CN110496633B - Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation - Google Patents
Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 78
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title description 24
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- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 claims description 2
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/0316—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing iron group metals, noble metals or copper
- B01J29/0325—Noble metals
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- B01J35/615—
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- B01J35/635—
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- B01J35/643—
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- B01J35/647—
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- 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
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/03—Catalysts comprising molecular sieves not having base-exchange properties
Abstract
The invention relates to the field of catalysts, and discloses a method for preparing an isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation. The method for preparing the isobutane dehydrogenation catalyst comprises the following steps: (a) preparing a filter cake of the mesoporous molecular sieve; (b) preparing a silica gel filter cake; (c) mixing the mesoporous molecular sieve filter cake and the silica gel filter cake, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling with water, performing spray drying, and removing the template agent in the obtained product to obtain a spherical double-hole alumina-silica gel-containing mesoporous molecular sieve composite material carrier; (d) the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier is dipped in a solution containing a Pt component precursor and a Zn component precursor, and then is subjected to solvent removal treatment, drying and roasting in sequence. The obtained isobutane dehydrogenation catalyst has better compressive strength, dehydrogenation activity and carbon deposition resistance.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for preparing an isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from an apparatus for producing ethylene by steam cracking of naphtha, the by-product C4 fraction from a refinery Fluid Catalytic Cracking (FCC) apparatus, and the by-product tert-butyl alcohol (TAB) in the synthesis of propylene oxide by the Halcon method.
In recent years, with the development and utilization of downstream products of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of the chemical industry on isobutene, so the research and development work of a new isobutene production technology becomes a hot spot of the chemical industry. Among the most competitive technologies, isobutane dehydrogenation, n-butene skeletal isomerization and isobutene production by a novel FCC unit are known. Among the methods, the research on the reaction for preparing isobutene by directly dehydrogenating isobutane is early, and the industrial production is realized. China has abundant C4 resources, but the chemical utilization rate of C4 fraction is low in China, most of isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resource is an urgent task in the petrochemical research field. Therefore, the isobutene prepared by dehydrogenating isobutane has a great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly comprise two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr2O3、V2O5、Fe2O3、MoO3ZnO, etc., and a composite oxide thereof, such as V-Sb-O, V-Mo-O, Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate, etc. Compared with noble metal catalysts, oxide catalysts are less expensive. However, the catalyst is easy to deposit carbon, and the catalytic activity, selectivity and stability are low. In addition, most oxide catalysts contain components with high toxicity, which is not favorable for environmental protection. The research on dehydrogenation reactions on noble metal catalysts has a long history, and noble metal catalysts have higher activity, better selectivity, and are more environmentally friendly than other metal oxide catalysts. However, the noble metal is expensive, which results in a catalystThe cost is high, and the performance of the catalyst is not satisfactory.
In order to improve the reaction performance of the catalyst for preparing isobutene by isobutane dehydrogenation, researchers have done a lot of work. Such as: the catalyst performance is improved by changing the preparation method of the catalyst (industrial catalysis, 2014, 22(2): 148-. However, the specific surface area of the currently used carrier is small, which is not beneficial to the dispersion of the active metal component on the surface of the carrier, and is also not beneficial to the diffusion of raw materials and products in the reaction process.
Therefore, how to improve the reaction performance of the isobutane dehydrogenation catalyst is a problem to be solved in the field of preparing isobutene by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of uneven dispersion of noble metal active components and poor catalytic activity and stability of the existing isobutane dehydrogenation catalyst, and provides a method for preparing the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
In order to accomplish the above object, an aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent, a silicon source is contacted with an ammonia water solution, and a mixture obtained after the contact is crystallized and filtered to obtain a mesoporous molecular sieve filter cake;
(b) contacting water glass with inorganic acid and n-butyl alcohol, and filtering a mixture obtained after the contact to obtain a silica gel filter cake;
(c) mixing the mesoporous molecular sieve filter cake and the silica gel filter cake, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, performing spray drying on the obtained slurry, and removing the template agent from the obtained product to obtain a spherical double-hole alumina-silica gel-containing mesoporous molecular sieve composite material carrier;
(d) and (c) dipping the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier obtained in the step (c) in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
A second aspect of the invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
The third aspect of the invention provides a method for preparing isobutene by dehydrogenating isobutane, which comprises the following steps: and (2) carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and hydrogen, wherein the catalyst is the isobutane dehydrogenation catalyst prepared by the method.
The inventor of the invention discovers through research that the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material with a two-dimensional hexagonal pore channel distribution structure is prepared firstly in the preparation process of the isobutane dehydrogenation catalyst and is used as a carrier to load a Pt component and a Zn component, so that the characteristics of the regular ordered mesoporous spatial characteristics and the spherical shape advantages of the mesoporous molecular sieve and the silica gel with the two-dimensional hexagonal pore channel distribution structure are combined, the characteristics of high specific surface area and large pore volume of the ordered mesoporous material are retained, the advantages of large pore diameter and narrow distribution are increased, the pore diameter distribution of the ordered mesoporous molecular sieve composite material is unique bimodal distribution, the advantages of the ordered mesoporous material with the bimodal distribution of the pore diameter and the microsphere structure are combined skillfully, and the loading of the active Pt component and the Zn component is facilitated. In addition, the introduction of the aluminum component in the ball milling process increases the compressive strength of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material, can effectively prevent the sphere from being broken when the active component is loaded, improves the stability of the carrier and prolongs the service life of the catalyst. The spherical double-hole mesoporous molecular sieve composite material containing the aluminum-silicon gel has spherical double-hole substances, has the characteristics of no toxicity, no odor, no pulverization and insolubility in water and ethanol, and also has a unique framework structure, so the affinity with a Pt component and a Zn component is strong, the mesoporous molecular sieve structure of the composite material is uniform in distribution, proper in pore size, large in pore volume, good in mechanical strength, and good in structural stability, and is beneficial to good dispersion of a noble metal component on the surface of a carrier, so that the prepared catalyst can achieve good dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of very low noble metal loading capacity.
