[0058] According to the present invention, the pore-forming agent is selected from at least one of activated carbon, graphite, polystyrene and cellulose and its derivatives (such as methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, ethyl cellulose, carboxymethyl cellulose, microcrystalline cellulose, etc.), preferably, the pore-forming agent is one of activated carbon, graphite, ethyl cellulose, hydroxypropyl methylcellulose, hydroxypropyl cellulose, sodium carboxymethyl cellulose and polystyrene microspheres.

[0059] According to a preferred embodiment of the present invention, the amount of the pore-forming agent added is 1-6% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source, preferably 2-5% by weight; the amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source added is calculated as oxide.

[0060] According to a preferred embodiment of the present invention, preferably, the amount of the solvent added is 15-35% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group element source and IIIB group metal source except Ce, preferably 18-30% by weight; the amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source and IIIB group metal source added are all calculated as oxides.

[0061] According to the method of the present invention, the method further includes molding the mixed material before drying; preferably, the drying conditions include: temperature of 30-250°C, time of 2-24h; more preferably, the drying conditions include: drying at 30-120°C for 2-24h, then heating to 150-200°C and drying for 2-24h.

[0062] According to the method of the present invention, preferably, the calcination conditions include: temperature of 300-1200°C, time of 1-12 hours; more preferably, the calcination conditions include: calcination at 300-700°C for 1-12 hours, then heating to 800-1200°C and calcination for 1-12 hours.

[0063] The catalyst of the present invention is particularly suitable for use in the dehydrogenation reaction of alkyl aromatics. The present invention provides the use of the dehydrogenation catalyst of the present invention in the dehydrogenation reaction of alkyl aromatics. Preferably, the alkyl aromatics are one or more of ethylbenzene, diethylbenzene, methylethylbenzene, isopropylbenzene and tert-butylethylbenzene.

[0064] According to the present invention, a method for preparing alkenyl aromatics by dehydrogenating alkyl aromatics is provided. The method comprises: contacting the alkyl aromatics with the dehydrogenation catalyst of the present invention under alkyl aromatic dehydrogenation reaction conditions to carry out a reaction.

[0065] According to the present invention, preferably, the alkyl aromatic dehydrogenation reaction conditions include: temperature of 590-630 ° C, volume space velocity of 0.8-1.5h -1 , the weight ratio of water to alkyl aromatic hydrocarbon is 0.9-1.3, and the pressure is -40kPa to 1.01MPa.

[0066] According to the present invention, preferably, the alkyl aromatic hydrocarbon is ethylbenzene.

[0067] The present invention provides a low water ratio and high activity alkyl aromatic dehydrogenation catalyst, which comprises the following components in weight percentage:

[0068] (a) 63-81% Fe2O3;

[0069] (b) 7-14% K2O;

[0070] (c) 6-13% CeO2;

[0071] (d) 0.1-4% WO3;

[0072] (e) 0.1 to 5% of alkaline earth metal oxides;

[0073] (f) 0.05-6% of VB group metal oxide;

[0074] (g) 0.01-2% of a Group IIIB metal oxide;

[0075] According to the present invention, preferably, the mass ratio of the contained Group VB oxide to the Group IIIB metal oxide is 0.1-30.

[0076] According to a preferred embodiment of the present invention, the following components are included in weight percentage:

[0077] (a) 64-78% Fe2O3; (b) 8-13% K2O; (c) 7-12% CeO2;

[0078] (d) 0.2-3% WO3; (e) 0.5-4% alkaline earth metal oxide;

[0079] (f) 0.1-5% of at least one metal oxide selected from Group VB; (g) 0.05-1.5% of at least one metal oxide selected from Group IIIB except Ce;

[0080] The weight ratio of the VB group metal oxide to the IIIB group metal oxide is 0.2 to 15.

[0081] According to the present invention, a method for preparing a catalyst is preferably provided, the method comprising:

[0082] (1) One or more K source dry powders are sequentially ground in a ball mill or sand mill for a first mixing process. The speed is controlled at 0-1000 r / min, preferably 0-800 r / min, and the mixing time is 1 min-5 h, preferably 15 min-3 h. The ground K source powder is obtained by screening.

[0083] (2) Grinding one or more Ce source dry powders in sequence using a ball mill or sand mill for a second mixing process. The speed is controlled at 0-800 r / min, preferably 0-500 r / min, and the mixing time is 0.5 min-3 h, preferably 10 min-2 h. The ground Ce source powder is obtained by screening.

