CN110732343A - Isobutane dehydrogenation catalyst with carrier of three-hole hollow spherical mesoporous molecular sieve silica gel composite material and preparation method and application thereof - Google Patents
Isobutane dehydrogenation catalyst with carrier of three-hole hollow spherical mesoporous molecular sieve silica gel composite material and preparation method and application thereof Download PDFInfo
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- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 title claims abstract description 280
- 239000003054 catalyst Substances 0.000 title claims abstract description 141
- 239000001282 iso-butane Substances 0.000 title claims abstract description 140
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 126
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- 239000000741 silica gel Substances 0.000 title claims description 94
- 229910002027 silica gel Inorganic materials 0.000 title claims description 94
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims description 94
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- 238000002360 preparation method Methods 0.000 title claims description 31
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 73
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
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- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
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- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
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- 101000968043 Homo sapiens Desmocollin-1 Proteins 0.000 description 1
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- JHKXZYLNVJRAAJ-WDSKDSINSA-N Met-Ala Chemical compound CSCC[C@H](N)C(=O)N[C@@H](C)C(O)=O JHKXZYLNVJRAAJ-WDSKDSINSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
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- 229920002367 Polyisobutene Polymers 0.000 description 1
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- 150000007513 acids Chemical class 0.000 description 1
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- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- 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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- Chemical Kinetics & Catalysis (AREA)
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- Materials Engineering (AREA)
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (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 catalyst and noble metalA metal catalyst. 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.
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 hollow spherical mesoporous molecular sieve filter cake with an -dimensional through-channel distribution structure;
(b) mixing the filter cake of the hollow spherical mesoporous molecular sieve with the -dimensional through channel structure with silica gel, performing ball milling at , mixing the obtained -th ball-milling slurry with water for pulping, performing second ball milling to obtain second ball-milling slurry, performing spray drying on the second ball-milling slurry, screening by adopting a cyclone separation technology, and removing a template agent in the screened product to obtain a three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier;
(c) and (c) carrying out thermal activation on the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier obtained in the step (b), then carrying out immersion treatment 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 the obtained slurry is more exquisite by adopting a secondary ball milling technology, a spray drying technology and a cyclone separation technology, the structure of the spherical particles obtained after spray drying is stable, the spherical particles can be repeatedly used as a catalyst carrier, the strength is high, the spherical particles are not easy to break, and a binder is not needed in the preparation process of the isobutane dehydrogenation catalyst, so that the structure of a sample can be prevented from being damaged in the process of removing the binder at high temperature. In addition, the invention adopts the cyclone separation technology, the obtained catalyst has small particle size, uniform particle size distribution and narrow particle size distribution curve, can avoid the agglomeration of the ordered mesoporous material in the use process, improve the fluidity of the ordered mesoporous material, and bring convenience to the storage, transportation, post-processing and application of the ordered mesoporous material.
The three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier serving as the carrier in the isobutane dehydrogenation catalyst prepared by the method provided by the invention is small in particle size, uniform in distribution and stable in mesoporous structure, and combines the advantages of hollow spherical mesoporous molecular sieve with -dimensional through channel distribution structure, regular ordered mesoporous space characteristic of silica gel and hollow spherical shape, so that the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier is suitable for serving as the carrier of a supported catalyst, and is particularly suitable for serving as the carrier of the supported catalyst used in the reaction of preparing isobutene through isobutane dehydrogenation.
In the isobutane dehydrogenation catalyst, compared with a solid spherical material, the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier has higher activity and better poisoning resistance to catalytic dehydrogenation of isobutane, and the strong adsorption capacity of the silica gel material due to the large specific surface area and the microporous structure is combined, so that the good dispersion of metal components on the surface of the carrier is facilitated, and the prepared catalyst can achieve better dehydrogenation activity, selectivity, stability and carbon deposition resistance under the condition of very low noble 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 silica gel composite support of a three-pore hollow spherical mesoporous molecular sieve of example 1;
FIG. 2 is an SEM scanning electron microscope image of the micro-morphology of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier of example 1;
FIG. 3 is a graph showing the particle size distribution of a silica gel composite support of a three-pore hollow spherical mesoporous molecular sieve of example 1;
fig. 4 is a pore size distribution diagram of a three-pore hollow spherical mesoporous molecular sieve silica gel composite 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.