Compared with the prior art, the isobutane dehydrogenation catalyst prepared by the method provided by the invention has the following advantages:
(1) the method for preparing the isobutane dehydrogenation catalyst provided by the invention has the advantages of simple preparation process, easily controlled conditions and good product repeatability;
(2) the isobutane dehydrogenation catalyst prepared by the method provided by the invention can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of low loading of main active components (namely noble metals), and can effectively reduce the preparation cost of the isobutane dehydrogenation catalyst;
(3) in the isobutane dehydrogenation catalyst prepared by the method provided by the invention, the stability of a Zn center with an oxidized structure under a high-temperature reduction condition is very high, the inactivation of a single Pt component loaded on a carrier can be inhibited, carbon deposition is reduced, a strong acid center on the surface of the carrier is effectively neutralized, the surface of the carrier is free from acidity, and the dispersion degree of the Pt component is improved through a geometric effect, so that the carbon deposition risk in the reaction process of preparing isobutene by anaerobic dehydrogenation of isobutane can be remarkably reduced, the selectivity of a target product is improved, and the stability of the isobutane dehydrogenation catalyst is improved;
(4) the dispersity of the noble metal active component on the isobutane dehydrogenation catalyst prepared by the method provided by the invention is higher, so that the isobutane dehydrogenation catalyst is not easy to deactivate due to the agglomeration of active metal particles in the reaction process;
(5) the isobutane dehydrogenation catalyst prepared by the method provided by the invention shows good catalytic performance when used for preparing isobutene by anaerobic dehydrogenation of isobutane, and has the advantages of high isobutane conversion rate, high isobutene selectivity, good catalyst stability and low carbon deposition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction (XRD) spectrum of a spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier of example 1;
FIG. 2 is an SEM scanning electron micrograph of the microstructure of the spherical double-pore aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier of example 1.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent, a silicon source is contacted with an ammonia water solution, and a mixture obtained after the contact is crystallized and filtered to obtain a mesoporous molecular sieve filter cake;
(b) contacting water glass with inorganic acid and n-butyl alcohol, and filtering a mixture obtained after the contact to obtain a silica gel filter cake;
(c) mixing the mesoporous molecular sieve filter cake and the silica gel filter cake, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, performing spray drying on the obtained slurry, and removing the template agent from the obtained product to obtain a spherical double-hole alumina-silica gel-containing mesoporous molecular sieve composite material carrier;
(d) and (c) dipping the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier obtained in the step (c) in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
In the process of forming the isobutane dehydrogenation catalyst, the pore size distribution of the carrier is controlled to be bimodal distribution mainly through the composition of a mesoporous molecular sieve filter cake and a silica gel filter cake, so that the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material has a double-pore distribution structure, the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve filter cake and the silica gel filter cake are firstly mixed and ball-milled in a high-aluminum ceramic pot through a control forming method, then the obtained solid powder is slurried with water and then spray-dried, the micro-morphology of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material is controlled to be spherical, and the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material is introduced with an aluminum component.
According to the present invention, in the step (a), the process for preparing the mesoporous molecular sieve filter cake may comprise: and (2) contacting the template agent, a silicon source and an ammonia water solution, and crystallizing and filtering a mixture obtained after the contacting. The order of the contacting is not particularly limited, and the templating agent, the silicon source, and the aqueous ammonia solution may be mixed at the same time, or any two of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the template and the silicon source are added into the ammonia water solution together and mixed evenly. The contact mode is that the template agent and the silicon source are added into an ammonia water solution and mixed evenly, the obtained mixture is placed into a water bath with the temperature of 25-100 ℃ to be stirred until being dissolved, then the temperature is kept unchanged, and the mixture is stirred and reacts for 20-40 hours.
According to the invention, the amount of each substance used in the preparation of the mesoporous molecular sieve filter cake can be selected and adjusted within a wide range. For example, the silicon source, the template agent, and the ammonia and water in the ammonia water are used in a molar ratio of 1: 0.1-1: 0.1-5: 100-200, preferably 1: 0.2-0.5: 1.5-3.5: 120-180.
According to the present invention, in order to make the obtained mesoporous sieving cake have the two-dimensional hexagonal pore distribution structure with the aforementioned pore size, the template agent is preferably cetyl trimethyl ammonium bromide, the silicon source can be various silicon sources conventionally used in the art, and the silicon source is preferably at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and is more preferably ethyl orthosilicate.
According to the invention, the conditions under which the silicon source and the aqueous ammonia solution are contacted may include: the temperature is 25-100 ℃, and the time is 10-72 h. In order to facilitate uniform mixing of the materials, the contacting of the silicon source, the templating agent, and the aqueous ammonia is preferably performed under stirring conditions.
