CN110732340A - Isobutane dehydrogenation catalyst with spherical double-mesoporous zeolite composite material as carrier and preparation method and application thereof - Google Patents
Isobutane dehydrogenation catalyst with spherical double-mesoporous zeolite composite material as carrier and preparation method and application thereof Download PDFInfo
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- CN110732340A CN110732340A CN201810797563.6A CN201810797563A CN110732340A CN 110732340 A CN110732340 A CN 110732340A CN 201810797563 A CN201810797563 A CN 201810797563A CN 110732340 A CN110732340 A CN 110732340A
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- isobutane
- dehydrogenation catalyst
- mesoporous
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- isobutane dehydrogenation
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 262
- 239000003054 catalyst Substances 0.000 title claims abstract description 135
- 239000001282 iso-butane Substances 0.000 title claims abstract description 131
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 120
- 239000010457 zeolite Substances 0.000 title claims description 98
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 93
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 93
- 239000002131 composite material Substances 0.000 title claims description 68
- 238000002360 preparation method Methods 0.000 title claims description 29
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000034 method Methods 0.000 claims abstract description 63
- 239000011148 porous material Substances 0.000 claims description 74
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000012065 filter cake Substances 0.000 claims description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000003795 chemical substances by application Substances 0.000 claims description 34
- 238000000498 ball milling Methods 0.000 claims description 30
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- 238000009826 distribution Methods 0.000 claims description 26
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- 239000002253 acid Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000013335 mesoporous material Substances 0.000 claims description 21
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
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- 239000000047 product Substances 0.000 claims description 16
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
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- FLTJDUOFAQWHDF-UHFFFAOYSA-N trimethyl pentane Natural products CCCCC(C)(C)C FLTJDUOFAQWHDF-UHFFFAOYSA-N 0.000 claims description 10
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 description 5
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- 238000001354 calcination Methods 0.000 description 4
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- 229910001415 sodium ion Inorganic materials 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 3
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- 229910052680 mordenite Inorganic materials 0.000 description 3
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
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- JEWHCPOELGJVCB-UHFFFAOYSA-N aluminum;calcium;oxido-[oxido(oxo)silyl]oxy-oxosilane;potassium;sodium;tridecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.O.[Na].[Al].[K].[Ca].[O-][Si](=O)O[Si]([O-])=O JEWHCPOELGJVCB-UHFFFAOYSA-N 0.000 description 2
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- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- 230000001276 controlling effect Effects 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
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- 229920002367 Polyisobutene Polymers 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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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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- B01J35/394—
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- B01J35/40—
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- B01J35/615—
-
- B01J35/635—
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- B01J35/638—
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- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
-
- 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
- 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
-
- 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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to the field of catalysts, and discloses a method for preparing an isobutane dehydrogenation catalyst and the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for preparing an isobutane dehydrogenation catalyst by , the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is very important organic chemical raw materials 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, and the main sources of isobutene are a C4 fraction which is a byproduct of a naphtha steam cracking ethylene preparation device, a C4 fraction which is a byproduct of a refinery Fluid Catalytic Cracking (FCC) device and tert-butyl alcohol (TAB) which is a byproduct in the synthesis of propylene oxide by a 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 isobutene in the chemical industry, so the research and development work of a new isobutene production technology becomes a major hotspot in the chemical industry.
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 catalyst cost is high due to the expensive price of noble metals, and the performance of such catalysts has not yet reached a satisfactory level.
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. And the pore diameter of the commonly used mesoporous material is small (the average pore diameter is 6-9 nm), and if macromolecule catalytic reaction is carried out, the macromolecule is difficult to enter a pore channel, so that the catalytic effect is influenced, the dispersion of the noble metal active component of the conventional isobutane dehydrogenation catalyst is uneven, and the catalytic activity, the stability and the carbon deposition resistance are poor.
Therefore, how to improve the reaction performance of the isobutane dehydrogenation catalyst is problems to be solved urgently in the field of isobutene preparation by isobutane dehydrogenation.
Natural zeolites are hydrated, framework-structured, porous aluminosilicate minerals, which are a generic name for minerals of the zeolite family. The zeolite being composed predominantly of SiO2、Al2O3、H2O and alkali and alkaline earth metal ions, and the proportion of the four parts is greatly changed, thereby forming various zeolite minerals. 40 natural zeolite minerals have been found to be common, such as analcite, chabazite, clinoptilolite, heulandite, erionite, ferrierite, laumontite, mordenite, phillipsite. At present, more than 10 natural zeolite minerals such as analcime, clinoptilolite, mordenite, ferrierite, phillipsite, epidesmine and the like are found in China. The most widely used are clinoptilolite and mordenite, and analcime and epidesmine. The specific physical properties of zeolites, which consist of SiO, depend on the lattice structure of the zeolite2And Al2O3The staggered arrangement of tetrahedral units into a spatial network is due to the openness of the crystal structure. Zeolites contain many pores and cavities of non-uniform size. These channels and cavities are often occupied by alkali or alkaline earth metal ions and zeolite water molecules due to the need to compensate for the positive charge resulting from the valence imbalance of aluminum-substituted silicon in the tetrahedra. The structure of zeolite determines its unique physical and chemical properties such as ion exchange property and adsorption selectivity. In addition, zeolites also have good thermal stability, acid resistance, dehydratability, catalytic cracking properties for chemical reactions, radiation resistance, and low bulk density, porosity, and the like.