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 hollow spherical mesoporous molecular sieve filter cake with an -dimensional through-channel distribution structure;
(b) mixing the filter cake of the hollow spherical mesoporous molecular sieve with the -dimensional through channel structure with silica gel, performing ball milling at , mixing the obtained -th ball-milling slurry with water for pulping, performing second ball milling to obtain second ball-milling slurry, performing spray drying on the second ball-milling slurry, screening by adopting a cyclone separation technology, and removing a template agent in the screened product to obtain a three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier;
(c) and (c) carrying out thermal activation on the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier obtained in the step (b), then carrying out immersion treatment 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 composition of a hollow spherical mesoporous molecular sieve filter cake with an -dimensional through channel distribution structure and a silica gel filter cake is mainly controlled to enable the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier to have a three-hole distribution structure, and the micro-morphology of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier is controlled to be spherical by controlling a forming method (i.e., firstly, mixing the mesoporous molecular sieve filter cake with the -dimensional through channel structure and the silica gel filter cake, carrying out -th ball milling, mixing the obtained -th ball-milling slurry with water for pulping, then carrying out second ball-milling to obtain a second ball-milling slurry, and carrying out spray drying on the second ball-milling slurry).
In the present invention, in step (a), the amount of each substance can be selected and adjusted within a wide range. For example, the molar ratio of the template, 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 kind of the template is not particularly limited, but onlyThe obtained cake of hollow spherical mesoporous molecular sieve with D straight-through channel distribution structure can have the aforementioned D straight-through channel structure, and preferably, the template can be triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol, wherein the template can be obtained commercially (for example, from Aldrich company, under the trade name of P123, the formula of EO)20PO70EO20) It can also be prepared by various conventional methods. When the template agent is polyethylene glycol-polyglycerol-polyethylene glycol, the mole number of the template agent is calculated according to the average molecular weight of the polyethylene glycol-polyglycerol-polyethylene glycol.
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, more preferably, the acid agent is a buffer solution of acetic acid and sodium acetate, further , preferably, the acid agent has a pH of 1 to 6, 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.
Further, in the above-mentioned process of preparing a filter cake of a mesoporous molecular sieve having a -dimensional through-channel structure, the process of obtaining the filter cake by filtration may include washing repeatedly with distilled water (the number of washing may be 2 to 10) after the filtration, and then performing suction filtration.
According to the present invention, in the step (b), the preparation method of the silica gel is not particularly limited, and may be a method for preparing a silica gel, which is conventional in the art, for example, the method includes: the water glass, the inorganic acid and the glycerol are contacted.
Preferably, the conditions for contacting the water glass, the inorganic acid and the glycerol comprise: 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 increase the pore size of the prepared silica gel, preferably, the amount of water glass, inorganic acid and glycerin 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 glycerol 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.
According to the invention, the inorganic acid can be selected from the conventional inorganic acid in the field, for example, inorganic acids in sulfuric acid, nitric acid and hydrochloric acid can be used in a pure state or an aqueous solution of the inorganic acid, and the inorganic acid is preferably used in an amount such that the pH value of the reaction system under the contact condition of water glass and the inorganic acid is 2-4.
Further, in the above-mentioned process for preparing silica gel, it is preferable to obtain a silica gel cake by filtration, which 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 silica gel filter cake results in a sodium ion content of less than 0.02 wt.%.
According to the invention, in order to improve the strength of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier and further improve the catalytic performance of the prepared isobutane dehydrogenation catalyst, a secondary ball milling method for slurry is utilized for realizing the method.
According to the invention, in the step (b), the th ball milling and the second ball milling can be carried out in a ball mill, the inner wall of a ball milling pot in the ball mill is preferably an agate lining, the diameter of the grinding balls in the ball mill can be 2-3mm, the number of the grinding balls can be reasonably selected according to the size of the ball milling pot, 1 grinding ball can be generally used for the ball milling pot with the size of 50-150mL, the material of the grinding balls can be agate, polytetrafluoroethylene and the like, preferably agate, the conditions of the th ball milling and the second ball milling are the same or different, and the conditions of the th ball milling and the second ball milling respectively and independently comprise that the rotating speed of the grinding balls is 200-
According to the present invention, in the step (b), the th ball-milling slurry and water are used in a weight ratio of 1: 0.1 to 5, preferably 1: 0.5 to 3.5, and the th ball-milling slurry may be mixed with water to prepare slurry at a temperature of 25 to 60 ℃.
