CN116532147A - Spherical non-noble metal propane dehydrogenation catalyst and preparation method and application thereof - Google Patents

Spherical non-noble metal propane dehydrogenation catalyst and preparation method and application thereof Download PDF

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CN116532147A
CN116532147A CN202210090040.4A CN202210090040A CN116532147A CN 116532147 A CN116532147 A CN 116532147A CN 202210090040 A CN202210090040 A CN 202210090040A CN 116532147 A CN116532147 A CN 116532147A
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catalyst
sba
composite carrier
alumina
metal component
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刘红梅
张蓝溪
刘东兵
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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Sinopec Beijing Chemical Research Institute Co ltd
China Petroleum and Chemical Corp
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
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    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
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    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • B01J35/69—Pore distribution bimodal
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • B01J37/20—Sulfiding
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3332—Catalytic processes with metal oxides or metal sulfides
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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    • B01J2229/10—After treatment, characterised by the effect to be obtained
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    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of catalysts, and discloses a spherical non-noble metal propane dehydrogenation catalyst, and a preparation method and application thereof. The catalyst comprises a composite carrier, a metal component and a non-metal component which are loaded on the composite carrier,the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve, and the specific surface area of the composite carrier is 400-900m 2 And/g, wherein the pore volume is 0.4-1.2mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4-7nm and 12-25nm respectively. The spherical non-noble metal propane dehydrogenation catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metals and metal components with serious pollution.

Description

Spherical non-noble metal propane dehydrogenation catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, in particular to a spherical non-noble metal propane dehydrogenation catalyst, and a preparation method and application thereof.
Background
Propylene is an important organic chemical raw material and can be used for producing chemical products such as polypropylene, acrolein, acrylic acid, glycerol, isopropanol, polyacrylonitrile, butanol and octanol. At present, propylene is mainly derived from refinery byproducts and steam cracking co-production. Recently, with the great development of coal chemical industry, the realization of MTP process effectively increases the source of propylene. Even so, the supply gap of propylene is still not complemented. Under the above background, the dehydrogenation of propane to propylene is one of the important ways to increase propylene yield. The propane dehydrogenation technology is mainly classified into direct dehydrogenation and oxidative dehydrogenation, wherein the direct dehydrogenation technology has achieved industrial production in the 90 th century of 20 th. The industrial propane direct dehydrogenation catalysts mainly comprise Cr-based catalysts and Pt-based catalysts. The catalyst used for Cr was a Catofin process developed by Lummes, a Linde process developed by Linde & BASF, and an FBD process developed by Snamprogetti, and the catalyst used for Pt was an Oleflex process developed by UOP and a Star process developed by Phillips. Cr-based catalysts are low in price but easy to deactivate, and heavy metal chromium causes serious environmental pollution. Relatively, pt-based catalysts have high activity, good selectivity and stability, but noble metal platinum is expensive and the catalyst cost is high. Therefore, for various processes for preparing propylene by dehydrogenating propane, the development of a catalyst which does not use nonmetallic components with serious environmental pollution, has higher dehydrogenation catalytic activity and better stability is a main technical problem to be solved at present.
In order to improve various performance indexes of propane dehydrogenation catalysts, researchers have made many efforts to improve Cr-based catalysts and Pt-based catalysts.
The reactivity of the Pt catalyst is improved by a method of modifying an oxide carrier (CN 106607100A, CN 106607099A), the catalyst activity is improved by improving a catalyst preparation method (CN 103418376A, CN 106944081A), the catalytic performance of the Cr catalyst is improved by a method of adding an auxiliary agent (CN 104549220A), and the addition of Cr components is avoided by developing a multicomponent catalyst formula (CN 102451677B, CN 104607168A). Although the prior art improves the Cr-based catalyst for industrial application to a certain extent, the problems of complex catalyst components, complicated preparation process and catalyst performance to be improved still exist. The Cr catalysts currently used in industry are prepared with alumina as a support. The alumina carrier has low price, but the pore canal size distribution is uneven, and the specific surface area is smaller, which is not beneficial to the dispersion of active metal components on the surface of the carrier and the diffusion of raw materials and products in the reaction process.
Therefore, developing a suitable support with excellent performance is an effective way to improve the performance of propane dehydrogenation catalysts.
Disclosure of Invention
The invention aims to overcome the defects of high cost or easiness in causing environmental pollution of a propylene preparation catalyst by propane dehydrogenation in the prior art, and provides a spherical non-noble metal propane dehydrogenation catalyst and a preparation method and application thereof. The spherical non-noble metal propane dehydrogenation catalyst can achieve better propane dehydrogenation activity, propylene selectivity and stability under the condition of not using noble metals and metal components with serious pollution.
In order to achieve the above object, a first aspect of the present invention provides a spherical non-noble metal propane dehydrogenation catalyst, wherein the catalyst comprises a composite support, and a metal component and a non-metal component supported on the composite support, the composite support being packed withComprises alumina and SBA-16 mesoporous molecular sieve, and the specific surface area of the composite carrier is 400-900m 2 And/g, wherein the pore volume is 0.4-1.2mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4-7nm and 12-25nm respectively.
The second aspect of the invention provides a preparation method of a spherical non-noble metal propane dehydrogenation catalyst, wherein the preparation method comprises the following steps:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a metal component precursor and a composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical non-noble metal propane dehydrogenation catalyst.
In a third aspect, the present invention provides a spherical non-noble metal propane dehydrogenation catalyst prepared by the aforementioned preparation method.
The fourth aspect of the invention provides an application of the spherical non-noble metal propane dehydrogenation catalyst in preparing propylene by propane dehydrogenation.