In the conventional supported catalysts, a mesoporous molecular sieve material is generally used as a carrier. The mesoporous molecular sieve material has the advantages of ordered pore channels, adjustable pore diameter, larger specific surface area and pore volume and the like, so that the supported catalyst prepared by using the mesoporous molecular sieve material as a carrier has many advantages in the preparation process of organic catalytic reaction, such as high catalytic activity, less side reaction, simple post-treatment and the like, however, the large specific surface area and the high pore volume ensure that the mesoporous molecular sieve material has stronger water absorption and moisture absorption capacity, and the supported catalyst can be agglomerated in the catalytic reaction process.
Therefore, if the advantages of the mesoporous material and the zeolite can be combined, novel composite materials are synthesized, so that the novel composite materials have the advantages of the zeolite and the advantages of the mesoporous material, the characteristics of the mesoporous molecular sieve material such as high specific surface area, large pore volume, large pore diameter, special pore channel structure and the like can be kept, the uniform dispersion, catalytic activity, stability and anti-carbon deposition of the noble metal active component of the isobutane dehydrogenation catalyst are improved, the agglomeration of the mesoporous molecular sieve material can be reduced, and the fluidity of the mesoporous molecular sieve material is increased.
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 achieve 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) under the existence of a template agent, trimethylpentane and ethanol, tetramethoxysilane is contacted with an acid agent, and a product obtained after the contact is crystallized and filtered to obtain a mesoporous material filter cake;
(b) contacting water glass with inorganic acid, and filtering a product obtained after the contact to obtain a silica gel filter cake;
(c) mixing and ball-milling the mesoporous material filter cake, the silica gel filter cake and the zeolite, pulping solid powder obtained after ball-milling with water, then carrying out spray drying, and removing the template agent in the obtained product to obtain a spherical double mesoporous zeolite composite material carrier;
(d) and (c) dipping the spherical double-mesoporous zeolite 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 isobutane dehydrogenation catalysts prepared by the aforementioned process.
The third aspect of the invention provides applications of the isobutane dehydrogenation catalyst prepared by the method in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the step of carrying out dehydrogenation reaction on isobutane in the presence of the catalyst and hydrogen.
The carrier structure of the noble metal catalyst (including physical structures such as specific surface area, pore volume, pore size distribution and the like and chemical structures such as surface acid sites, electronic properties and the like) not only has important influence on the dispersion degree of active metal components, but also directly influences mass transfer and diffusion in the reaction process. Thus, the catalytic properties of heterogeneous catalysts, such as activity, selectivity and stability, depend both on the catalytic characteristics of the active component and on the characteristics of the catalyst support. In order to reduce the content of noble metal in the catalyst as much as possible and improve the activity and stability of the catalyst at the same time, the preparation process of the carrier is of great importance. Most commercially available activated alumina has too many surface hydroxyl groups and too strong acidity. When the aluminum oxide is used as a carrier to prepare the dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon in the reaction process, and the rapid inactivation is caused.
The inventor of the invention discovers through research that by introducing zeolite in the preparation process of the isobutane dehydrogenation catalyst, common and easily-obtained raw materials can be used, a supported catalyst carrier with a special pore channel structure can be obtained under simple operation conditions, the carrier has the characteristics of a porous structure, a large specific surface area and a large pore volume of a mesoporous molecular sieve material, and the zeolite has strong adsorption capacity due to the large specific surface area and a microporous structure, so that the good dispersion of a precious metal component on the surface of the carrier is facilitated, and the prepared catalyst can achieve good dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of low precious metal loading.
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 is very high under a high-temperature reduction condition, the inactivation of a single Pt 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 are included to provide a further understanding of the invention and constitute a part of this specification, and together with the following detailed description , serve to explain the invention without limiting it.
FIG. 1 is an X-ray diffraction pattern of a spherical mesoporous zeolite composite support of example 1;
fig. 2 is an SEM scanning electron micrograph of the micro-morphology of the spherical mesoporous zeolite composite support 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.
For numerical ranges, between the endpoints of each range and the individual points, and between the individual points may be combined with each other to yield new numerical ranges or ranges, which should be considered as specifically disclosed herein.