[0084] (3) performing a third mixing of the dry powder obtained by mixing the first and second steps with an Fe source, a W source, an alkaline earth metal source, a IIIB and VB group metal source, a pore-forming agent, and an optional binder;

[0085] (4) performing a fourth mixing of the dry powder obtained by the third mixing and the solvent.

[0086] According to the present invention, preferably, in the particle size distribution of the dry powder obtained by the first mixing, D 50 It is 1.0-500.0 μm, preferably 5.0-350.0 μm, and more preferably 10.0-200.0 μm.

[0087] According to the present invention, preferably, in the particle size distribution of the dry powder obtained by the second mixing, D 50 It is 0.1-1000.0 μm, preferably 0.5-750.0 μm, and more preferably 1.0-500.0 μm.

[0088] According to the present invention, the raw material particle size matching degree D 50K / D 50IIIB金属 =0.005-200, preferably D 50K / D 50IIIB金属 =0.2-50.

[0089] According to a preferred embodiment of the present invention, in the above technical solution, preferably, the drying conditions include: temperature of 30-250°C, time of 2-24h; more preferably, the drying conditions include: drying at 30-120°C for 2-24h, then heating to 150-200°C and drying for 2-24h.

[0090] According to a preferred embodiment of the present invention, preferably, the calcination conditions include: a temperature of 300-1200°C and a time of 1-12 hours; more preferably, the calcination conditions include: calcining at 300-700°C for 1-12 hours, then heating to 800-1200°C and calcining for 1-12 hours.

[0091] The particle size range and distribution of the ground K and Ce raw materials in the present invention are measured by a Malvern MS3000 laser particle size analyzer in a dry mode with a test range of 0.1-3500 μm and a dispersion pressure range of 0-4 bar.

[0092] The pore size distribution (median pore size) and porosity (pore volume) of the calcined catalyst in the present invention were measured using a Thermo Fisher Scientific PASCAL-140, 240 model fully automatic mercury intrusion porosimeter with a measurement range of 0.01-400 kPa and 0.1-200 MPa; the pore size distribution and porosity tests complied with ISO 15901-1:2016 standards.

[0093] The catalyst prepared by the above method was used to evaluate the performance of ethylbenzene dehydrogenation in an isothermal fixed bed. The process is briefly described as follows:

[0094] 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 respectively fed into the preheating mixer via metering pumps. After being preheated and mixed into a gaseous state, they enter the reactor. The reactor is heated by an electric heating wire to reach the predetermined temperature.

[0095] Preferably, the alkyl aromatic dehydrogenation reaction conditions include: temperature of 580-650°C, more preferably 590-630°C; volume space velocity of 0.5-1.5h -1 , more preferably 0.8-1.5h -1 The weight ratio of water to alkyl aromatic hydrocarbon is 0.5-1.3, preferably 0.9-1.3; the pressure is -60 kPa to 1.01 MPa, more preferably -40 kPa to 1.01 MPa. The reactants flowing out of the reactor are condensed with water and analyzed for their composition using a gas chromatograph.

[0096] The ethylbenzene conversion rate (referred to as conversion rate) and styrene selectivity (referred to as selectivity) are calculated according to the following formula:

[0097]

[0098]

[0099] Example 1

[0100] The potassium carbonate equivalent to 10.59 parts was ground with a sand mill at a speed of 500 r / min for 30 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 150.7μm.

[0101] Cerium carbonate equivalent to 9.08 parts of CeO2, 0.30 parts of Sc2O3, and neodymium nitrate equivalent to 0.25 parts of Nd2O3 were ground in a sand mill at a speed of 600 r / min for 30 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 14.2μm.

[0102] The ground potassium source, cerium source and IIIB metal source mixed powders were stirred in a mixer for 1 hour with 49.57 parts of iron oxide red equivalent to Fe2O3, 22.19 parts of iron oxide yellow equivalent to Fe2O3, 1.72 parts of ammonium tungstate equivalent to WO3, 2.31 parts of magnesium carbonate equivalent to MgO, 2.54 parts of Nb2O5, 3.0 parts of polystyrene microspheres and 1.45 parts of cement until the mixture was uniform.

[0103] The mixed dry powder was then poured into a kneader, and deionized water accounting for 18.7% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0104] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 287.2 nm and the pore volume was 0.138 cm 3 / g.