Through the technical scheme, the technical scheme of the invention has the following advantages:
(1) The spherical non-noble metal propane dehydrogenation catalyst does not contain noble metal, so that the preparation cost of the propane dehydrogenation catalyst can be effectively reduced;
(2) The spherical non-noble metal propane dehydrogenation catalyst does not contain chromium element and is environment-friendly;
(3) The spherical non-noble metal propane dehydrogenation catalyst provided by the invention has good catalytic performance when being used for the reaction of preparing propylene by propane dehydrogenation, and has the advantages of high propane conversion rate, high propylene selectivity and good catalyst stability;
(4) The preparation method of the spherical non-noble metal propane dehydrogenation catalyst has the advantages of simple process, easy control of conditions and good product repeatability.
Drawings
FIG. 1 is a photograph of spherical alumina-SBA-16 carrier A prepared in example 1;
FIG. 2 is a pore size distribution diagram of the spherical alumina-SBA-16 carrier A prepared in example 1;
FIG. 3 is a small angle XRD spectrum of spherical alumina-SBA-16 carrier A prepared in example 1;
FIG. 4 is a wide-angle XRD spectrum of spherical alumina-SBA-16 carrier A prepared in example 1.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As described above, the first aspect of the present invention provides a spherical non-noble metal propane dehydrogenation catalyst, wherein the catalyst comprises a composite carrier and a metal component and a non-metal component supported on the composite carrier, the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve, and the specific surface area of the composite carrier is 400-900m 2 And/g, wherein the pore volume is 0.4-1.2mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4-7nm and 12-25nm respectively.
The inventors of the present invention have found when conducting a study of the preparation of a propane dehydrogenation catalyst: in the prior art, the Cr-based catalyst has lower cost than the Pt-based dehydrogenation catalyst, but the Cr-based catalyst has poor stability and serious pollution. Based on this, in order to maintain low catalyst cost while considering environmental requirements, the dehydrogenation catalyst is prepared by using a non-noble metal element instead of Cr in the prior art. The research of the alternative catalyst has been continued for almost twenty years, but the performance of the alternative catalyst still cannot completely reach the level of the Cr-series catalyst, and the performance is mainly represented by low selectivity, poor stability and the like. For the non-noble metal catalyst, if the oxidized metal component is deeply reduced in the reducing atmosphere of the propane dehydrogenation reaction, a pure metal component is easily formed, and the pure metal component has very strong dehydrogenation performance, resulting in deep dehydrogenation or hydrogenolysis of propane, and the selectivity of propylene is severely reduced.
Further, the present inventors have found that, when carrying out a study of preparing a propane dehydrogenation catalyst, the prior art prepares a propane dehydrogenation catalyst by supporting a non-noble metal component with gamma-alumina or silica as a carrier, and has disadvantages of poor propylene selectivity and poor stability. Commercially available alumina carriers or silica carriers are low in cost, but the pore size distribution is uneven, the specific surface area is small, and the dispersion of active metal components on the surface of the carrier and the diffusion of raw materials and products in the reaction process are not facilitated. In comparison, the SBA-16 all-silicon mesoporous molecular sieve material has large specific surface area, large pore volume and uniform pore channel size, and is more beneficial to the diffusion of reactant molecules and product molecules in the reaction. However, SBA-16 all-silicon mesoporous molecular sieve materials have smaller bulk density, and the volume is too large after the catalyst is prepared, so that the industrial application of the catalyst is limited. The inventor of the invention discovers that the structural advantages of alumina and SBA-16 all-silicon mesoporous molecular sieve material are combined, and the spherical alumina-SBA-16 carrier is prepared by a specific molding method, and the propane dehydrogenation catalyst with excellent performance can be obtained after loading non-noble metal active components.
Further, the inventors of the present invention found that: if the non-noble metal catalyst is subjected to sulfuration treatment, the S element exists on the surface of the catalyst, and the S element can be combined with the active metal component to generate sulfide in the reducing atmosphere of the propane dehydrogenation reaction. The existence of the non-noble metal sulfide can effectively avoid the deep reduction of the metal component, thereby reducing the pure metal component on the surface of the catalyst and obviously inhibiting the occurrence of side reactions such as hydrogenolysis and the like. The selectivity and stability of the dehydrogenation catalyst after vulcanization treatment in the reaction of preparing propylene by propane dehydrogenation are obviously improved. For the non-noble metal propane dehydrogenation catalyst, the S element content on the surface of the non-noble metal propane dehydrogenation catalyst has a remarkable influence on the performance of the catalyst. If the S content is too low, the protection effect on the active metal component is limited, and the partial oxidation state metal component is still completely reduced to a pure metal state in the reaction process; if the S content is too high, the "oxidation-reduction" cycle rate of the active sites of the catalyst is slowed, resulting in a slow reaction rate, which is manifested as lower catalyst activity.
According to the present invention, the composite support preferably has a specific surface area of 450 to 800m 2 The pore volume is 0.5-1.0mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4.5-6.5nm and 14-20nm respectively; more preferably, the specific surface area of the composite carrier is 516-628m 2 The pore volume is 0.6-0.8mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 5.2-6.3nm and 15-18nm respectively;
according to the invention, the content of the alumina is 55-75 wt% based on the total weight of the composite carrier, and the content of the SBA-16 mesoporous molecular sieve is 25-45 wt%; preferably, the content of the alumina is 58.3 to 69.5 weight percent and the content of the SBA-16 mesoporous molecular sieve is 30.5 to 41.7 weight percent based on the total weight of the composite carrier.
According to the present invention, the metal component element is selected from one or more of iron, nickel, zinc, tungsten, tin, manganese, molybdenum and copper; preferably, the metal component element is selected from one or more of iron, nickel, zinc, tungsten and tin; more preferably, the metal component element is selected from one or more of iron, nickel and zinc.