According to the present invention, the crystallization conditions may include: the temperature is 30-150 ℃ and the time is 10-72 h. Preferably, the crystallization conditions include: the temperature is 40-100 ℃ and the time is 20-40 h. The crystallization may be performed by a hydrothermal crystallization method.
The conditions for contacting the water glass, the inorganic acid and the n-butanol are not particularly limited in the present invention, and for example, in the step (b), the conditions for contacting the water glass, the inorganic acid and the n-butanol generally include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time can be 1-5h, preferably 1.5-3h, and the pH value is 2-4. In order to increase the pore size of the prepared silica gel, preferably, the amount of water glass, inorganic acid and n-butanol may be used in a weight ratio of 3 to 6: 1: 1. in order to further facilitate uniform mixing between the substances, the contact of the water glass, the inorganic acid and the n-butanol is preferably carried out under stirring.
According to the invention, the water glass is an aqueous solution of sodium silicate conventional in the art, and its concentration may be 10 to 50% by weight, preferably 12 to 30% by weight.
According to the present invention, the kind of the inorganic acid may be conventionally selected in the art, and for example, may be one or more of sulfuric acid, nitric acid and hydrochloric acid. The inorganic acid may be used in a pure form or in the form of an aqueous solution thereof. The inorganic acid is preferably used in such an amount that the reaction system has a pH of 2 to 4 under the contact conditions of the water glass and the inorganic acid.
Further, in the above-described process for preparing the mesoporous molecular sieve cake and the silica gel cake, the process for obtaining the cake by filtration may include: after filtration, washing with distilled water was repeated (the number of washing may be 2 to 10), followed by suction filtration. Preferably, the washing during the preparation of the mesoporous molecular sieve filter cake results in a filter cake pH of 7 and the washing during the preparation of the silica gel filter cake results in a sodium ion content of less than 0.02 wt.%.
According to the present invention, in step (c), the amount of the mesoporous molecular sieve cake and the silica gel cake may be selected according to the components of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material expected to be obtained, and preferably, the silica gel cake is used in an amount of 1 to 90 parts by weight, preferably 2 to 85 parts by weight, relative to 100 parts by weight of the amount of the mesoporous molecular sieve cake.
According to the invention, in order to enable the finally prepared spherical double-hole aluminum-silicon-gel-containing mesoporous molecular sieve composite material to contain the aluminum component with the content, so as to improve the mechanical strength of the composite material, and prevent powder segregation after ball milling on the basis of not damaging or basically not damaging a carrier structure and enabling silica gel to enter a carrier pore channel, in the step (c), the specific operation method and conditions of the ball milling are preferably carried out in a high-aluminum ceramic ball milling tank, wherein the diameter of a milling ball in the high-aluminum ceramic ball milling tank can be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the high-alumina ceramic ball-milling tank, and 1 grinding ball can be generally used for the high-alumina ceramic ball-milling tank with the size of 50-150 mL; the grinding balls are made of high-alumina ceramic balls. The high-alumina ceramic ball milling conditions comprise: the rotation speed of the grinding ball can be 300-.
In the present invention, the process of slurrying the solid powder obtained after ball milling with water may be performed at 25 to 60 ℃. The weight ratio of solid powder to water used in the pulping process may be 1:0.5-5, preferably 1: 1-2.
In the present invention, the specific operation method and conditions of the spray drying are conventional in the art. Specifically, a slurry prepared from the solid powder and water is added into an atomizer and rotated at a high speed to realize spray drying. Wherein the spray drying conditions comprise: the temperature can be 100-300 ℃, and the rotating speed can be 10000-15000 r/min; preferably, the spray drying conditions include: the temperature is 150-250 ℃, and the rotating speed is 11000-13000 r/min; most preferably, the spray drying conditions include: the temperature is 200 ℃, and the rotating speed is 12000 r/min.
According to the invention, the method for removing the template agent is generally a calcination method. The conditions for removing the template agent may be selected conventionally in the art, and for example, the conditions for removing the template agent include: the temperature can be 300-600 ℃, preferably 350-550 ℃, and most preferably 500 ℃; the time may be 10-80h, preferably 20-30h, most preferably 24 h.
According to the invention, in the step (d), the metal component loaded on the spherical double-hole aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier can adopt an impregnation mode, the metal component enters the pore channel of the spherical double-hole aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier by virtue of the capillary pressure of the pore channel structure of the carrier, and meanwhile, the metal component can be adsorbed on the surface of the spherical double-hole aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier until the metal component reaches adsorption balance on the surface of the carrier. The dipping treatment may be a co-dipping treatment or a stepwise dipping treatment. In order to save the preparation cost and simplify the experimental process, the dipping treatment is preferably co-dipping treatment; further preferably, the conditions of the co-impregnation treatment include: the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier is mixed and contacted with a solution containing a Pt component precursor and a Zn component precursor, the dipping temperature can be 25-50 ℃, and the dipping time can be 2-6 h.
According to the invention, the Pt component precursor is preferably H2PtCl6The Zn component precursor is preferably Zn (NO)3)2。
The concentration of the solution containing the Pt component precursor and the Zn component precursor is not particularly limited in the present invention, and may be conventionally selected in the art, for example, the concentration of the Pt component precursor may be 0.001 to 0.003mol/L, and the concentration of the Zn component precursor may be 0.015 to 0.1 mol/L.