[0105] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0106] Example 2

[0107] The potassium bicarbonate equivalent to 12.95 parts was ground in a sand mill at a speed of 700 r / min for 170 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K is 13.5μm.

[0108] Cerium oxalate equivalent to 11.98 parts of CeO2, yttrium nitrate equivalent to 0.19 parts of Y2O3, and praseodymium carbonate equivalent to 0.15 parts of Pr2O3 were ground in a sand mill at a speed of 200 r / min for 10 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 495.3μm.

[0109] The ground potassium source, cerium source and Group IIIB metal source mixed powders were stirred in a mixer for 1 hour until the mixture was uniformly mixed with red iron oxide equivalent to 45.44 parts of Fe2O3, yellow iron oxide equivalent to 20.34 parts of Fe2O3, ammonium tungstate equivalent to 0.42 parts of WO3, calcium hydroxide equivalent to 0.32 parts of CaO, 0.21 parts of SrO, ammonium metavanadate equivalent to 2.63 parts of V2O5, 2.37 parts of Ta2O5, 3.0 parts of polystyrene microspheres and 3.0 parts of cement.

[0110] The mixed dry powder was then poured into a kneader, and deionized water accounting for 27.5% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0111] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 439.9 nm and the pore volume was 0.083 cm 3 / g.

[0112] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0113] Example 3

[0114] The potassium hydroxide equivalent to 8.05 parts was ground with a sand mill at a speed of 200 r / min for 15 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 197.6μm.

[0115] Cerium oxalate equivalent to 7.13 parts of CeO2, lanthanum carbonate equivalent to 0.52 parts of La2O3, and 0.21 parts of Sm2O3 were ground in a sand mill at a speed of 700 r / min for 100 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 4.01μm.

[0116] The ground potassium source, cerium source and Group IIIB metal source mixed powders were stirred in a mixer for 1 hour until the mixture was uniformly mixed with 53.14 parts of Fe2O3 of red iron oxide, 23.79 parts of Fe2O3 of yellow iron oxide, 2.88 parts of ammonium metatungstate, 2.56 parts of CaO of calcium carbonate, 1.3 parts of BaO of barium carbonate, 0.08 parts of V2O5 of ammonium metavanadate, 0.07 parts of Nb2O5, 3.0 parts of polystyrene microspheres and 0.27 parts of cement.

[0117] The mixed dry powder was then poured into a kneader, and deionized water accounting for 24.1% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0118] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 213.8 nm and the pore volume was 0.186 cm 3 / g.

[0119] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0120] Example 4

[0121] Compared with the catalyst prepared in Example 1, the same first mixed K source, second mixed Ce source and Group IIIB metal source are used, but the difference is that the content of the metal source is different.

[0122] The potassium carbonate equivalent to 13.59 parts was ground with a sand mill at a speed of 500 r / min for 30 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 150.7μm.

[0123] Cerium carbonate equivalent to 6.08 parts of CeO2, 0.90 parts of Sc2O3, and neodymium nitrate equivalent to 0.65 parts of Nd2O3 were ground in a sand mill at a speed of 600 r / min for 30 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 14.5μm.

[0124] The ground potassium source, cerium source and IIIB metal source mixed powders were stirred in a mixer for 1 hour with 43.59 parts of iron oxide red equivalent to Fe2O3, 19.51 parts of iron oxide yellow equivalent to Fe2O3, 3.20 parts of ammonium tungstate equivalent to WO3, 4.23 parts of magnesium carbonate equivalent to MgO, 5.45 parts of Nb2O5, 3.0 parts of polystyrene microspheres and 3.20 parts of cement until the mixture was uniform.

[0125] The mixed dry powder was then poured into a kneader, and deionized water accounting for 18.7% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0126] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 265.2 nm and the pore volume was 0.143 cm 3 / g.

[0127] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0128] Example 5

[0129] The potassium hydroxide equivalent to 11.62 parts was ground using a sand mill at a speed of 900 r / min for 180 min, and the particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50K It is 8.79μm.

[0130] Cerium oxalate equivalent to 10.37 parts of CeO2, 0.69 parts of Y2O3, and samarium nitrate equivalent to 0.21 parts of Sm2O3 were ground in a sand mill at a speed of 150 r / min for 15 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 561.5μm.