As previously mentioned, an th aspect of the invention provides a process for the preparation of an isobutane dehydrogenation catalyst, the process comprising the steps of:
(a) under the existence of a template agent, trimethylpentane and ethanol, tetramethoxysilane is contacted with an acid agent, and a product obtained after the contact is crystallized and filtered to obtain a mesoporous material filter cake;
(b) contacting water glass with inorganic acid, and filtering a product obtained after the contact to obtain a silica gel filter cake;
(c) mixing and ball-milling the mesoporous material filter cake, the silica gel filter cake and the zeolite, pulping solid powder obtained after ball-milling with water, then carrying out spray drying, and removing the template agent in the obtained product to obtain a spherical double mesoporous zeolite composite material carrier;
(d) and (c) dipping the spherical double-mesoporous zeolite 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 formation process of the isobutane dehydrogenation catalyst, the mesoporous material filter cake is a mesoporous molecular sieve material with an -dimensional hexagonal pore channel distribution structure.
In the process of forming the spherical double-mesoporous zeolite composite material carrier, the pore size distribution is controlled to be bimodal distribution mainly by controlling the composition of the mesoporous material filter cake, the silica gel filter cake and the zeolite, so that the spherical double-mesoporous zeolite composite material carrier has a double-pore distribution structure, and the micro-morphology of the spherical double-mesoporous zeolite composite material carrier is controlled to be spherical by controlling a forming method (namely, firstly mixing and ball-milling the mesoporous material filter cake, the silica gel filter cake and the zeolite, then pulping the obtained solid powder with water and then spray-drying).
According to the present invention, the amount of each substance can be selected and adjusted within a wide range in the process of preparing the mesoporous material filter cake. For example, in step (a), the molar ratio of the templating agent, ethanol, trimethylpentane, and tetramethoxysilane may be 1: 100-500: 200-600: 50-200, preferably 1: 200-400: 250-400: 70-150.
According to the present invention, the type of the template is not particularly limited as long as the obtained spherical mesoporous zeolite composite support can have the above pore structure, and preferably, the template may be a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene. Wherein the templating agent is commercially available (e.g., from Aldrich under the trade name P123, formula EO)20PO70EO20) It can also be prepared by various conventional methods. When the template is polyoxyethylene-polyoxypropylene-polyoxyethylene, the number of moles of the template is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
According to the present invention, the kind of the acid agent is not particularly limited, and may be selected conventionally in the art, and may be any of various acids or acid mixtures, wherein the acid or acid mixture may be used in a pure state, or in the form of an aqueous solution thereof, preferably in the form of an aqueous solution, preferably the acid agent is a buffered solution of acetic acid and sodium acetate, more preferably the acid agent has a pH of 1 to 6, and further preferably the acid agent has a pH of 3 to 5.
According to the present invention, the condition under which the tetramethoxysilane is contacted with the acid agent is not particularly limited, and for example, the condition under which the tetramethoxysilane is contacted with the acid agent may include: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-7; preferably, the condition for contacting the tetramethoxysilane with the acid agent may include: the temperature is 10-30 deg.C, the time is 20-40 hr, and the pH value is 3-6. In order to further facilitate uniform mixing between the respective substances, the tetramethoxysilane is preferably contacted with an acid agent under stirring. The acid agent is preferably used in an amount such that the pH of the reaction system in which the tetramethoxysilane and the acid agent are contacted is 1 to 7, more preferably 3 to 6.
The crystallization conditions are not particularly limited in the present invention, and may be selected conventionally in the art, for example, the crystallization conditions may include: the temperature is 30-150 ℃ and the time is 10-72 hours, and preferably, the crystallization conditions comprise: the temperature is 40-80 ℃ and the time is 20-40 hours. The crystallization is carried out by a hydrothermal crystallization method.
In the present invention, the contacting manner between the template, ethanol, acid agent, trimethylpentane and tetramethoxysilane is not particularly limited, and for example, the above five substances may be simultaneously mixed and contacted, or several of them may be mixed and contacted first, and the remaining substances may be added to the obtained mixture and then mixed and contacted. Preferably, the contacting mode is that the template agent, the ethanol, the acid agent and the trimethylpentane are stirred and mixed at 10-100 ℃, then the tetramethoxysilane is added and the stirring and mixing are continued.
The conditions for contacting the water glass with the inorganic acid in the present invention are not particularly limited, and for example, in the step (b), the conditions for contacting the water glass with the inorganic acid generally include: the temperature can be 10-60 ℃, preferably 20-40 ℃; the time may be 1 to 5 hours, preferably 1.5 to 3 hours, and the pH value is 2 to 4. In order to further facilitate uniform mixing between the substances, the contact of the water glass with the mineral acid is preferably carried out under stirring conditions.