According to the present invention, the solvent removal treatment can be carried out by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
According to the present invention, in the step (d), the drying may be performed in a drying oven, and the firing may be performed in a muffle furnace. The drying conditions may include: the temperature is 110-150 ℃ and the time is 3-6 h; the conditions for the firing may include: the temperature is 600 ℃ and 650 ℃, and the time is 5-8 h.
According to the invention, in the step (d), the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier, the Pt component precursor and the Zn component precursor are used in such amounts that the prepared isobutane dehydrogenation catalyst contains 98-99.4 wt% of the carrier, 0.1-0.5 wt% of the Pt component calculated by Pt element and 0.5-1.5 wt% of the Zn component calculated by Zn element, based on the total weight of the isobutane dehydrogenation catalyst.
Preferably, the usage amounts of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier, the Pt component precursor and the Zn component precursor are such that the content of the carrier is 98.4-99 wt%, the content of the Pt component calculated by Pt element is 0.2-0.4 wt%, and the content of the Zn component calculated by Zn element is 0.8-1.2 wt% in the prepared isobutane dehydrogenation catalyst based on the total weight of the isobutane dehydrogenation catalyst.
In a second aspect, the present invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
According to the invention, the isobutane dehydrogenation catalyst comprises a carrier, and a Pt component and a Zn component which are loaded on the carrier, wherein the carrier is a spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier, and the catalyst comprisesThe spherical double-hole aluminum-silicon-containing gel mesoporous molecular sieve composite material contains an aluminum component, a mesoporous molecular sieve material with a two-dimensional hexagonal pore structure and silica gel, wherein the compressive strength of a carrier of the spherical double-hole aluminum-silicon-containing gel mesoporous molecular sieve composite material is 12-16MPa, the average particle size is 20-80 mu m, and the specific surface area is 100-200m2The pore volume is 0.5-1.5mL/g, the pore diameter is in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 0.3-5nm and 30-40nm respectively.
According to the invention, in the isobutane dehydrogenation catalyst, the carrier has a special two-dimensional hexagonal pore channel distribution structure, the unique framework structure breaks through the limitation of one-dimensional pore channels on molecular transmission, the carrier is provided with a spherical porous substance, the mesoporous pore channel structure of the carrier is uniform in distribution, proper in pore size, large in pore volume, good in mechanical strength and good in structural stability, and the special two-dimensional hexagonal ordered mesoporous pore channel distribution structure and the pore channel structure of silica gel are combined to be favorable for the good dispersion of metal components in the pore channels of the carrier. In addition, the compressive strength of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material is remarkably increased due to the aluminum component contained in the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material, the ball can be effectively prevented from being crushed when an active component is loaded, and the stability of the carrier is improved. The spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material is used as a carrier, and the supported catalyst obtained by supporting the Pt component and the Zn component has the advantages of the supported catalyst, such as good dispersity of a noble metal active component, small load amount, high catalytic activity, few side reactions, simple post-treatment and the like, and has strong catalytic activity and high stability, so that the supported catalyst has better dehydrogenation activity, product selectivity and carbon deposition resistance when being used for isobutane dehydrogenation reaction, and the conversion rate of reaction raw materials is remarkably improved.
According to the invention, the average particle diameter of the particles of the support is determined using a laser particle size distribution instrument, and the specific surface area, pore volume and most probable pore diameter are determined according to a nitrogen adsorption method. In the present invention, the particle size refers to the particle size of the raw material particles, and is expressed by the diameter of the sphere when the raw material particles are spherical, by the side length of the cube when the raw material particles are cubic, and by the mesh size of the screen that can sieve out the raw material particles when the raw material particles are irregularly shaped.
According to the invention, the structural parameters of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier are controlled within the range, so that the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material is not easy to agglomerate, and the conversion rate of reaction raw materials in the reaction process of preparing isobutene by isobutane dehydrogenation can be improved by using the supported catalyst prepared by using the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material as the carrier. When the specific surface area of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material is less than 100m2When the volume/g and/or pore volume is less than 0.5mL/g, the catalytic activity of the supported catalyst prepared by using the supported catalyst is remarkably reduced; when the specific surface area of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material is more than 200m2When the volume/g and/or the pore volume is more than 1.5mL/g, the supported catalyst prepared by using the supported catalyst as the carrier is easy to agglomerate in the reaction process of preparing isobutene by isobutane dehydrogenation, so that the conversion rate of the reaction raw material in the reaction process of preparing isobutene by isobutane dehydrogenation is influenced.
Preferably, the compressive strength of the carrier is 14-16MPa, the average particle diameter is 20-70 μm, and the specific surface area is 100-180m2The pore volume is 1-1.4mL/g, the pore diameter is in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 1-5nm and 32-39nm respectively.
According to the invention, based on the total weight of the isobutane dehydrogenation catalyst, the content of the carrier is 98-99.4 wt%, the content of the Pt component calculated by Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by Zn element is 0.5-1.5 wt%.
Preferably, the content of the carrier is 98.4-99 wt%, the content of the Pt component calculated by Pt element is 0.2-0.4 wt%, and the content of the Zn component calculated by Zn element is 0.8-1.2 wt%, based on the total weight of the isobutane dehydrogenation catalyst.
Further preferably, the compression strength of the isobutane dehydrogenation catalyst is 14-16MPa, and the average particle size is20-70 μm, and specific surface area of 95-125m2The pore volume is 0.6-1.3mL/g, the pore diameter is in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 1-5nm and 32-39nm respectively.