According to the invention, the nonmetallic component is an S element.
According to the invention, the content of the metal component is 3-30 wt%, the content of the nonmetal component is 0.1-3 wt% and the content of the composite carrier is 67-97 wt%, based on the total weight of the catalyst; preferably, the content of the metal component is 5-20 wt%, the content of the nonmetal component is 0.2-1.5 wt%, and the content of the composite carrier is 79-95 wt%, based on the total weight of the catalyst; more preferably, the metal component is present in an amount of 7.9 to 18.4 wt%, the non-metal component is present in an amount of 0.5 to 1.2 wt%, and the composite support is present in an amount of 80.4 to 91.6 wt%, based on the total weight of the catalyst. In the invention, the contents of the metal component, the nonmetal component and the composite carrier (spherical alumina-SBA-16 carrier) are limited to be within the range, so that the uniform dispersion of the active components of the catalyst can be ensured, and the pore channel structure is beneficial to the diffusion of reactants and products.
According to the invention, the preparation method of the composite carrier comprises the following steps:
(1) Contacting and mixing an alumina precursor, an SBA-16 mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and performing pellet preparation on the obtained mixture to obtain a spherical alumina-SBA-16 precursor;
(2) And drying and roasting the spherical alumina-SBA-16 precursor to obtain the composite carrier.
According to the invention, the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, alumina sol, gibbsite and boehmite; preferably pseudo-boehmite.
According to the present invention, the pseudo-boehmite may be commercially available or prepared, and in the present invention, specifically, the pseudo-boehmite comprises: german original imported pseudo-boehmite powder (available from Beijing Asia Taiao chemical auxiliary agent Co., ltd., specific surface area of 241 m) 2 Per gram, pore volume of 0.53cm 3 Per g), pseudo-boehmite powder (model P-DF-09-LSi, manufactured by Shandong aluminum company Limited liability company, having a specific surface area of 286m 2 Per gram, pore volume of 1.08cm 3 Per g) and macroporous pseudo-boehmite powder (manufactured by Zibo constant Ji Fen New Material Co., ltd., specific surface area: 327 m) of type PB-0101 2 Per gram, pore volume of 1.02cm 3 /g).
According to the invention, the SBA-16 mesoporous molecular sieve can be a self-made SBA-16 mesoporous molecular sieve, and preferably, the specific surface area of the SBA-16 mesoporous molecular sieve is 600-1000m 2 Per gram, pore volume of 0.4-1.0cm 3 /g, average pore size of 5-8nm; more preferably, the specific surface area of the SBA-16 mesoporous molecular sieve is 700-900m 2 Per gram, pore volume of 0.5-0.8cm 3 And/g, the average pore diameter is 5.5-7.5nm.
In one embodiment of the present invention, the preparation of the SBA-16 mesoporous molecular sieve comprises:
uniformly mixing a template agent, an acidic aqueous solution, n-butanol and chitosan, and adding a silicon source; standing for crystallization after the contact reaction; separating to obtain a solid product; and washing, drying and roasting the solid product to obtain the SBA-16 all-silicon mesoporous molecular sieve.
In the preparation method of the SBA-16 mesoporous molecular sieve, the template agent can be an amphoteric triblock polymer, preferably F127 (polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer with a molecular formula of EO106PO70EO 106).
According to the preparation method of the SBA-16 mesoporous molecular sieve, the acidic aqueous solution can be an inorganic acid aqueous solution, preferably one or more of dilute hydrochloric acid or dilute nitric acid, and more preferably dilute hydrochloric acid; the concentration of the acidic aqueous solution may be 0.2 to 10%, preferably 0.5 to 3%.
The silicon source can be organic silicon-containing compound or inorganic silicon-containing compound, preferably one or more of methyl orthosilicate, ethyl orthosilicate, isopropyl orthosilicate or silica sol, and more preferably ethyl orthosilicate.
The invention discloses a preparation method of an SBA-16 mesoporous molecular sieve, which comprises the following steps: acidic aqueous solution: n-butanol: chitosan: the weight ratio of the silicon source may be 1: (10-200): (0.2-10): (0.05-1.0): (1-8), preferably 1: (20-100): (0.5-3): (0.1-0.5): (2-4).
The preparation method of the SBA-16 mesoporous molecular sieve comprises the following steps: the stirring speed is 50-300r/min, the temperature is 20-60 ℃ and the time is 0.5-6h; preferably, the stirring speed is 150-250r/min, the temperature is 20-40 ℃ and the time is 0.5-3h.
In the preparation method of the SBA-16 mesoporous molecular sieve, the condition of the contact reaction can be 50-150 ℃, preferably 80-120 ℃; the time is 3-40h, preferably 10-20h.
According to the preparation method of the SBA-16 mesoporous molecular sieve, the standing crystallization condition can be 50-150 ℃, and the preferable temperature is 80-120 ℃; the time is 10-48 hours, preferably 16-30 hours.
The preparation method of the SBA-16 mesoporous molecular sieve has no special requirement in the solid-liquid two-phase separation process, and can be a separation mode known in the art, including gravity filtration, pressure filtration, vacuum filtration or centrifugal filtration. Preferably, the separation process specifically includes: vacuum-pumping the bottom of the funnel by using a suction bottle or filtering by using a centrifugal filter.
The method for preparing the SBA-16 mesoporous molecular sieve in the invention is not particularly required, and the method for washing the solid product is as follows: the solid product may be washed with deionized water, the volume ratio of deionized water to solid product may be 5-20, and the number of washes may be 2-8.
According to the preparation method of the SBA-16 mesoporous molecular sieve, the drying condition can be at 80-150 ℃, preferably 100-130 ℃; the time is 2-30 hours, preferably 5-20 hours.