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.
The type of the inorganic acid may be conventionally selected in the art according to the present invention, and for example, or more of sulfuric acid, nitric acid and hydrochloric acid may be used.
In addition, in the above process for preparing the mesoporous material filter cake and the silica gel filter cake, the process for obtaining the filter cake by filtering 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 material 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 the step (c), the amounts of the mesoporous material filter cake, the silica gel filter cake and the zeolite may be selected according to the components of the spherical double mesoporous zeolite composite material carrier to be obtained, and preferably, the silica gel filter cake may be used in an amount of 1 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the mesoporous material filter cake; the zeolite may be used in an amount of 1 to 50 parts by weight, preferably 20 to 50 parts by weight.
According to the present invention, the specific operation method and conditions of the ball milling are not particularly limited, so as to allow the silica gel and the zeolite to enter the pore channels of the mesoporous material without destroying or substantially destroying the structure of the mesoporous material. One skilled in the art can select various suitable conditions to implement the present invention based on the above principles. Specifically, the ball milling is carried out in a ball mill, wherein the diameter of the milling balls in the ball mill can be 2-3 mm; the number of the grinding balls can be reasonably selected according to the size of the ball milling tank, and for the ball milling tank with the size of 50-150mL, 1 grinding ball can be generally used; the material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred. The ball milling conditions include: the rotation speed of the grinding ball can be 300-500r/min, the temperature in the ball milling tank can be 15-100 ℃, and the ball milling time can be 0.1-100 hours.
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 to 80 hours, preferably 20 to 30 hours, most preferably 24 hours.
According to the invention, in the step (d), the metal component loaded on the spherical double-mesoporous zeolite composite carrier can enter the pore channel of the spherical double-mesoporous zeolite composite carrier by adopting an impregnation mode, and the metal component can be adsorbed on the surface of the spherical double-mesoporous zeolite composite carrier by means of capillary pressure of the pore channel structure of the carrier until the metal component reaches adsorption equilibrium on the surface of the carrier, wherein the impregnation treatment can be co-impregnation treatment or step-by-step impregnation treatment, in order to save preparation cost and simplify an experimental process, the impregnation treatment is preferably co-impregnation treatment, and the condition of the co-impregnation treatment preferably comprises the step of mixing and contacting the spherical double-mesoporous zeolite composite carrier in a solution containing a Pt component precursor and a Zn component precursor, the impregnation temperature can be 25-50 ℃, and the impregnation time can be 2-6 hours.
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 dual-mesoporous zeolite composite material carrier, the Pt component precursor and the Zn component precursor are used in such amounts that 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% in the prepared isobutane dehydrogenation catalyst based on the total weight of the isobutane dehydrogenation catalyst.
Preferably, the spherical dual-mesoporous zeolite composite material carrier, the Pt component precursor and the Zn component precursor are used in amounts such that, in the prepared isobutane dehydrogenation catalyst, based on the total weight of the isobutane dehydrogenation catalyst, the content of the carrier is 98.4 to 99 wt%, the content of the Pt component calculated by the Pt element is 0.2 to 0.4 wt%, and the content of the Zn component calculated by the Zn element is 0.8 to 1.2 wt%.
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-mesoporous zeolite composite material carrier, the spherical double-mesoporous zeolite composite material carrier contains zeolite and a mesoporous molecular sieve material with an -dimensional hexagonal pore channel distribution structure, the average particle diameter of the spherical double-mesoporous zeolite composite material carrier is 30-60 mu m, and the specific surface area of the spherical double-mesoporous zeolite composite material carrier is 150-350m2The pore volume is 0.5-1.5mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 5-15nm and 30-50nm respectively.
According to the invention, in the isobutane dehydrogenation catalyst, the carrier is combined with a mesoporous molecular sieve material with a special -dimensional hexagonal pore channel distribution structure and a pore channel structure of zeolite, so that the noble metal component can be well dispersed in and on the surface of a pore channel of the catalyst, and the supported catalyst obtained by loading the Pt component and the Zn component has the advantages of the supported catalyst, such as high catalytic activity, less side reactions, simple post-treatment and the like, and also has stronger catalytic activity and higher stability, so that the supported catalyst has better dehydrogenation activity, selectivity and carbon deposition resistance in the isobutane dehydrogenation reaction, and the conversion rate of reaction raw materials is obviously improved.
According to the present invention, the spherical mesoporous zeolite composite support has a specific -dimensional hexagonal pore channel distribution structure, the average particle diameter of particles is measured by a laser particle size distribution instrument, and the specific surface area, the pore volume and the most probable pore diameter are measured according to a nitrogen adsorption method.