According to the invention, the increase of the content of the aluminum component is beneficial to improving the compressive strength of the carrier, the content of the mesoporous molecular sieve material and the content of the silica gel can adjust the pore structure of the carrier, and in order to ensure that the carrier has higher compressive strength and better pore structure parameters, in the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material, the content of the aluminum component is 1-20 parts by weight, preferably 5-19 parts by weight, and the content of the silica gel is 1-90 parts by weight, preferably 2-85 parts by weight, relative to 100 parts by weight of the mesoporous molecular sieve material with a two-dimensional hexagonal pore structure.
As described above, the third aspect of the present invention provides a method for producing isobutene by dehydrogenating isobutane, including: and (2) carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and hydrogen, wherein the catalyst is the isobutane dehydrogenation catalyst prepared by the method.
When the isobutane dehydrogenation catalyst prepared by the method provided by the invention is used for catalyzing isobutane to dehydrogenate to prepare isobutene, the conversion rate of isobutane and the selectivity of isobutene can be greatly improved.
According to the present invention, in order to increase the isobutane conversion rate and prevent the catalyst from coking, it is preferable that the molar ratio of the amount of isobutane to the amount of hydrogen is 0.5 to 1.5: 1.
the conditions for the dehydrogenation reaction in the present invention are not particularly limited and may be conventionally selected in the art, and for example, the conditions for the dehydrogenation reaction may include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the reagents used were all commercially available analytical reagents;
in the following examples and comparative examples, the X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8 Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; pore structure parameter analysis was performed on an ASAP2020-M + C adsorption apparatus manufactured by Micromeritics, USA; the specific surface area and the pore volume of the sample are calculated by adopting a BET method; the result of the aluminum content is measured by a photoelectron spectrum analyzer; the particle size distribution of the sample is carried out on a Malvern laser particle sizer; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. Axios-Advanced; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
In the following experimental examples and experimental comparative examples, the conversion (%) of isobutane was equal to the amount of isobutane consumed by the reaction/initial amount of isobutane × 100%;
the selectivity (%) of isobutylene was defined as the amount of isobutane consumed for producing isobutylene/total consumption of isobutane × 100%.
Example 1
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Adding hexadecyl trimethyl ammonium bromide and tetraethoxysilane into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the tetraethoxysilane is 1g, the feeding ratio of the massages is as follows: cetyl trimethylammonium bromide: ammonia (25%): deionized water 1: 0.37: 2.8: 142, stirring the solution at the temperature of 80 ℃ until the solution is dissolved, carrying out suction filtration on the solution to obtain a mesoporous material filter cake, and washing the filter cake until the pH value is 7 to obtain a mesoporous molecular sieve filter cake A1 with a two-dimensional hexagonal pore structure;
adding 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol, and mixing the water glass: sulfuric acid: the weight ratio of n-butyl alcohol is 5: 1:1, fully reacting at 30 ℃ for 1.5h, adjusting the pH to 3 by using 98 wt% sulfuric acid, and performing suction filtration and washing with distilled water until the content of sodium ions is 0.02 wt% to obtain a silica gel filter cake B1.
And putting 10g of the prepared filter cake A1 and 10g of the prepared filter cake B1 into a 100ml ball milling tank together, wherein the ball milling tank is made of high-alumina ceramic, the grinding balls are made of high-alumina ceramic, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. Sealing the ball milling tank, and carrying out ball milling for 1h in the ball milling tank at the temperature of 60 ℃ to obtain 30g of solid powder; dissolving the solid powder in 30g of deionized water, and spray-drying at 200 ℃ at a rotating speed of 12000 r/min; calcining the product obtained after spray drying in a muffle furnace at 500 ℃ for 24h, and removing the template agent to obtain 30g of a target product spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C1 from which the template agent is removed. According to the result of photoelectron spectroscopy, the content of aluminum in C1 was 20% by weight.
(2) Preparation of isobutane dehydrogenation catalyst
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C1 prepared in the step (1) in the mixture solution, soaking at 25 ℃ for 5h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying oven at 120 ℃ for drying for 3 h. And then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-1 (based on the total weight of the isobutane dehydrogenation catalyst Cat-1, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
The spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material C1 and the isobutane dehydrogenation catalyst Cat-1 are characterized by an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
fig. 1 is an X-ray diffraction (XRD) spectrum of the spherical double-pore aluminum-silicon-containing gel mesoporous molecular sieve composite carrier C1, wherein the abscissa is 2 θ and the ordinate is intensity, and the XRD spectrum of the spherical double-pore aluminum-silicon-containing gel mesoporous molecular sieve composite carrier C1 has a two-dimensional hexagonal cavity structure specific to a mesoporous material, as can be seen from a small-angle spectrum peak appearing in the XRD spectrum;
fig. 2 is an SEM scanning electron microscope image of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier C1, and it can be seen from the image that the microscopic morphology of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier C1 is microspheres with a particle size of 10-80 μm, and the monodispersity thereof is good.
Table 1 shows the pore structure parameters of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier C1 and the isobutane dehydrogenation catalyst Cat-1.