According to the preparation method of the SBA-16 mesoporous molecular sieve, the roasting condition can be 400-700 ℃, and the preferable temperature is 500-600 ℃; the time is 2-24 hours, preferably 4-12 hours.
According to the present invention, the acidic aqueous solution may be an aqueous organic acid solution or an aqueous inorganic acid solution, preferably, the acidic aqueous solution is one or more selected from an aqueous formic acid solution, an aqueous acetic acid solution, an aqueous citric acid solution, an aqueous nitric acid solution and an aqueous hydrochloric acid solution, more preferably, the acidic aqueous solution is an aqueous nitric acid solution or an aqueous citric acid solution; in the present invention, the mass concentration of the acidic aqueous solution is 1 to 20%, preferably 2 to 10%.
According to the invention, the extrusion aid is selected from one or more of sesbania powder, polyethylene glycol, polyvinyl alcohol, polyacrylamide and cellulose; preferably, the auxiliary agent is sesbania powder.
According to the invention, the weight ratio of the alumina precursor, the SBA-16 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.2-1): (0.02-0.5): (0.2-5); preferably, the weight ratio of the alumina precursor, the SBA-16 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.3-0.5): (0.07-0.12): (0.6-0.8).
According to the present invention, in step (1), an alumina precursor, the SBA-16 mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid are contacted and mixed, and the mixing conditions include: the stirring speed is 50-300r/min, the temperature is 20-60 ℃ and the time is 0.5-6h; preferably, the stirring speed is 150-250r/min, the temperature is 20-40 ℃ and the time is 0.5-1h.
According to the present invention, in step (2), the drying conditions include: the temperature is 70-150 ℃ and the time is 3-24 hours; preferably, the temperature is 100-130 ℃ and the time is 6-12h.
According to the present invention, in step (2), the conditions of the firing include: the temperature is 400-700 ℃ and the time is 2-30h; preferably, the temperature is 550-700 ℃ and the time is 12-15h.
According to the present invention, in step (1), the method of pelleting the pellets comprises:
(1-1) extruding the mixture into strips, and then cutting and extruding into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard spheres to obtain spherical precursors.
According to the invention, in the step (1-1), after uniformly mixing an alumina precursor, the SBA-16 mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, transferring the obtained mixture into a miniature ball making machine to extrude a strip with a circular section, and then extruding the strip into raw material balls after cutting; wherein the conditions of extrusion into a strip include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm; the conditions of the cutting include: the cutting speed is 100-3500 grains/min.
According to the invention, in the step (1-2), the raw material balls are put into a pellet shaper for shaping, so that the raw material balls become standard spherical balls; wherein the shaping conditions include: the rounding time is 0.5-10 min/time, the number of times of rounding is 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min.
According to the invention, in step (1-3), the standard spheres are placed in a pellet screening machine to screen out spherical precursors of suitable size.
The second aspect of the invention provides a preparation method of a spherical non-noble metal propane dehydrogenation catalyst, wherein the preparation method comprises the following steps:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a metal component precursor and a composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical non-noble metal propane dehydrogenation catalyst.
The inventor of the invention also discovers that an ultrasonic auxiliary method is introduced in the preparation process of the spherical non-noble metal propane dehydrogenation catalyst, so that active components can be promoted to be better dispersed on the surface of the spherical alumina-SBA-16 carrier, and further the propane dehydrogenation catalyst with better catalytic activity can be obtained.
According to the invention, the ultrasound-assisted conditions include: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W; preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
According to the invention, the solution containing the metal component precursor is an aqueous solution or an ethanol solution containing the metal component precursor; preferably, the mass concentration of the solution containing the metal component precursor is 0.5-10%.
According to the invention, the metal component precursor is selected from one or more of nitrate, sulfite or metal chloride containing iron, nickel, zinc, tungsten, tin, manganese, molybdenum, copper.
According to the present invention, in step (Z1), the contact reaction conditions include: the temperature is 20-100deg.C, preferably 40-80deg.C; the time is 0.5-10h, preferably 2-8h.
The method for removing the solvent according to the present invention is not particularly limited, and may be a method known in the art, such as: the solvent is removed by evaporation using a rotary evaporator or by heating and stirring.
According to the present invention, the conditions for drying are not particularly limited, and may be conventional conditions in the art. Preferably, the drying conditions include: the temperature is 60-150deg.C, preferably 80-130deg.C; the time is 1-20h, preferably 3-15h.
According to the invention, the conditions of the calcination include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15 hours, preferably 3-10 hours.
According to the invention, the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide; the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1 to 5% by volume, preferably 0.3 to 2% by volume.
According to the present invention, in step (Z2), the vulcanization treatment conditions include: the temperature is 400-700 ℃ and the time is 1-15h; preferably, the processing conditions include: the temperature is 450-650 ℃ and the time is 2-8h.
In a third aspect, the present invention provides a spherical non-noble metal propane dehydrogenation catalyst prepared by the aforementioned preparation method.
The fourth aspect of the invention provides an application of the spherical non-noble metal propane dehydrogenation catalyst in preparing propylene by propane dehydrogenation.
According to the invention, the reaction comprises: and (3) contacting the reaction raw material propane with the spherical non-noble metal propane dehydrogenation catalyst to react.