According to the present invention, in the step (b), the spray drying can be carried out according to a conventional manner, and can be at least selected from a pressure spray drying method, a centrifugal spray drying method and a pneumatic spray drying method, according to preferred embodiments, the spray drying adopts the centrifugal spray drying method, the spray drying can be carried out in an atomizer, the spray drying conditions can comprise a temperature of 150-.
According to the invention, the step of screening the second ball-milling slurry by adopting a cyclone separation technology after spray drying comprises the following steps: and carrying out spray drying on the second ball-milling slurry, and carrying out cyclone separation on the discharged gas containing the powder particles so as to collect the powder particles. Specifically, the cyclone separation technology is adopted to separate the powder particles contained in the discharged gas, the recovered powder particles fall into the powder collecting cylinder, the waste gas is delivered to the centrifugal fan from the outlet of the separator, the butterfly valve is installed at the lower part of the cyclone separator, and when the cyclone separator works, the butterfly valve is opened, and the obtained sample has uniformly distributed particle sizes.
According to the invention, in step (b), 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 present invention, in step (c), in order to remove hydroxyl groups and residual moisture from the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier, a thermal activation treatment is first required before the metal component is loaded on the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier, and the conditions of the thermal activation treatment may include: in the presence of nitrogen, the carrier is calcined at the temperature of 300-900 ℃ for 7-10 h.
According to the invention, in the step (c), the metal component loaded on the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier can enter the pore channel of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier by adopting an impregnation mode, and the metal component can be adsorbed on the surface of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier by virtue of capillary pressure of the pore channel structure of the carrier until the metal component reaches adsorption balance on the surface of the carrier, wherein the impregnation treatment can be co-impregnation treatment or step-by-step impregnation treatment, the impregnation treatment is preferably co-impregnation treatment for saving the preparation cost and simplifying the experimental process, and the co-impregnation treatment condition comprises that the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier is in mixed contact with a Pt precursor 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 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 (c), 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 (c), the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier, the Pt component precursor and the Zn component precursor are used in amounts such 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 three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier, the Pt component precursor and the Zn component precursor are used in amounts 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 three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier, the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier contains silica gel and a hollow spherical mesoporous molecular sieve with an -dimensional through pore channel distribution structure, the average particle size of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier is 20-30 mu m, and the specific surface area of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier is 200-400 m-2The pore volume is 0.5-1.5mL/g, the pore size distribution is trimodal, and the most probable pore sizes corresponding to the trimodal are 3-10nm, 30-50nm and 50-70nm, respectively.
The average particle size in the present invention means the particle size of the raw material particles, and when the raw material particles are spheres, the average particle size is represented by the diameter of the spheres, when the raw material particles are cubes, the average particle size is represented by the side length of the cubes, and when the raw material particles are irregularly shaped, the average particle size is represented by the mesh size of a screen mesh which can exactly screen out the raw material particles.
According to the invention, the structural parameters of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material are controlled within the range, the three-hole hollow spherical mesoporous molecular sieve silica gel composite material is ensured not to be easily agglomerated, and the supported catalyst prepared by using the three-hole hollow spherical mesoporous molecular sieve silica gel composite material as a carrier can improve isobutane dehydrogenationThe conversion rate of reaction raw materials in the reaction process of preparing isobutene. When the specific surface area of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material is less than 200m2When 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 hollow spherical mesoporous molecular sieve silica gel composite material is more than 400m2When 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.
According to the invention, as the secondary ball milling technology, the spray drying technology and the cyclone separation technology are adopted in the preparation process of the isobutane dehydrogenation catalyst, the prepared three-hole hollow spherical mesoporous molecular sieve silica gel composite material has smaller size and uniformly distributed particle size, and meanwhile, the three-hole hollow spherical mesoporous molecular sieve silica gel composite material has stable particle structure and higher mechanical strength.