TABLE 1
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data in table 1, the specific surface area and the pore volume of the spherical double-pore aluminum-silica-containing silica-alumina gel mesoporous molecular sieve composite material carrier are reduced after the Pt component and the Zn component are loaded, which indicates that the Pt component and the Zn component enter the interior of the spherical double-pore aluminum-silica-containing silica-alumina gel mesoporous molecular sieve composite material carrier during the loading reaction.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that the same weight of alumina carrier was used instead of the spherical double-pore alumina-silica gel containing mesoporous molecular sieve composite carrier C1 in the preparation of the carrier, thereby preparing the carrier D1 and the isobutane dehydrogenation catalyst Cat-D-1, respectively.
Comparative example 2
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that the catalyst used was an oxide catalyst such as ZnO, thereby obtaining an isobutane dehydrogenation catalyst Cat-D-2.
Comparative example 3
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that no aluminum component was introduced during the preparation of the carrier, the material of the ball-milling jar used during the ball-milling process was teflon, and the material of the milling balls was agate, thereby preparing the carrier D3 and the isobutane dehydrogenation catalyst Cat-D-3, respectively.
Comparative example 4
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that there was no spray-drying step in the preparation of the isobutane dehydrogenation catalyst, and a Pt component and a Zn component were supported on the support only by the impregnation method, thereby preparing a support D4 and an isobutane dehydrogenation catalyst Cat-D-4, respectively.
Comparative example 5
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that Zn (NO) was not added during the impregnation process for preparing the isobutane dehydrogenation catalyst3)2·6H2O, addition of only 0.080g H2PtCl6·6H2And O, only loading a single Pt component on the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier by a co-impregnation method, thereby preparing the isobutane dehydrogenation catalyst Cat-D-5, wherein the content of the Pt component in terms of Pt element is 0.3 wt% and the balance is the carrier on the basis of the total weight of the isobutane dehydrogenation catalyst Cat-D-5).
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Adding hexadecyl trimethyl ammonium bromide and tetraethoxysilane into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the tetraethoxysilane is 1g, the feeding ratio of the massages is as follows: cetyl trimethylammonium bromide: ammonia (25%): deionized water 1: 0.5: 3.5: 150, stirring the solution at the temperature of 80 ℃ until the solution is dissolved, carrying out suction filtration on the solution to obtain a mesoporous material filter cake, and washing the filter cake until the pH value is 7 to obtain a mesoporous molecular sieve filter cake A2 with a two-dimensional hexagonal pore structure;
adding 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol, and mixing the water glass: sulfuric acid: the weight ratio of n-butyl alcohol is 6: 1:1, fully reacting at 60 ℃ for 1 hour, adjusting the pH to 2 by using 98 wt% sulfuric acid, and performing suction filtration and washing with distilled water until the content of sodium ions is 0.02 wt% to obtain a silica gel filter cake B2.
And (3) putting 20g of the prepared filter cake A2 and 40g of the prepared filter cake B2 into a 100ml ball milling tank together, wherein the ball milling tank is made of high-alumina ceramic, the grinding balls are made of high-alumina ceramic, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 300 r/min. Sealing the ball milling tank, and ball milling for 0.5h in the ball milling tank at the temperature of 100 ℃ to obtain 40g of solid powder; dissolving the solid powder in 30g of deionized water, and spray-drying at 150 ℃ at the rotating speed of 11000 r/min; calcining the product obtained after spray drying in a muffle furnace at 300 ℃ for 72h, and removing the template agent to obtain 35g of a target product spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C2 from which the template agent is removed. According to the result of photoelectron spectroscopy, the content of aluminum in C2 was 9% by weight.
(2) Preparation of isobutane dehydrogenation catalyst
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C2 prepared in the step (1) in the mixture solution, soaking at 25 ℃ for 5h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying oven at 120 ℃ for drying for 3 h. Then roasting the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain the isobutane dehydrogenation catalystCat-2 (based on the total weight of the isobutane dehydrogenation catalyst Cat-2, the content of a Pt component calculated by a Pt element is 0.3 wt%, the content of a Zn component calculated by a Zn element is 1 wt%, and the balance is a carrier).
Table 2 shows the pore structure parameters of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier C2 and the isobutane dehydrogenation catalyst Cat-2.
TABLE 2
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data in table 2, the specific surface area and the pore volume of the spherical double-pore aluminum-silica-containing silica-alumina gel mesoporous molecular sieve composite material carrier are reduced after the Pt component and the Zn component are loaded, which indicates that the Pt component and the Zn component enter the interior of the spherical double-pore aluminum-silica-containing silica-alumina gel mesoporous molecular sieve composite material carrier during the loading reaction.
Example 3
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Adding hexadecyl trimethyl ammonium bromide and tetraethoxysilane into an ammonia water solution with the concentration of 25 weight percent, wherein the adding amount of the tetraethoxysilane is 1g, the feeding ratio of the massages is as follows: cetyl trimethylammonium bromide: ammonia (25%): deionized water 1: 0.4: 3: 130, stirring at the temperature of 60 ℃ until the solution is dissolved, carrying out suction filtration on the solution to obtain a mesoporous material filter cake, and washing the filter cake until the pH value is 7 to obtain a mesoporous molecular sieve filter cake A3 with a two-dimensional hexagonal pore structure;
adding 15 wt% of water glass, 12 wt% of sulfuric acid solution and n-butyl alcohol, and mixing the water glass: sulfuric acid: the weight ratio of n-butyl alcohol is 3: 1:1, fully reacting at 10 ℃ for 5 hours, adjusting the pH to 4 by using 98 wt% sulfuric acid, and performing suction filtration and washing with distilled water until the content of sodium ions is 0.02 wt% to obtain a silica gel filter cake B3.