According to the invention, the conditions of the contact include: the contact temperature can be 550-650 ℃, the partial pressure of raw material gas is 0.02-0.5MPa, and the mass airspeed of propane is 1.0-10.0h -1 。
In the following examples and comparative examples:
the pore structure parameter analysis of the samples was performed on an ASAP2020-M+C type adsorber available from Micromeritics, inc. Vacuum degassing for 4 hours at 350 ℃ before sample measurement, calculating the specific surface area of the sample by adopting a BET method, and calculating the pore volume by adopting a BJH model;
elemental analysis experiments of the samples were performed on an Eagle III energy dispersive X-ray fluorescence spectrometer manufactured by EDAX corporation, USA;
the ultrasonic generator is a KQ-300GTDV high-frequency constant-temperature numerical control ultrasonic cleaner manufactured by Kunshan ultrasonic instrument Co., ltd, the ultrasonic frequency is 80kHz, and the working voltage is 220V;
the rotary evaporator is manufactured by IKA corporation in Germany, and the model is RV10 digital;
the drying oven is manufactured by Shanghai-Heng scientific instrument Co., ltd, and the model is DHG-9030A.
The muffle furnace is available from CARBOLITE company under the model CWF1100.
The kneader is an FN-NH2 kneader manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the miniature ball making machine is a HWJ-100 miniature ball making machine manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the pellet shaper is an FN-XZXJ pellet shaper manufactured by Tianshuihua round pharmaceutical equipment science and technology Co., ltd; the micropill screening machine is SWP-1200 micropill screening machine produced by Tianshuihua round pharmaceutical equipment science and technology Co.
F127 was purchased from Acros reagent company. The other reagents used in the examples and comparative examples were purchased from national pharmaceutical chemicals, inc., and the purity of the reagents was analytically pure.
The calculation method of the propane conversion rate is as follows:
propane conversion = amount of propane consumed by the reaction/initial amount of propane x 100%;
the propylene selectivity was calculated as follows:
propylene selectivity = amount of propane consumed to produce propylene/total amount of propane consumed x 100%.
Example 1
This example is intended to illustrate a spherical non-noble metal propane dehydrogenation catalyst prepared in accordance with the present invention.
(1) Preparation of spherical alumina-SBA-16 carrier
1) Preparation of SBA-16 mesoporous molecular sieve
In a 1000mL round bottom flask, 10g of polyether F127, 20g of concentrated hydrochloric acid and 500mL of deionized water are added, mixed and stirred for 30min; continuously adding 15g of n-butanol and 2g of chitosan into the flask, and stirring for 1h; slowly adding 25g of ethyl orthosilicate, heating to 100 ℃, stirring and crystallizing for 16 hours, and standing and crystallizing for 24 hours at 100 ℃. After crystallization, filtering to obtain a white solid product, washing with deionized water for 8 times, drying in air at 120 ℃ for 10 hours, and roasting at 550 ℃ for 8 hours to obtain the SBA-16 mesoporous molecular sieve.
The specific surface area of the SBA-16 mesoporous molecular sieve is 794m 2 Per gram, pore volume of 0.65cm 3 And/g, average pore diameter of 6.5nm.
2) Preparation of spherical alumina-SBA-16 carrier
120g of pseudo-boehmite powder with the model of P-DF-09-LSi, 60g of SBA-16 mesoporous molecular sieve, 85g of dilute nitric acid with the concentration of 5 percent and 10g of sesbania powder are mixed, transferred into a kneader and stirred and mixed uniformly. The kneading temperature was 35℃and the main shaft rotation speed of the kneader was 150r/min, and the kneading time was 1h. Putting the uniformly mixed raw materials into a hopper of a miniature ball making machine, selecting a strip extruding die with the aperture of 1.8mm, adjusting the strip extruding speed to be 2m/min and the cutting speed to be 1200 grains/min, extruding the raw materials into strips, and extruding and cutting the strips into round small grains. Putting the round small particles into a pellet shaper for shaping, wherein shaping conditions are as follows: the rounding time is 3 min/time, the rounding time is 3 times, and the rotating speed of the sample cavity is 300r/min. And (5) placing the shaped standard spherical raw material balls into a pellet screening machine to screen out spherical precursors with the size of 1.7 mm. Drying the spherical precursor at 110 ℃ for 8 hours, and roasting at 600 ℃ for 15 hours to obtain the spherical alumina-SBA-16 carrier A.
The spherical alumina-SBA-16 support A was characterized and its structural parameters are shown in Table 1.
FIG. 1 is a photograph of a spherical alumina-SBA-16 carrier A. As can be seen from FIG. 1, the carrier has the appearance of white spheres, good sphericity, smooth sphere and uniform particle size.
FIG. 2 is a pore size distribution diagram of spherical alumina-SBA-16 carrier A. The pore diameter of the sample is in bimodal distribution, the first most probable pore diameter is 5.8nm, and the contribution of the SBA-16 mesoporous molecular sieve is mainly generated; the second most probable pore size is 16.5nm, contributed mainly by alumina.
FIG. 3 is a small angle XRD spectrum of spherical alumina-SBA-16 carrier A prepared in example 1; as can be seen from fig. 3: the sample shows a stronger diffraction peak at the 2 theta=0.78° position, a characteristic diffraction peak belonging to the (110) crystal plane, and a weaker diffraction peak at the 2 theta=1.2° position, a characteristic diffraction peak belonging to the (200) crystal plane. This shows that the SBA-16 molecular sieve in the spherical alumina-SBA-16 carrier A has a better Im3m type body-centered cubic mesoporous structure. After the alumina precursor is mixed, molded and baked, diffraction peaks corresponding to the mesoporous structure are still obvious, which indicates that the Im3m type body-centered cubic mesoporous structure of the SBA-16 molecular sieve is not changed in the molding process, and the order of the pore space structure is still high.