According to the invention, the structural parameters of the spherical double mesoporous zeolite composite material carrier are controlled aboveWithin the range, the spherical double-mesoporous zeolite composite material carrier 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 from the spherical double-mesoporous zeolite composite material carrier as the carrier. When the specific surface area of the spherical double mesoporous zeolite composite material carrier is less than 150m2When 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 mesoporous zeolite composite material carrier is more than 350m2When 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 average particle diameter of the spherical double mesoporous zeolite composite material carrier is 30-60 μm, and the specific surface area is 250-310m2The pore volume is 1-1.5mL/g, the pore diameter distribution is bimodal, and the most probable pore diameters corresponding to the bimodal are 7-12nm and 35-45nm 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.
step, the average particle diameter of the isobutane dehydrogenation catalyst is 30-60 μm, and the specific surface area is 120-300m2The pore volume is 0.3-1.3mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7-12nm and 35-45nm respectively.
According to the present invention, in the spherical dual mesoporous zeolite composite carrier, the weight of the zeolite is 1 to 50 parts by weight, preferably 20 to 50 parts by weight, based on 100 parts by weight of the mesoporous molecular sieve material having a -dimensional hexagonal pore distribution structure.
According to the present invention, the spherical mesoporous zeolite composite support may further include silica introduced through silica gel, and the "silica introduced through silica gel" refers to a silica component carried by silica gel as a preparation raw material into the spherical mesoporous zeolite composite support finally prepared during the preparation of the spherical mesoporous zeolite composite support, and in the spherical mesoporous zeolite composite support, the content of the silica introduced through silica gel may be 1 to 200 parts by weight, preferably 50 to 150 parts by weight, with respect to 100 parts by weight of the mesoporous molecular sieve material having a hexagonal pore distribution structure of dimensions.
According to the present invention, the mesoporous molecular sieve material having a distribution structure of -dimensional hexagonal pores can be a mesoporous molecular sieve material conventionally used in the art, and can be prepared according to the aforementioned method.
As mentioned above, the third aspect of the invention provides applications of the isobutane dehydrogenation catalyst prepared by the method in preparing isobutene through isobutane dehydrogenation, wherein the method for preparing isobutene through isobutane dehydrogenation comprises the step of carrying out dehydrogenation reaction on isobutane in the presence of the catalyst and hydrogen.
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 triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, available from Aldrich, is abbreviated as P123 and has the formula EO20PO70EO20The substance having a registration number of 9003-11-6 in the American chemical Abstract had an average molecular weight Mn of 5800.
In the following examples and comparative examples, X-ray diffraction analysis was carried out on an X-ray diffractometer, model D8Advance, available from Bruker AXS, Germany; scanning electron microscopy analysis was performed on a scanning electron microscope, model XL-30, available from FEI, USA; the nitrogen adsorption and desorption experiments of the samples are carried out on an ASAP2020M + C type full-automatic physicochemical adsorption analyzer produced by Micromeritics in America, the samples are degassed for 4 hours in vacuum at 350 ℃ before being measured, the specific surface area of the samples is calculated by adopting a BET method, and the pore volume and the average pore diameter are calculated by adopting a BJH model; the particle size distribution of the sample is carried out on a Malvern laser particle sizer; NH of sample3TPD experiments were carried out on an AUTOCHEM2920 full-automatic chemisorption apparatus, manufactured by Micromeritics, USA: the sample was first incubated at 480 ℃ and 10% H2Reduction in an Ar atmosphere of-90% for 1 hour. Heating to 700 ℃ in He atmosphere, standing for 1 hour, cooling to 40 ℃ to adsorb ammonia gas until saturation, purging for 1 hour in He atmosphere, heating to 700 ℃ from 40 ℃ at a speed of 10 ℃/min, and recording ammonia desorption data by using a TCD (thermal desorption detector); 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 1g (0.0002mol) of triblock copolymer surfactant P123 and 1.69g (0.037mol) of ethanol into 28ml of acetic acid and sodium acetate buffer solution with the pH value of 4, stirring at 15 ℃ until the P123 is completely dissolved, then adding 6g (0.053mol) of trimethylpentane into the obtained solution, stirring at 15 ℃ for 8h, then adding 2.13g (0.014mol) of tetramethoxysilane into the solution, stirring at 15 ℃ and the pH value of 4.5 for 20h, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 60 ℃ for 24h, then filtering and washing with deionized water for 4 times, and then carrying out suction filtration to obtain a mesoporous molecular sieve material filter cake A1 with a hexagonal pore channel single pore distribution structure of dimensions;
mixing 15 wt% water glass and 12 wt% sulfuric acid solution in a weight ratio of 5:1, carrying out contact reaction at 30 ℃ for 1.5h, adjusting the pH value to 3 by using 98 wt% sulfuric acid, carrying out suction filtration on the obtained reaction material, and washing by using distilled water until the content of sodium ions is 0.02 wt% to obtain a silica gel filter cake B1.