And (3) putting 20g of the prepared filter cake A3 and 60g of the prepared filter cake B3 into a 100ml ball milling tank together, wherein the ball milling tank is made of high-alumina ceramic, the grinding balls are made of high-alumina ceramic, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 500 r/min. Sealing the ball milling tank, and carrying out ball milling for 10 hours in the ball milling tank at the temperature of 25 ℃ to obtain 40g of solid powder; dissolving the solid powder in 30g of deionized water, and spray-drying at 300 ℃ at the rotating speed of 13000 r/min; calcining the product obtained after spray drying in a muffle furnace at 600 ℃ for 12h, and removing the template agent to obtain 30g of a target product spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C3 from which the template agent is removed. According to the results of photoelectron spectroscopy, the content of aluminum in C3 was 15% by weight.
(2) Preparation of isobutane dehydrogenation catalyst
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier C3 prepared in the step (1) in the mixture solution, soaking at 25 ℃ for 5h, evaporating solvent water in a system by using a rotary evaporator to obtain a solid product, and placing the solid product in a drying oven at 120 ℃ for drying for 3 h. And then roasting the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain the isobutane dehydrogenation catalyst Cat-3 (based on the total weight of the isobutane dehydrogenation catalyst Cat-3, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
Table 3 shows the pore structure parameters of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier C3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 3
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data in Table 3, the specific surface area and the pore volume of the spherical double-pore aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier are reduced after the Pt component and the Zn component are loaded, which shows that the Pt component and the Zn component enter the interior of the spherical double-pore aluminum-containing silica-alumina gel mesoporous molecular sieve composite material carrier in the loading reaction process.
Experimental example 1
This example is intended to illustrate the preparation of isobutene using the isobutane dehydrogenation catalyst of the present invention
0.5g of isobutane dehydrogenation catalyst Cat-1 was loaded into a fixed bed quartz reactor, the reaction temperature was controlled at 590 ℃, the reaction pressure was 0.1MPa, and the isobutane: the molar ratio of hydrogen is 1:1, the reaction time is 24 hours, and the mass space velocity of the isobutane is 4 hours-1. By Al2O3The reaction product separated by the S molecular sieve column directly enters an Agilent 7890A gas chromatograph provided with a hydrogen flame detector (FID) for on-line analysis. The determination of the carbon deposit amount of the dehydrogenation catalyst was carried out on a TGA/DSC1 thermogravimetric analyzer of the company METTLER-TOLEDO. Isobutane conversion, isobutene selectivity and catalyst carbon deposition are shown in table 4.
Experimental examples 2 to 3
Isobutene was prepared by dehydrogenation of isobutane according to the method of experimental example 1, except that isobutane dehydrogenation catalyst Cat-2 and isobutane dehydrogenation catalyst Cat-3 were used instead of isobutane dehydrogenation catalyst Cat-1, respectively. Isobutane conversion, isobutene selectivity and catalyst carbon deposition are shown in table 4.
Experimental comparative examples 1 to 5
Isobutene is prepared by isobutane dehydrogenation according to the method of the experimental example 1, except that isobutane dehydrogenation catalysts Cat-D-1 to Cat-D-5 are respectively adopted to replace the isobutane dehydrogenation catalyst Cat-1. Isobutane conversion, isobutene selectivity and catalyst carbon deposition are shown in table 4.
TABLE 4
As can be seen from Table 4, the isobutane dehydrogenation catalyst prepared by using the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier has higher compressive strength, and when the catalyst is used for preparing isobutene by isobutane dehydrogenation, higher isobutane conversion rate and isobutene selectivity can be still obtained after 24-hour reaction, which shows that the isobutane dehydrogenation catalyst disclosed by the invention not only has better catalytic performance, but also has good stability and low carbon deposition amount.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (19)
1. A method for preparing an isobutane dehydrogenation catalyst, characterized in that the method comprises the following steps:
(a) in the presence of a template agent, a silicon source is contacted with an ammonia water solution, and a mixture obtained after the contact is crystallized and filtered to obtain a mesoporous molecular sieve filter cake;
(b) contacting water glass with inorganic acid and n-butyl alcohol, and filtering a mixture obtained after the contact to obtain a silica gel filter cake;
(c) mixing the mesoporous molecular sieve filter cake and the silica gel filter cake, performing ball milling in a high-alumina ceramic pot, pulping solid powder obtained after ball milling by using water, performing spray drying on the obtained slurry, and removing the template agent from the obtained product to obtain a spherical double-hole alumina-silica gel-containing mesoporous molecular sieve composite material carrier;
(d) dipping the spherical double-hole aluminum-containing silica gel mesoporous molecular sieve composite material carrier obtained in the step (c) in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting;
in the step (d), the use amounts of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier, the Pt component precursor and the Zn component precursor are such that the content of the carrier in the prepared isobutane dehydrogenation catalyst is 98.4-99 wt%, the content of the Pt component calculated by Pt element is 0.2-0.4 wt%, and the content of the Zn component calculated by Zn element is 0.8-1.2 wt%, based on the total weight of the isobutane dehydrogenation catalyst;
wherein the compressive strength of the spherical double-pore aluminum-containing silica gel mesoporous molecular sieve composite material carrier is 12-16MPa, the average particle size is 20-80 mu m, and the specific surface area is 100-200m2The pore volume is 0.5-1.5mL/g, the pore diameter is in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 0.3-5nm and 30-40nm respectively.