Preferably, the compressive strength of the carrier is 14-16MPa, the average particle diameter is 22-28 μm, and the specific surface area is 250-350m2The pore volume is 0.6-1.3mL/g, the pore size distribution is trimodal, and the most probable pore sizes corresponding to the trimodal are 5-8nm, 30-40nm and 55-65nm 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 22-28 μm, the specific surface area is 220-320m2Per g, pore volume of 0.5 to 1.2mL/g, pore size distribution of trimodal distribution, andthe most probable pore diameters corresponding to the three peaks are respectively 5-8nm, 30-40nm and 55-65 nm.
According to the invention, in the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier, the weight ratio of the content of the hollow spherical mesoporous molecular sieve with the -dimensional through channel distribution structure to the content of the silica gel is 1: 0.5-1.5.
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, polyethylene glycol-polyglycerol-polyethylene glycol, abbreviated as P123, was purchased from Aldrich and represented by the formula EO20PO70EO209003-11-6, average molecular weight 5800, of chemical abstracts in the United states;
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 experiment of the sample is in the United statesThe method is carried out on an ASAP2020M + C type full-automatic physical and chemical adsorption analyzer produced by Micromerics corporation of China, the sample is degassed for 4 hours in vacuum at 350 ℃ before being measured, the BET method is adopted to calculate the specific surface area of the sample, and the BJH model is adopted to calculate the pore volume and the average pore diameter; 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
(1) Preparation of three-hole hollow spherical mesoporous molecular sieve silica gel composite material
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 hollow spherical mesoporous molecular sieve filter cake A1 with an -dimensional straight-through channel distribution structure;
mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and glycerol in a weight ratio of 5: 1:1, then adjusting the pH value to 3 with sulfuric acid with the concentration of 98 weight percent, then carrying out suction filtration on the obtained reaction material, and washing the reaction material with distilled water until the content of sodium ions is 0.02 weight percent to obtain a silica gel filter cake B1.
And (2) putting 20g of the filter cake A1 and 10g of the filter cake B1 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, the ball milling tank is sealed, the ball milling is carried out in the ball milling tank at the th time at the 25 ℃ for 5 hours, the obtained th ball milling slurry is mixed with 15g of deionized water at the 25 ℃ for pulping, then the second ball milling is carried out at the 25 ℃ for 5 hours, the obtained second ball milling slurry is sprayed and dried at the 200 ℃ at the rotating speed of 12000r/min, then the cyclone separation technology is adopted for screening, the screened product is calcined in a muffle furnace at the 600 ℃ for 10 hours, and P123 (template agent) is removed, so that 30g of the three-hole hollow spherical mesoporous silica gel composite material carrier C1 is obtained.
(2) Preparation of isobutane dehydrogenation catalyst
Calcining 30g of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1 obtained in the step (1) at 400 ℃ for 10h under the protection of nitrogen, and performing thermal activation treatment to remove hydroxyl and residual moisture of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml deionized water to obtain mixture solution, soaking the above three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier subjected to thermal activation treatment in the mixture solution, and soaking at 25 deg.CSoaking for 5 hours, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying box at the temperature of 120 ℃, drying for 3 hours, then placing the solid product in a muffle furnace at the temperature of 600 ℃, and roasting 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 the Pt component is 0.3 weight percent based on the Pt element, the content of the Zn component is 1 weight percent based on the Zn element, and the balance is a carrier).
The three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier 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 pattern of a three-hole hollow spherical mesoporous molecular sieve silica gel 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 three-hole hollow spherical mesoporous molecular sieve silica gel composite C1 has a -dimensional through-channel distribution structure specific to mesoporous materials.
Fig. 2 is an SEM scanning electron microscope image of a three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1, and it can be seen from the image that the microscopic morphology of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1 is microspheres with a particle size of about 25 μm, and the monodispersity thereof is good.
Fig. 3 is a particle size distribution curve of a three-hole hollow spherical mesoporous molecular sieve silica composite carrier C1, and it can be seen that the three-hole hollow spherical mesoporous molecular sieve silica composite carrier C1 has a uniform particle size distribution.
Fig. 4 is a pore size distribution diagram of a three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1, the abscissa is the pore size (unit is 0.1nm), the ordinate is the pore volume (unit is mL/g), it can be seen from the diagram that the pore size distribution of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C1 is a trimodal distribution, and the most probable pore sizes corresponding to the trimodal distributions are 6nm, 40nm and 60nm, respectively.