FIG. 4 is a wide-angle XRD spectrum of spherical alumina-SBA-16 carrier A prepared in example 1; the XRD wide-angle diffraction pattern of the spherical alumina-SBA-16 carrier A is identical to that of alumina, because the structure of SBA-16 mesoporous molecular sieve has no diffraction signal in the wide-angle part. The x-ray diffraction angles are mainly: 2θ=37.1 °, 39.3 °, 46.1 °, 60.7 °, and 66.6 °, these five diffraction signals are associated with γ -Al 2 O 3 The diffraction patterns are identical, which shows that the spherical alumina-SBA-16 carrier A shows typical gamma-Al after being dehydrated by pseudo-boehmite with the model of P-DF-09-LSi after being roasted at 600 DEG C 2 O 3 A crystalline phase. In addition, XRD signals of the spherical alumina-SBA-16 carrier A were not shown in one figure, nor were they detected by the same characterization means. The XRD patterns given in the present invention are two, one wide angle and one small angle.
(2) Preparation of spherical non-noble metal propane dehydrogenation catalyst
10.8g of ferric nitrate nonahydrate are dissolved in 100g of deionized water, mixed with 10g of spherical alumina-SBA-16 carrier A and reacted for 60min at 50 ℃ under stirring with the aid of ultrasonic waves with the power of 200W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then, the mixture was calcined in a muffle furnace at 550℃for 5 hours to obtain an initial catalyst A.
10g of the initial catalyst A was taken and used in H 2 S containsThe mixture was treated at 550℃for 3 hours in a nitrogen stream at an amount of 1.5% to obtain a spherical non-noble metal propane dehydrogenation catalyst A.
The specific gravity of each component of the spherical non-noble metal propane dehydrogenation catalyst A is as follows: 13.6% by weight of elemental iron (based on metallic iron content), 0.8% by weight of elemental sulfur, the remainder being a carrier.
The composition and structural parameters of catalyst a are listed in table 2.
(3) Performance evaluation of catalyst in propylene preparation reaction by propane dehydrogenation
The reactivity of the catalyst was evaluated on a fixed bed reactor. 5.0 g of catalyst A is filled in a fixed bed quartz reactor, the reaction temperature is controlled to be 600 ℃, the reaction pressure is controlled to be 0.1MPa, and propane: the molar ratio of helium is 1:1, propane mass space velocity of 5.0h -1 The reaction time was 6h. Through Al 2 O 3 The reaction product separated by the S molecular sieve column was directly fed to an agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis. The results of the reaction evaluation are shown in Table 3.
Examples 2 to 3
This example is intended to illustrate a spherical non-noble metal propane dehydrogenation catalyst prepared in accordance with the present invention.
Spherical non-noble metal propane dehydrogenation catalysts B and C were prepared in the same manner as in example 1, wherein the SBA-16 mesoporous molecular sieve prepared in the same manner as in step (1) of example 1 was used, except that:
examples 2-3 were conducted by varying the parameters during the preparation of the spherical alumina-SBA-16 support of step (1) of example 1, to obtain spherical alumina-SBA-16 supports B and C, respectively. The structural parameters of the spherical alumina-SBA-16 supports B and C are listed in Table 1.
The parameters during the preparation of the catalyst in step (2) of example 1 were changed to carry out examples 2 to 3, to obtain catalysts B and C, respectively. The preparation conditions, composition and structural parameters of catalysts B and C are listed in table 2.
The propylene preparation reaction performance test of catalysts B and C by propane dehydrogenation was performed in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Examples 4 to 7
This example is intended to illustrate a spherical non-noble metal propane dehydrogenation catalyst prepared in accordance with the present invention.
Spherical alumina-SBA-16 carrier A was prepared by the method of step (1) of example 1, and each of the parameters during the catalyst preparation in step (2) of example 1 was changed to carry out examples 4 to 7, to obtain catalysts D, E, F and G, respectively. The preparation conditions, composition and structural parameters of catalysts D, E, F and G are listed in table 2.
The reaction performance test of catalysts D, E, F and G for propylene production by propane dehydrogenation was performed in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 1
This comparative example is to illustrate the differences in vectors.
Step (1) in example 1 was omitted and catalyst D1 was prepared in the same manner as in step (2) in example 1 except that "alumina" was used as the catalyst support instead of "spherical alumina-SBA-16 support A"; wherein the specific surface area of the commercial alumina is 224m 2 Per gram, the pore volume was 0.69ml/g, the average particle diameter was 1.5mm, and the particle crush strength was 12.6N.
The content of metallic element iron was 13.6 wt%, the content of S was 0.8 wt% based on the total weight of the catalyst D1, and the balance was alumina as a support.
The propylene preparation reaction performance test of catalyst D1 by propane dehydrogenation was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 2
This comparative example is to illustrate the different preparation conditions-different catalyst components.
Spherical alumina-SBA-16 carrier A was prepared by the method of step (1) in example 1. Catalyst D2 was prepared according to the procedure of step (2) in example 1, and the catalyst preparation conditions, specifically:
1.8g of ferric nitrate nonahydrate was dissolved in 100g of deionized water, mixed with 10g of spherical alumina-SBA-16 carrier A, and reacted for 60 minutes with stirring at 50℃under the assistance of ultrasonic waves having a power of 200W. After the reaction is finished, water in the system is distilled off by a rotary evaporator, and a solid product is obtained. The solid product was placed in a drying oven at 110℃and dried for 6 hours. Then, the mixture was calcined in a muffle furnace at 550℃for 5 hours to obtain an initial catalyst D2.
10g of the initial catalyst D2 were taken and reacted in H 2 And (3) treating the mixture in a nitrogen gas stream with the S content of 1.5% at 600 ℃ for 15 hours to obtain the spherical non-noble metal propane dehydrogenation catalyst D2.
So that the content of metallic element iron was 2.3 wt.%, the content of S was 3.2 wt.%, and the rest was a carrier, based on the total weight of the catalyst D2.