2. The method of claim 1, wherein in step (a), the silicon source, the template, ammonia in ammonia water, and water are used in a molar ratio of 1: 0.1-1: 0.1-5: 100-200.
3. The method of claim 2, wherein in step (a), the silicon source, the template, the ammonia in the ammonia water, and the water are used in a molar ratio of 1: 0.2-0.5: 1.5-3.5: 120-180.
4. The method of claim 1, wherein in step (a), the templating agent is cetyltrimethylammonium bromide and the silicon source comprises at least one of ethyl orthosilicate, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate, and silica sol.
5. The method of claim 4, wherein the silicon source is tetraethyl orthosilicate.
6. The method of claim 1, wherein in step (a), the conditions of the contacting comprise: the temperature is 25-100 ℃, and the time is 10-72 h; the crystallization conditions include: the temperature is 30-150 ℃ and the time is 10-72 h.
7. The method according to claim 1, wherein, in step (b), the conditions under which the water glass, the inorganic acid and the n-butanol are contacted comprise: the weight ratio of the water glass to the inorganic acid to the n-butyl alcohol is 3-6: 1:1, the temperature is 10-60 ℃, the time is 1-5h, and the pH value is 2-4; the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
8. The method according to claim 1, wherein, in step (c), the silica gel cake is used in an amount of 1-90 parts by weight with respect to 100 parts by weight of the mesoporous molecular sieve cake.
9. The process according to claim 8, wherein, in step (c), the silica gel cake is used in an amount of 2-85 parts by weight with respect to 100 parts by weight of the mesoporous molecular sieve cake.
10. The method of claim 1, wherein in step (c), the conditions under which ball milling is performed in the high alumina ceramic pot comprise: the rotation speed of the grinding ball is 300-; the conditions of the spray drying include: the temperature is 100-300 ℃, and the rotating speed is 10000-15000 r/min.
11. The method of claim 1, wherein in step (c), the templating agent removal process comprises: calcining at 600 ℃ for 10-80 h.
12. An isobutane dehydrogenation catalyst produced by the process of any one of claims 1-11.
13. The isobutane dehydrogenation catalyst according to claim 12, wherein the isobutane dehydrogenation catalyst comprises a carrier and a Pt component and a Zn component supported on the carrier, wherein the carrier is a spherical dual-pore aluminum-containing silica gel mesoporous molecular sieve composite carrier containing an aluminum component, a mesoporous molecular sieve material having a two-dimensional hexagonal pore structure and silica gel.
14. The isobutane dehydrogenation catalyst according to claim 12, wherein the compressive strength of the carrier is 14-16MPa, the average particle size is 20-70 μm, the specific surface area is 100-180m2The pore volume is 1-1.4mL/g, the pore diameter is in bimodal distribution, and the most probable pore diameters corresponding to the bimodal distribution are 1-5nm and 32-39nm respectively.
15. The isobutane dehydrogenation catalyst according to claim 13, wherein the content of the aluminum component is 1-20 parts by weight and the content of the silica gel is 1-90 parts by weight with respect to 100 parts by weight of the mesoporous molecular sieve material having a two-dimensional hexagonal pore structure.
16. The isobutane dehydrogenation catalyst according to claim 15, wherein the content of the aluminum component is 5-19 parts by weight and the content of the silica gel is 2-85 parts by weight with respect to 100 parts by weight of the mesoporous molecular sieve material having a two-dimensional hexagonal pore structure.
17. A method for preparing isobutene by dehydrogenating isobutane, comprising the following steps: isobutane is subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen, characterized in that said catalyst is an isobutane dehydrogenation catalyst according to any of the claims 12-16.
18. The process according to claim 17, wherein the molar ratio of the amount of isobutane to the amount of hydrogen is between 0.5 and 1.5: 1.
19. the method of claim 18, wherein the dehydrogenation reaction conditions comprise: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass of the isobutane is emptyThe speed is 2-5h-1。
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| CN103420769A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation |
| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN106622378A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminium-containing mesoporous composite material, supported catalyst, preparation method and applications of spherical aluminium-containing mesoporous composite material and supported catalyst, and method used for preparing cyclohexanone glyceryl |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103420769A (en) * | 2012-05-16 | 2013-12-04 | 中国石油化工股份有限公司 | Method for preparing low-carbon olefin from low-carbon alkane through dehydrogenation |
| CN106311311A (en) * | 2015-06-19 | 2017-01-11 | 中国石油化工股份有限公司 | Catalyst for preparing propylene through propane dehydrogenation, preparation method of catalyst, and method for propylene through propane dehydrogenation |
| CN106622378A (en) * | 2015-11-04 | 2017-05-10 | 中国石油化工股份有限公司 | Spherical aluminium-containing mesoporous composite material, supported catalyst, preparation method and applications of spherical aluminium-containing mesoporous composite material and supported catalyst, and method used for preparing cyclohexanone glyceryl |
Non-Patent Citations (1)
| Title |
|---|
| Zn-modified MCM-41 as support for Pt catalysts;J. Silvestre-Albero等;《Applied Catalysis A: General》;20080829;第351卷;第16-23页 * |
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