[0131] The ground potassium source, cerium source and Group IIIB metal source mixed powders were stirred in a mixer for 1 hour with red iron oxide equivalent to 47.96 parts of Fe2O3, yellow iron oxide equivalent to 21.47 parts of Fe2O3, 1.11 parts of WO3, 1.24 parts of CaO, magnesium hydroxide equivalent to 0.58 parts of MgO, ammonium metavanadate equivalent to 0.08 parts of V2O5, 0.83 parts of Nb2O5, 0.76 parts of Ta2O5, 3.0 parts of polystyrene microspheres and 2.59 parts of cement until the mixture was uniformly mixed.

[0132] The mixed dry powder was then poured into a kneader, and deionized water accounting for 21.0% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0133] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 509.7 nm and the pore volume was 0.072 cm 3 / g.

[0134] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0135] Example 6

[0136] The potassium carbonate equivalent to 9.99 parts was ground with a sand mill at a speed of 350 r / min for 20 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 172.4μm.

[0137] Cerium carbonate equivalent to 12.33 parts of CeO2, lanthanum acetate equivalent to 0.11 parts of La2O3, and praseodymium nitrate equivalent to 0.10 parts of Pr2O3 were ground in a sand mill at a speed of 400 r / min for 10 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 132.8μm.

[0138] The ground mixed powder of potassium source, cerium source and IIIB metal source was stirred in a mixer for 1 hour with red iron oxide equivalent to 44.76 parts of Fe2O3, yellow iron oxide equivalent to 20.04 parts of Fe2O3, ammonium tungstate equivalent to 2.52 parts of WO3, magnesium carbonate equivalent to 1.98 parts of MgO, strontium hydroxide equivalent to 1.44 parts of SrO, 4.61 parts of Ta2O5, 3.0 parts of polystyrene microspheres and 2.91 parts of cement until the mixture was uniform.

[0139] The mixed dry powder was then poured into a kneader, and deionized water accounting for 16.3% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0140] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 343.1 nm and the pore volume was 0.112 cm 3 / g.

[0141] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0142] Example 7

[0143] The potassium bicarbonate equivalent to 8.36 parts was ground with a sand mill at a speed of 250 r / min for 130 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 101.3μm.

[0144] Cerium oxalate equivalent to 7.59 parts of CeO2, scandium nitrate equivalent to 0.24 parts of Sc2O3, and lanthanum oxalate equivalent to 0.94 parts of La2O3 were ground in a sand mill at a speed of 450 r / min for 35 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 21.5μm.

[0145] The ground potassium source, cerium source and Group IIIB metal source powders were mixed, and stirred in a mixer for 1 hour until the mixture was uniformly mixed with 51.96 parts of red iron oxide equivalent to Fe2O3, 23.27 parts of yellow iron oxide equivalent to Fe2O3, 2.03 parts of ammonium tungstate equivalent to WO3, 1.28 parts of strontium hydroxide equivalent to SrO, 1.57 parts of barium carbonate equivalent to BaO, 0.16 parts of ammonium metavanadate equivalent to V2O5, 3.0 parts of polystyrene microspheres and 2.59 parts of cement.

[0146] The mixed dry powder was then poured into a kneader, and deionized water accounting for 29.3% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0147] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 296.3 nm and the pore volume was 0.135 cm 3 / g.

[0148] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0149] Example 8

[0150] The potassium hydroxide equivalent to 10.13 parts was ground with a sand mill at a speed of 400 r / min for 75 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 43.8μm.

[0151] Basic cerium carbonate equivalent to 9.71 parts of CeO2, 0.29 parts of Y2O3, and lanthanum carbonate equivalent to 0.23 parts of La2O3 were ground in a sand mill at a speed of 300 r / min for 15 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 201.7μm.

[0152] The ground potassium source, cerium source and Group IIIB metal source mixed powders were stirred in a mixer for 1 hour with red iron oxide equivalent to 48.67 parts of Fe2O3, yellow iron oxide equivalent to 21.79 parts of Fe2O3, ammonium metatungstate equivalent to 0.79 parts of WO3, calcium carbonate equivalent to 1.23 parts of CaO, ammonium metavanadate equivalent to 2.51 parts of V2O5, 1.70 parts of Nb2O5, 0.79 parts of Ta2O5, 3.0 parts of polystyrene microspheres and 2.02 parts of cement until the mixture was uniformly mixed.

[0153] The mixed dry powder was then poured into a kneader, and deionized water accounting for 25.6% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0154] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 365.4 nm and the pore volume was 0.104 cm 3 / g.