The propylene preparation reaction performance test of catalyst D2 by propane dehydrogenation was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 3
This comparative example is intended to illustrate a vulcanization-free treatment process.
Spherical alumina-SBA-16 carrier A was prepared by the method of step (1) in example 1. Catalyst D3 was prepared by the method of step (2) in example 1, and the sulfiding treatment of the initial catalyst was omitted so that the content of elemental iron was 13.6% by weight based on the total weight of catalyst D3, with the remainder being the carrier.
The propylene preparation reaction performance test of catalyst D3 by propane dehydrogenation was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 3.
Comparative example 4
This comparative example is to illustrate the differences in vectors.
A spherical propane dehydrogenation catalyst was prepared in the same manner as in example 1 except that: catalyst D4 was prepared by the method of step (2) in example 1, except that "SBA-16 mesoporous molecular sieve" was used as the catalyst support instead of "spherical alumina-SBA-16 support A" except that step (1) in example 1 was omitted; wherein, the specific surface area of the SBA-16 mesoporous molecular sieve is 794m 2 Per gram, pore volume of 0.65cm 3 And/g, average pore diameter of 6.5nm.
13.6% by weight of elemental iron (based on the metallic iron content), 0.8% by weight of elemental sulfur, the remainder being the carrier, based on the total weight of catalyst D4.
The reaction performance of catalyst D4 was evaluated in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
Comparative example 5
This comparative example is to illustrate the difference in component content in the composite carrier.
A spherical propane dehydrogenation catalyst was prepared in the same manner as in example 1 except that: in the preparation of the spherical alumina-SBA-16 carrier, 120g of pseudo-boehmite powder with the model of P-DF-09-LSi, 60g of SBA-16 mesoporous molecular sieve, 85g of dilute nitric acid with the concentration of 5 percent and 10g of sesbania powder are mixed, 45g of pseudo-boehmite powder with the model of P-DF-09-LSi is replaced by the mixture of 45g of pseudo-boehmite powder with the model of P-DF-09-LSi, 70g of SBA-16 mesoporous molecular sieve, 60g of dilute nitric acid with the concentration of 5 percent and 7g of sesbania powder; spherical alumina-SBA-16 carrier D5 is prepared.
As a result, the content of elemental iron (based on the metal iron content) was 31.0% by weight and the content of SBA-16 mesoporous molecular sieve was 69.0% by weight, based on the total weight of the spherical alumina-SBA-16 carrier D5.
Wherein the specific surface area of the spherical alumina-SBA-16 carrier D5 is 651m 2 Per gram, pore volume was 0.7ml/g.
Catalyst D5 was prepared according to the procedure of step (2) in example 1.
13.6% by weight of elemental iron (based on the metallic iron content), 0.8% by weight of elemental sulfur, the remainder being the carrier, based on the total weight of catalyst D5.
The propylene preparation reaction performance test of catalyst D5 by propylene dehydrogenation was carried out in the same manner as in step (3) of example 1, and the reaction results are shown in Table 2.
TABLE 1
TABLE 2
Table 2 (subsequent)
TABLE 3 Table 3
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As can be seen from table 3:
(1) The spherical non-noble metal propane dehydrogenation catalyst prepared by the method has excellent performance when being used for the reaction of preparing propylene by propane dehydrogenation.
(2) As a result of experiments of comparative example 1 and comparative example 1, it was found that the catalyst A prepared using the spherical alumina-SBA-16 carrier had significantly improved properties over the catalyst D1 prepared using alumina as a carrier, and that the conversion of propane, the selectivity of propylene, and the stability of the catalyst were significantly improved. The above results demonstrate that the spherical alumina-SBA-16 support is more favorable for the reaction of preparing propylene by dehydrogenating propane.
(3) The results of experiments in comparative example 1 and comparative example 2 revealed that the D2 catalyst having the contents of the components not within the ranges of the claims was inferior in performance (propane conversion, propylene selectivity and catalyst stability), indicating that the propane dehydrogenation catalyst excellent in performance could be obtained only in a certain content range of the active components and the auxiliary agent supported on the carrier.
(4) The experimental results of the comparative example 1 and the comparative example 3 show that the performance of the catalyst A after the vulcanization treatment is obviously better than that of the catalyst D3 without sulfur, and the conversion rate of propane and the selectivity of propylene are obviously improved; the performance of catalyst a was hardly degraded during the 6 hours reaction, while the propane conversion and propylene selectivity of the D3 catalyst were significantly degraded. The above results demonstrate that the presence of the S element on the catalyst surface can effectively improve the dehydrogenation activity of the catalyst, the selectivity of the target olefin, and the stability of the catalyst.
(5) The experimental results of comparative example 1 and comparative example 4 revealed that the catalyst could not be industrially applied regardless of the catalyst performance by using the SBA-16 mesoporous molecular sieve instead of the spherical alumina-SBA-16 carrier A as the catalyst carrier. Because the SBA-16 mesoporous molecular sieve is powder, the molding can not be carried out without the help of a binder. The catalysts used in industry are all shaped samples.
(6) As a result of experiments in comparative examples 1 and 5, it was found that the ratio of alumina to SBA-16 mesoporous molecular sieve in the spherical alumina-SBA-16 carrier D5 was not within the range specifically defined in the present invention, and the shape of the prepared molded carrier was not regular enough and the dispersion of the internal components was not uniform enough. The uniform dispersion of the active ingredient is also affected after the active ingredient is supported as a carrier. Therefore, the performance of catalyst D5 is inferior to that of catalyst a.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims (14)

1. A spherical non-noble metal propane dehydrogenation catalyst is characterized by comprising a composite carrier, a metal component and a non-metal component which are supported on the composite carrier, wherein the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve, and the specific surface area of the composite carrier is 400-900m 2 And/g, wherein the pore volume is 0.4-1.2mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4-7nm and 12-25nm respectively.