Putting 10g of the prepared filter cake A1, 10g of the prepared filter cake B1 and 10g of zeolite into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, the rotating speed is 400r/min, closing the ball milling tank, carrying out ball milling for 1 hour at the temperature of 60 ℃ in the ball milling tank to obtain 30g of solid powder, dissolving the solid powder in 30g of deionized water, carrying out spray drying at the rotating speed of 12000r/min at the temperature of 200 ℃, calcining the obtained product after spray drying in a muffle furnace for 24 hours at the temperature of 500 ℃, and removing a template agent to obtain 30g of a spherical double-mesoporous zeolite composite material carrier C1 with a -dimensional hexagonal pore channel double-pore distribution structure.
(2) Preparation of isobutane dehydrogenation catalyst
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml deionized water to obtain a mixture solution, and carrying out the stepsSoaking 10g of the spherical double-mesoporous zeolite composite material carrier C1 prepared in the step (1) in the mixture solution for 5h at 25 ℃, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, and drying the solid product in a drying oven at 120 ℃ 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).
Characterizing the spherical double mesoporous zeolite composite material carrier C1 and the isobutane dehydrogenation catalyst Cat-1 by using an XRD, a scanning electron microscope and an ASAP2020-M + C type adsorption instrument;
fig. 1 is an X-ray diffraction pattern of a spherical double-mesoporous zeolite composite carrier C1, wherein the abscissa is 2 θ and the ordinate is intensity, and the small-angle spectral peak appearing in the XRD pattern shows that the XRD pattern of the spherical double-mesoporous zeolite composite carrier C1 has a -dimensional hexagonal channel structure specific to the mesoporous material;
FIG. 2 is an SEM scanning electron micrograph of a spherical double mesoporous zeolite composite carrier C1, which shows that the microscopic morphology of the spherical double mesoporous zeolite composite carrier C1 is mesoporous spheres with a granularity of 30-60 μm;
table 1 shows the pore structure parameters of the spherical double mesoporous zeolite composite material carrier C1 and the isobutane dehydrogenation catalyst Cat-1.
TABLE 1
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector C1 | 290 | 1.1 | 8，40 | 30-60 |
| Catalyst Cat-1 | 266 | 1 | 7.6，38.2 | 30-60 |
the most probable aperture and the second most probable aperture are separated by commas, in order from left to right, the most probable aperture and the second most probable aperture.
As can be seen from the data of table 1, the spherical double mesoporous zeolite composite material C1 as a support has a reduced specific surface area and pore volume after supporting the Pt component and the Zn component, which indicates that the Pt component and the Zn component enter the interior of the spherical double mesoporous zeolite composite material C1 during the supporting reaction.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
An isobutane dehydrogenation catalyst was prepared according to the method of example 1, except that the same weight of alumina carrier was used instead of the spherical dual mesoporous zeolite composite carrier C1 in the process of preparing 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.
Prepared according to the method of example 1A carrier and an isobutane dehydrogenation catalyst, except that Zn (NO) is 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 mesoporous zeolite composite material carrier by a co-impregnation method, thereby preparing the isobutane dehydrogenation catalyst Cat-D-2, wherein the content of the Pt component in terms of Pt element is 0.3 wt% and the balance is the carrier by taking the total weight of the isobutane dehydrogenation catalyst Cat-D-2 as a reference).
Comparative example 3
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The same weight of an oxide catalyst such as ZnO was used as the isobutane dehydrogenation catalyst Cat-D-3.
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of the support
Adding 1g (0.0002mol) of triblock copolymer surfactant P123 and 1.84g (0.04mol) of ethanol into 28ml of acetic acid and sodium acetate buffer solution with the pH value of 5, stirring at 15 ℃ until the P123 is completely dissolved, then adding 9.12g (0.08mol) of trimethylpentane into the obtained solution, stirring at 15 ℃ for 8h, then adding 3.04g (0.02mol) of tetramethoxysilane into the solution, stirring at 25 ℃ and the pH value of 5.5 for 15h, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing at 100 ℃ for 10h, then filtering and washing with deionized water for 4 times, and then carrying out suction filtration to obtain a mesoporous molecular sieve material filter cake A2 with -dimensional hexagonal pore single-pore distribution structure;
mixing 15 wt% water glass and 12 wt% sulfuric acid solution in a weight ratio of 4:1, reacting at 40 deg.c for 1.5 hr, regulating the pH value to 2 with 98 wt% sulfuric acid, suction filtering the obtained reaction material, and washing with distilled water to sodium ion content of 0.02 wt% to obtain silica gel filter cake B2.