[0155] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0156] Example 9

[0157] The potassium carbonate equivalent to 11.62 parts was ground in a sand mill at a speed of 600 r / min for 50 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer.50K It is 50.7μm.

[0158] Cerium carbonate equivalent to 8.04 parts of CeO2, 0.10 parts of Sc2O3, yttrium nitrate equivalent to 0.10 parts of Y2O3, 0.10 parts of Pr2O3, and neodymium nitrate equivalent to 0.10 parts of Nd2O3 were ground in a sand mill at a speed of 250 r / min for 10 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 419.1μm.

[0159] The ground potassium source, cerium source and IIIB metal source mixed powders were stirred in a mixer for 1 hour with red iron oxide equivalent to 46.23 parts of Fe2O3, yellow iron oxide equivalent to 20.7 parts of Fe2O3, ammonium tungstate equivalent to 1.28 parts of WO3, magnesium carbonate equivalent to 1.81 parts of MgO, strontium hydroxide equivalent to 1.49 parts of SrO, barium carbonate equivalent to 0.66 parts of BaO, ammonium metavanadate equivalent to 1.38 parts of V2O5, 1.96 parts of Nb2O5, 1.60 parts of Ta2O5, 3.0 parts of polystyrene microspheres and 2.82 parts of cement until the mixture was uniform.

[0160] The mixed dry powder was then poured into a kneader, and deionized water accounting for 23.2% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0161] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 412.6 nm and the pore volume was 0.091 cm 3 / g.

[0162] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0163] Example 10

[0164] The potassium bicarbonate equivalent to 8.01 parts was ground with a sand mill at a speed of 300 r / min for 60 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 118.9μm.

[0165] Cerium oxalate equivalent to 11.02 parts of CeO2 and 0.21 parts of Sc2O3, yttrium nitrate equivalent to 0.25 parts of Y2O3, lanthanum carbonate equivalent to 0.25 parts of La2O3, praseodymium oxalate equivalent to 0.21 parts of Pr2O3, neodymium acetate equivalent to 0.25 parts of Nd2O3, and samarium hydroxide equivalent to 0.25 parts of Sm2O3 were ground in a sand mill at a speed of 300 r / min for 30 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 55.32μm.

[0166] The ground potassium source, cerium source and Group IIIB metal source powders were mixed, and stirred in a mixer for 1 hour until the mixture was uniformly mixed with 50.03 parts of Fe2O3 of red iron oxide, 22.4 parts of Fe2O3 of yellow iron oxide, 2.28 parts of WO3, 0.92 parts of calcium hydroxide of CaO, 0.83 parts of magnesium hydroxide of MgO, 0.85 parts of strontium carbonate of SrO, 0.77 parts of BaO of barium hydroxide, 0.37 parts of ammonium metavanadate of V2O5, 0.58 parts of Nb2O5, 3.0 parts of polystyrene microspheres and 0.51 parts of cement.

[0167] The mixed dry powder was then poured into a kneader, and deionized water accounting for 20.8% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0168] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 307.5 nm and the pore volume was 0.128 cm 3 / g.

[0169] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0170] Comparative Example 1

[0171] The potassium carbonate equivalent to 10.94 parts was ground in a sand mill at a speed of 500 r / min for 5 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 214.7μm.

[0172] The cerium carbonate equivalent to 9.37 parts of CeO2 was ground by a sand mill at a speed of 1000 r / min for 180 min, and the particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 0.537μm.

[0173] The ground potassium source and cerium source mixed powders were stirred in a mixer for 1 hour with 51.17 parts of Fe2O3 equivalent to 51.17 parts of iron oxide red, 22.91 parts of Fe2O3 equivalent to ...

[0174] The mixed dry powder was then poured into a kneader, and deionized water accounting for 18.7% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0175] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 75.3 nm and the pore volume was 0.241 cm 3 / g.

[0176] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0177] Comparative Example 2

[0178] The catalyst was prepared according to the method described in Example 2, except that the K source, Ce source and Group IIIB metal source were not ground, and no Group VB and Group IIIB additives were included.

[0179] The particle size distribution D of the solution was measured by Malven MS3000 laser particle size analyzer. 50K It is 310.5μm.

[0180] The particle size distribution D of cerium oxalate equivalent to 12.66 parts of CeO2 was measured by Malven MS3000 laser particle size analyzer. 50IIIB金属 It is 1071.8μm.