2. The catalyst according to claim 1, wherein the specific surface area of the composite carrier is 450-800m 2 The pore volume is 0.5-1.0mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 4.5-6.5nm and 14-20nm respectively;
preferably, the specific surface area of the composite carrier is 516-628m 2 The pore volume is 0.6-0.8mL/g, the pore size distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 5.2-6.3nm and 15-18nm respectively;
and/or, based on the total weight of the composite carrier, the content of the alumina is 55-75 wt%, and the content of the SBA-16 mesoporous molecular sieve is 25-45 wt%;
preferably, the content of the alumina is 58.3 to 69.5 weight percent and the content of the SBA-16 mesoporous molecular sieve is 30.5 to 41.7 weight percent based on the total weight of the composite carrier.
3. The catalyst according to claim 1 or 2, wherein the metal component element is selected from one or more of iron, nickel, zinc, tungsten, tin, manganese, molybdenum and copper;
and/or, the nonmetallic component is S element.
4. A catalyst according to any one of claims 1 to 3, wherein the metal component is present in an amount of 3 to 30% by weight, the non-metal component is present in an amount of 0.1 to 3% by weight, and the composite support is present in an amount of 67 to 97% by weight, based on the total weight of the catalyst;
preferably, the content of the metal component is 5-20 wt%, the content of the nonmetal component is 0.2-1.5 wt%, and the content of the composite carrier is 79-95 wt%, based on the total weight of the catalyst;
more preferably, the metal component is present in an amount of 7.9 to 18.4 wt%, the non-metal component is present in an amount of 0.5 to 1.2 wt%, and the composite support is present in an amount of 80.4 to 91.6 wt%, based on the total weight of the catalyst.
5. The catalyst according to any one of claims 1 to 4, wherein the preparation method of the composite carrier comprises:
(1) Contacting and mixing an alumina precursor, an SBA-16 mesoporous molecular sieve, an acidic aqueous solution and an extrusion aid, and performing pellet preparation on the obtained mixture to obtain a spherical alumina-SBA-16 precursor;
(2) And drying and roasting the spherical alumina-SBA-16 precursor to obtain the composite carrier.
6. The catalyst of claim 5, wherein the alumina precursor is selected from one or more of pseudo-boehmite, aluminum hydroxide gel, aluminum sol, gibbsite, and boehmite;
and/or the weight ratio of the alumina precursor, the SBA-16 mesoporous molecular sieve, the extrusion aid and the acidic aqueous solution is 1: (0.2-1): (0.02-0.5): (0.2-5).
7. The catalyst of claim 5, wherein the method of pelletizing the pellets comprises:
(1-1) extruding the mixture into strips, and then cutting and extruding into raw material balls;
(1-2) shaping the raw material ball to obtain a standard ball;
(1-3) screening the standard spheres to obtain spherical precursors.
8. The catalyst of claim 5, wherein the extrusion conditions include: the extrusion speed is 0.5-5m/min, and the diameter of the circular section of the strip is 1.5-5.0mm;
and/or, the conditions of the cutting include: the cutting speed is 100-3500 grains/min;
and/or, the shaping conditions include: the rounding time is 0.5-10 min/time, the number of times of rounding is 1-5 times, and the rotating speed of the sample cavity is 50-1400r/min.
9. The preparation method of the spherical non-noble metal propane dehydrogenation catalyst is characterized by comprising the following steps of:
(Z1) under the ultrasonic auxiliary condition, carrying out contact reaction on a solution containing a metal component precursor and a composite carrier, and removing a solvent, drying and roasting to obtain an initial catalyst; wherein the composite carrier comprises alumina and SBA-16 mesoporous molecular sieve;
(Z2) vulcanizing the initial catalyst by sulfur-containing gas to obtain the spherical non-noble metal propane dehydrogenation catalyst.
10. The method of preparation of claim 9, wherein the ultrasound-assisted conditions comprise: the temperature is 10-100deg.C, the time is 10-180min, and the power is 100-300W;
preferably, the ultrasound-assisted conditions include: the temperature is 20-80 ℃, the time is 30-120min, and the power is 150-250W.
11. The production method according to claim 9, wherein the solution containing the metal component precursor is an aqueous solution or an ethanol solution containing the metal component precursor;
preferably, the metal component precursor is selected from one or more of nitrate, sulfite or metal chloride containing iron, nickel, zinc, tungsten, tin, manganese, molybdenum, copper.
12. The production method according to claim 9, wherein the sulfur-containing gas is nitrogen, helium or argon containing hydrogen sulfide;
and/or the volume content of the hydrogen sulfide in the sulfur-containing gas is 0.1 to 5% by volume, preferably 0.3 to 2% by volume;
and/or, in step (Z1), the conditions of the firing include: the temperature is 400-700 ℃, preferably 500-650 ℃; the time is 2-15h, preferably 3-10h;
and/or, in step (Z1), the contacting reaction conditions include: the temperature is 20-100 ℃ and the time is 0.5-10h;
and/or, in step (Z2), the vulcanization treatment conditions include: the temperature is 400-700 ℃ and the time is 1-15h; preferably, the processing conditions include: the temperature is 450-650 ℃ and the time is 2-8h.
13. A spherical non-noble metal propane dehydrogenation catalyst prepared by the preparation method of any one of claims 9 to 13.
14. Use of a spherical non-noble metal propane dehydrogenation catalyst according to any one of claims 1-8 in the production of propylene by dehydrogenation of propane.
CN202210090040.4A 2022-01-25 2022-01-25 Spherical non-noble metal propane dehydrogenation catalyst and preparation method and application thereof Pending CN116532147A (en)

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