The preparation method comprises the steps of putting 20g of the prepared filter cake A2, 10g of the prepared filter cake B2 and 8g of zeolite into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, the rotating speed is 300r/min, closing the ball milling tank, carrying out ball milling for 0.5 hour at the temperature of 80 ℃ in the ball milling tank to obtain 38g of solid powder, dissolving the solid powder into 12g of deionized water, carrying out spray drying at the rotating speed of 11000r/min at the temperature of 250 ℃, calcining the spray-dried product for 15 hours at the temperature of 500 ℃ in a muffle furnace, and removing a template agent to obtain 35g of spherical double-mesoporous zeolite composite material carrier C2 with a -dimensional hexagonal pore passage double-pore distribution structure.
(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 mesoporous zeolite 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. And then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-2 (based on the total weight of the isobutane dehydrogenation catalyst Cat-2, 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 2 shows the pore structure parameters of the spherical double mesoporous zeolite composite material carrier C2 and the isobutane dehydrogenation catalyst Cat-2.
TABLE 2
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector C2 | 275 | 1 | 8.3，37.5 | 35-50 |
| Catalyst Cat-2 | 248 | 0.9 | 7.5，35.2 | 35-50 |
the most probable aperture and the second most probable aperture are separated by commas, in order from left to right, the most probable aperture and the second most probable aperture.
As can be seen from the data of table 2, the spherical double mesoporous zeolite composite material C2 as a support has a reduced specific surface area and pore volume after supporting the Pt component and the Zn component, which indicates that the Pt component and the Zn component enter the interior of the spherical double mesoporous zeolite composite material C2 during the supporting 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 1g (0.0002mol) of triblock copolymer surfactant P123 and 2.76g (0.06mol) of ethanol into 28ml of acetic acid and sodium acetate buffer solution with the pH value of 3, stirring at 15 ℃ until the P123 is completely dissolved, then adding 5.7g (0.05mol) of trimethylpentane into the obtained solution, stirring at 15 ℃ for 8h, then adding 2.13g (0.014mol) of tetramethoxysilane into the solution, stirring at 40 ℃ and the pH value of 3.5 for 10h, then transferring the obtained solution into a reaction kettle lined with polytetrafluoroethylene, crystallizing at 40 ℃ for 40h, then filtering and washing with deionized water for 4 times, and then carrying out suction filtration to obtain a mesoporous molecular sieve material filter cake A3 with -dimensional hexagonal pore channel single pore distribution structure;
mixing 15 wt% water glass and 12 wt% sulfuric acid solution in the weight ratio of 6:1, contacting and reacting at 20 deg.c for 3 hr, regulating the pH value to 4 with 98 wt% sulfuric acid, suction filtering the obtained reaction material, and washing with distilled water to sodium ion content of 0.02 wt% to obtain silica gel filter cake B3.
The preparation method comprises the steps of putting 20g of the prepared filter cake A3, 30g of the prepared filter cake B3 and 12g of zeolite into a 100ml ball milling tank, wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, the rotating speed is 550r/min, closing the ball milling tank, carrying out ball milling for 10 hours at the temperature of 40 ℃ in the ball milling tank to obtain 55g of solid powder, dissolving the solid powder in 30g of deionized water, carrying out spray drying at the rotating speed of 13000r/min at the temperature of 150 ℃, calcining the obtained product after spray drying in a muffle furnace for 70 hours at the temperature of 450 ℃, and removing a template agent to obtain 53g of a spherical double-mesoporous zeolite composite material carrier C3 with a -dimensional hexagonal pore passage double-pore distribution structure.
(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 mesoporous zeolite 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. 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 is 0.3 weight percent calculated by Pt element, and a Zn componentContent of 1 wt% in terms of Zn element, and the balance of carrier).
Table 3 shows the pore structure parameters of the spherical double mesoporous zeolite composite material carrier C3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 3
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector C3 | 295 | 1.3 | 8.9，37.3 | 40-55 |
| Catalyst Cat-3 | 277 | 1.1 | 7.8，36.3 | 40-55 |
the most probable aperture and the second most probable aperture are separated by commas, in order from left to right, the most probable aperture and the second most probable aperture.
As can be seen from the data of table 3, the spherical dual mesoporous zeolite composite C3 as a support has a reduced specific surface area and pore volume after supporting the Pt component and the Zn component, which indicates that the Pt component and the Zn component enter the interior of the spherical dual mesoporous zeolite composite C3 during the supporting reaction.
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 was directly fed into an Agilent 7890A gas chromatograph equipped with a hydrogen flame detector (FID) for on-line analysis, and the isobutane conversion and isobutene selectivity were obtained as shown in Table 4. After the reaction, the amount of carbon deposition in the isobutane dehydrogenation catalyst Cat-1 was measured using a TGA/DSC1 thermogravimetric analyzer from METTLER-TOLEDO, as 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. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 4.