[0181] The unground mixed powder of potassium source and cerium source, iron oxide red equivalent to 48.0 parts of Fe2O3, iron oxide yellow equivalent to 21.49 parts of Fe2O3, ammonium tungstate equivalent to 0.44 parts of WO3, calcium hydroxide equivalent to 0.34 parts of CaO, 0.22 parts of SrO, 3.0 parts of polystyrene microspheres, and 3.17 parts of cement were stirred in a mixer for 1 hour until the mixture was uniform.

[0182] The mixed dry powder was then poured into a kneader, and deionized water accounting for 27.5% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0183] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 778.5 nm and the pore volume was 0.037 cm 3 / g.

[0184] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0185] Comparative Example 3

[0186] The potassium hydroxide equivalent to 8.05 parts was ground with a sand mill at a speed of 200 r / min for 15 min, and the particle size distribution D was measured by Malvern MS3000 laser particle size analyzer. 50K It is 197.6μm.

[0187] Cerium oxalate equivalent to 7.13 parts of CeO2, lanthanum carbonate equivalent to 0.017 parts of La2O3, and 0.007 parts of Sm2O3 were ground in a sand mill at a speed of 700 r / min for 100 min. The particle size distribution D was measured by a Malvern MS3000 laser particle size analyzer. 50IIIB金属 It is 4.01μm.

[0188] The ground potassium source, cerium source and Group IIIB metal source mixed powders were stirred in a mixer for 1 hour until the mixture was uniformly mixed with iron oxide red equivalent to 53.14 parts of Fe2O3, iron oxide yellow equivalent to 23.79 parts of Fe2O3, ammonium metatungstate equivalent to 2.88 parts of WO3, calcium carbonate equivalent to 2.56 parts of CaO, barium carbonate equivalent to 1.3 parts of BaO, ammonium metavanadate equivalent to 0.459 parts of V2O5, 0.401 parts of Nb2O5, 3.0 parts of polystyrene microspheres and 0.27 parts of cement.

[0189] The mixed dry powder was then poured into a kneader, and deionized water accounting for 24.1% of the total weight of the catalyst raw materials was added dropwise and kneaded for 2 hours. After being taken out, it was extruded and pelletized to obtain particles with a diameter of 3 mm and a length of 5-10 mm. The particles were placed in an oven and baked at 100°C for 4 hours and 180°C for 4 hours. Then, the particles were placed in a muffle furnace and calcined at 600°C for 2 hours and 1000°C for 2 hours to obtain the finished catalyst. The catalyst composition is listed in Table 1.

[0190] The median pore diameter of the fresh catalyst after calcination was measured by PASCAL mercury intrusion porosimeter to be 201.4 nm and the pore volume was 0.193 cm 3 / g.

[0191] 100 ml of catalyst was loaded into the reactor and heated at normal pressure and liquid space velocity of 1.0 h －1 The performance evaluation was carried out under the conditions of temperature 630℃ and water ratio 1.15 (wt%). The test results are listed in Table 2.

[0192] Table 1 Weight percentage composition of catalyst

[0193]

[0194]

[0195] If there is any deviation between the above table data and the examples, the table data shall prevail.

[0196] Table 2 Comparison of catalyst performance

[0197]

[0198]

[0199] The above examples and comparative examples illustrate the addition of a certain proportion of at least one Group VB metal oxide (V2O5, Nb2O5, Ta2O5) and at least one Group IIIB metal oxide (Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3, Sm2O3) to an iron-potassium-cerium-tungsten-alkaline earth metal system as additives. Simultaneously, the pore size distribution and pore volume of the catalyst are optimized by adjusting the particle size matching of the K and Ce sources. The catalyst exhibits high catalytic activity at low water ratios and is suitable for industrial dehydrogenation of alkyl aromatics under these conditions.

[0200] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A dehydrogenation catalyst, characterized in that The catalyst comprises the following active components by weight percentage: (a) 63-81% Fe2O3; (b) 7-14% K2O; (c) 6-13% CeO2; (d) 0.1-4% WO3; (e) 0.1-5% alkaline earth metal oxide; (f) 0.05-6% of at least one metal oxide selected from Group VB; (g) 0.01-2% of at least one metal oxide selected from Group IIIB except Ce; The weight ratio of the VB group metal oxide to the IIIB group metal oxide other than Ce is 0.1 to 30; The median pore diameter of the catalyst is 0.2-0.5 μm, and the pore volume is 0.05-0.2 cm 3 / g; The VB group metal oxide is selected from one or more of a mixture of V2O5 and Nb2O5, a mixture of V2O5 and Ta2O5, and a mixture of Nb2O5 and Ta2O5.