Experimental comparative examples 1 to 3
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-3 are respectively adopted to replace the isobutane dehydrogenation catalyst Cat-1. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 4.
TABLE 4
As can be seen from table 4, when the isobutane dehydrogenation catalyst prepared by using the spherical dual-mesoporous zeolite composite material carrier of the present invention is used in the reaction of preparing isobutene by isobutane dehydrogenation, a higher isobutane conversion rate and isobutene selectivity can be still obtained after 24 hours of reaction, which indicates that the isobutane dehydrogenation catalyst of the present invention has not only a better catalytic performance, but also 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 (11)
1, A process for the preparation of an isobutane dehydrogenation catalyst, characterized in that it comprises the steps of:
(a) under the existence of a template agent, trimethylpentane and ethanol, tetramethoxysilane is contacted with an acid agent, and a product obtained after the contact is crystallized and filtered to obtain a mesoporous material filter cake;
(b) contacting water glass with inorganic acid, and filtering a product obtained after the contact to obtain a silica gel filter cake;
(c) mixing and ball-milling the mesoporous material filter cake, the silica gel filter cake and the zeolite, pulping solid powder obtained after ball-milling with water, then carrying out spray drying, and removing the template agent in the obtained product to obtain a spherical double mesoporous zeolite composite material carrier;
(d) and (c) dipping the spherical double-mesoporous zeolite 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.
2. The method of claim 1, wherein in step (a), the molar ratio of the templating agent, ethanol, trimethylpentane, and tetramethoxysilane is 1: 100-500: 200-600: 50-200 parts of;
preferably, the template agent is triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, and the acid agent is a buffer solution of acetic acid and sodium acetate with the pH value of 1-6;
preferably, the tetramethoxysilane is contacted with the acid agent under the conditions of 10-60 deg.C for 10-72 hr and pH 1-7, and the crystallization is carried out at 30-150 deg.C for 10-72 hr.
3. The method according to claim 1, wherein in the step (b), the water glass is contacted with the inorganic acid or more selected from sulfuric acid, nitric acid and hydrochloric acid under the conditions of 10-60 ℃ for 1-5 hours and pH 2-4.
4. The method according to claim 1, wherein, in step (c), the silica gel cake is used in an amount of 1 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the mesoporous material cake; the zeolite is used in an amount of 1 to 50 parts by weight, preferably 20 to 50 parts by weight.
5. The method according to claim 1, wherein, in the step (d), the spherical mesoporous zeolite composite support, the Pt component precursor and the Zn component precursor are used in amounts such that the spherical mesoporous zeolite composite support has a content of 98-99.4 wt%, the Pt component has a content of 0.1-0.5 wt% calculated as Pt element, and the Zn component has a content of 0.5-1.5 wt% calculated as Zn element in the prepared isobutane dehydrogenation catalyst.
6. An isobutane dehydrogenation catalyst produced by the process of any of claims from 1 to 5.
7. An isobutane dehydrogenation catalyst according to claim 6, wherein said isobutane dehydrogenation catalyst comprises a carrier and a Pt component and a Zn component supported on said carrier, wherein said carrier is a sphereThe spherical double-mesoporous zeolite composite material carrier contains zeolite and a mesoporous molecular sieve material with an -dimensional hexagonal pore distribution structure, the average particle diameter of the spherical double-mesoporous zeolite composite material carrier is 30-60 mu m, and the specific surface area of the spherical double-mesoporous zeolite composite material carrier is 150-350m2The pore volume is 0.5-1.5mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 5-15nm and 30-50nm respectively.
8. An isobutane dehydrogenation catalyst according to claim 7, wherein the carrier is present in an amount of 98-99.4 wt%, the Pt component is present in an amount of 0.1-0.5 wt% calculated as Pt element, and the Zn component is present in an amount of 0.5-1.5 wt% calculated as Zn element, based on the total weight of the isobutane dehydrogenation catalyst;
preferably, the average particle diameter of the isobutane dehydrogenation catalyst is 30-60 mu m, and the specific surface area is 120-300m2The pore volume is 0.3-1.3mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 7-12nm and 35-45nm respectively.
9. The isobutane dehydrogenation catalyst according to claim 7, wherein the weight of the zeolite is 1-50 parts by weight based on 100 parts by weight of the mesoporous molecular sieve material having a -dimensional hexagonal pore distribution structure.
10. Use of the isobutane dehydrogenation catalyst of any of claims in the production of isobutene by the dehydrogenation of isobutane, wherein the isobutane dehydrogenation process for producing isobutene comprises subjecting isobutane to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
11. Use according to claim 10, wherein the molar ratio of the amount of isobutane to the amount of hydrogen is between 0.5 and 1.5: 1;
preferably, the dehydrogenation reaction conditions 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 is2-5h-1。
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