2. The catalyst according to claim 1, wherein The catalyst comprises the following components by weight percentage: (a) 64-78% Fe2O3; (b) 8-13% K2O; (c) 7-12% CeO2; (d) 0.2-3% WO3; (e) 0.5-4% alkaline earth metal oxide; (f) 0.1-5% of at least one metal oxide selected from Group VB; (g) 0.05-1.5% of at least one metal oxide selected from Group IIIB except Ce; The weight ratio of the VB group metal oxide to the IIIB group metal oxide is 0.2 to 15.

3. The catalyst according to claim 1 or 2, wherein The VB group metal oxide is a mixture of V2O5, Nb2O5 and Ta2O5; and / or The Group IIIB metal oxide other than Ce is selected from at least one of Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3 and Sm2O3; and / or The alkaline earth metal oxide is at least one of MgO, CaO, SrO and BaO.

4. The catalyst according to claim 3, wherein The Group IIIB metal oxide other than Ce is selected from at least three of Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3 and Sm2O3.

5. The catalyst according to claim 4, wherein The Group IIIB metal oxides other than Ce are selected from at least four of Sc2O3, Y2O3, La2O3, Pr2O3, Nd2O3 and Sm2O3. The catalyst according to claim 1 , wherein The catalyst contains an inorganic binder and / or an organic binder.

7. The catalyst according to claim 6, wherein The selected inorganic binder is derived from one or more of kaolin, diatomaceous earth, cement, silica sol, pseudo-boehmite, potassium silicate, montmorillonite, halloysite, pseudo-halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite; The organic binder is derived from at least one of polyacrylamide, sodium polyacrylate, starch and povidone.

8. The catalyst according to claim 6, wherein Based on the total weight of the catalyst, the binder content is 0.1-3%.

9. The catalyst according to claim 1, wherein The catalyst does not contain molybdenum oxide.

10. The method for preparing the dehydrogenation catalyst according to any one of claims 1 to 9, characterized in that: The method includes: (1) One or more K source dry powders are sequentially ground in a ball mill or a sand mill for first mixing; the grinding speed is controlled at 100-1000 r / min; the grinding time is 1 min-5 h; and the ground K source powder is obtained by screening; (2) Using a ball mill or a sand mill, grind one or more Ce sources and dry powders of group IIIB metal sources other than Ce in sequence, perform a second mixing, control the grinding speed to 50-1000 r / min, and the grinding time to 1 min-3 h; obtain a finely ground mixed powder of Ce source and group IIIB metal source by screening; (3) performing a third mixing of the K source powder, the Ce source and the mixed powder of the Group IIIB metal source with the Fe source, the W source, the alkaline earth metal source, the Group VB metal source, the pore-forming agent and optionally the binder; (4) performing a fourth mixing of the dry powder obtained by the third mixing and the solvent, optionally shaped and then optionally dried and then calcined, in, The particle size distribution of the dry powder K source powder obtained by the first mixing is: 50 K 1-500μm; The particle size distribution of the dry powder Ce source and the IIIB group metal mixed powder obtained by the second mixing is: 50 IIIB金属 0.1-1000μm; D 50 K / D 50 IIIB金属 =0.02-50。 11. The preparation method according to claim 10, wherein The method includes: (1) One or more K source dry powders are sequentially ground in a ball mill or a sand mill for first mixing; the grinding speed is controlled at 200-900 r / min; the grinding time is 15 min-3 h; and the ground K source powder is obtained by screening; (2) Use a ball mill or a sand mill to grind one or more Ce sources and dry powders of group IIIB metal sources other than Ce in sequence, and perform a second mixing. Control the grinding speed at 200-800 r / min and the time for 10 min-2 h. After screening, obtain the ground Ce source and group IIIB metal source mixed powder.

12. The preparation method according to claim 10, wherein The particle size distribution of the dry powder K source powder obtained by the first mixing is: 50 K 5-350μm.

13. The preparation method according to claim 12, wherein The particle size distribution of the dry powder K source powder obtained by the first mixing is: 50 K 10-200μm.

14. The preparation method according to claim 10, wherein The particle size distribution of the dry powder Ce source and the IIIB group metal mixed powder obtained by the second mixing is: 50 IIIB金属 0.5-750μm.

15. The preparation method according to claim 14, wherein The particle size distribution of the dry powder Ce source and the IIIB group metal mixed powder obtained by the second mixing is: 50 IIIB金属 1-500μm.

16. The preparation method according to claim 10, wherein The Fe source is selected from iron oxide red and / or iron oxide yellow; and / or The K source is selected from at least one of potassium carbonate, potassium bicarbonate and potassium hydroxide; and / or The Ce source is selected from at least one of cerium oxide, cerium oxalate, cerium acetate, cerium carbonate, cerium hydroxide and basic cerium carbonate; and / or The W source is selected from at least one of ammonium tungstate, ammonium metatungstate and tungsten trioxide; and / or The alkaline earth metal source is at least one selected from oxides, carbonates, and hydroxides; and / or The VB group metal source is at least one selected from VB group metal oxides, VB group metal hydroxides, VB group metal nitrates, VB group metal metal acid salts, VB group metal oxynitrates and VB group metal acetates; and / or The source of Group IIIB metals other than Ce is selected from at least one of Group IIIB metal oxides, Group IIIB metal hydroxides, Group IIIB metal oxalates, Group IIIB metal acetates, Group IIIB metal nitrates, Group IIIB metal carbonates and Group IIIB metal basic carbonates.

17. The preparation method according to claim 16, wherein The VB group metal source is selected from at least one of VB group metal oxides, VB group metal hydroxides, metal acid salts of VB group metals and VB group metal nitrates.

18. The preparation method according to claim 10, wherein The amount of the pore-forming agent added is 1-6% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source added. The amounts of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source added are all calculated as oxides.

19. The preparation method according to claim 18, wherein The amount of the pore-forming agent added is 2-5% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source added. The amounts of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source, and IIIB group metal source added are all calculated as oxides.

20. The preparation method according to claim 10, wherein The pore-forming agent is selected from at least one of activated carbon, graphite, polystyrene and cellulose and its derivatives, and the cellulose and its derivatives are selected from one or more of methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, carboxymethyl cellulose and microcrystalline cellulose.

21. The preparation method according to claim 10, wherein The amount of the solvent added is 15-35% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group element source and IIIB group metal source except Ce; the amounts of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source and IIIB group metal source added are all calculated as oxides.

22. The preparation method according to claim 21, wherein The amount of the solvent added is 18-30% by weight of the total amount of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group element source and IIIB group metal source except Ce; the amounts of the Fe source, K source, Ce source, W source, alkaline earth metal source, VB group metal source and IIIB group metal source added are all calculated as oxides.

23. The preparation method according to claim 10, wherein The method further comprises shaping the mixed material before the drying.

24. The preparation method according to claim 10, wherein The drying conditions include: a temperature of 30-250° C. and a drying time of 2-24 hours.

25. The preparation method according to claim 24, wherein The drying conditions include: drying at 30-120° C. for 2-24 hours, then heating to 150-200° C. and drying for 2-24 hours.

26. The preparation method according to claim 10, wherein The calcination conditions include: a temperature of 300-1200° C. and a time of 1-12 hours.

27. The preparation method according to claim 26, wherein The calcination conditions include: calcining at 300-700° C. for 1-12 hours, then heating to 800-1200° C. and calcining for 1-12 hours.

28. Use of the dehydrogenation catalyst according to any one of claims 1 to 9 in the dehydrogenation reaction of alkyl aromatic hydrocarbons.

29. The use according to claim 28, wherein The alkyl aromatic hydrocarbon is one or more of ethylbenzene, diethylbenzene, methylethylbenzene, isopropylbenzene and tert-butylethylbenzene.

30. A method for producing alkenyl aromatics by dehydrogenating alkyl aromatics, the method comprising: Under alkyl aromatic hydrocarbon dehydrogenation reaction conditions, the alkyl aromatic hydrocarbon is contacted with the dehydrogenation catalyst according to any one of claims 1 to 9 to carry out the reaction.

31. The method according to claim 30, wherein The alkyl aromatic dehydrogenation reaction conditions include: temperature of 590-630°C, volume space velocity of 0.8-1.5h -1 , the weight ratio of water to alkyl aromatic hydrocarbon is 0.9-1.3, and the pressure is -40kPa to 1.01MPa.

32. The method according to claim 30, wherein The alkyl aromatic hydrocarbon is ethylbenzene.

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