Table 1 shows the pore structure parameters of a three-pore hollow spherical mesoporous molecular sieve silica gel composite material carrier C1 and an 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 | 300 | 1.1 | 6，40，60 | 25 |
| Catalyst Cat-1 | 292 | 1 | 5.1，38.8，58.2 | 25 |
the most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas, in order from left to right, the most probable aperture, the second most probable aperture and the third most probable aperture.
As can be seen from the data of table 1, the specific surface area and pore volume of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C1 as a carrier were reduced after loading the Pt component and the Zn component, which indicates that the Pt component and the Zn component entered the inside of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C1 during the loading 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 three-hole hollow spherical mesoporous molecular sieve silica gel 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.
Specifically, 20g of the filter cake A1 and 10g of the filter cake B1 prepared above were put into a 100mL ball milling jar, the ball milling jar was closed, the th ball milling was carried out in the ball milling jar at a temperature of 25 ℃ for 5 hours, the obtained th ball milling slurry was mixed with 40g of water at 25 ℃ for slurrying, and the obtained slurry was spray-dried at 200 ℃ at a rotation speed of 12000r/min, thereby preparing the carrier D2 and the isobutane dehydrogenation catalyst Cat-D-2, respectively.
Table 2 shows the pore structure parameters of the carrier D2.
TABLE 2
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector D2 | 249 | 1.1 | 7，30，50 | 50 |
the most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas, in order from left to right, the most probable aperture, the second most probable aperture and the third most probable aperture.
As can be seen from the data in table 2, the particle size of the support D2 prepared by only ball mills was large and the specific surface area was small.
Comparative example 3
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
A carrier 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 type catalyst3)2·6H2O, addition of only 0.080gH2PtCl6·6H2And O, only loading a single Pt component on a three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier by a co-impregnation method, thereby preparing the isobutane dehydrogenation catalyst Cat-D-3, wherein the content of the Pt component in terms of Pt element is 0.3 wt% and the rest is the carrier by taking the total weight of the isobutane dehydrogenation catalyst Cat-D-3 as a reference.
Comparative example 4
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-4.
Comparative example 5
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 screening step was performed by using a cyclone separation technique during the preparation of the carrier, and the spray-dried product was directly thermally activated as the carrier D5, and then the Pt component and the Zn component were loaded on the thermally activated carrier by the impregnation method, thereby preparing the isobutane dehydrogenation catalyst Cat-D-5.
Table 3 shows the pore structure parameters of the carrier D5.
TABLE 3
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector D5 | 290 | 1.1 | 7，30，50 | 60 |
the most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas, in order from left to right, the most probable aperture, the second most probable aperture and the third most probable aperture.
As can be seen from the data in table 3, the particle size of the support D5 prepared without screening using the cyclone separation technique was large.
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 hollow spherical mesoporous molecular sieve filter cake A2 with an -dimensional straight-through channel distribution structure;
mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and glycerol in a weight ratio of 4: 1:1, then adjusting the pH value to 2 with sulfuric acid with the concentration of 98 weight percent, then carrying out suction filtration on the obtained reaction material, and washing the reaction material with distilled water until the content of sodium ions is 0.02 weight percent to obtain a silica gel filter cake B2.
Putting 15g of the filter cake A2 and 15g of the filter cake B2 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 the grinding balls is 3mm, the number of the grinding balls is 1, the rotating speed is 500r/min, sealing the ball milling tank, carrying out -th ball milling in the ball milling tank at the temperature of 35 ℃ for 20 hours, mixing the obtained -th ball milling slurry with 37.5g of deionized water at the temperature of 35 ℃ for pulping, carrying out second ball milling at the temperature of 25 ℃ for 10 hours, carrying out spray drying on the obtained second ball milling slurry at the temperature of 150 ℃ at the rotating speed of 13000r/min, screening by adopting a cyclone separation technology, calcining the screened product in a muffle furnace at the temperature of 600 ℃ for 15 hours, removing P123 (template agent), and obtaining 35g of a three-hole hollow mesoporous silica gel composite carrier C2.
(2) Preparation of isobutane dehydrogenation catalyst
Calcining the 35g of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C2 obtained in the step (1) at 400 ℃ for 10h under the protection of nitrogen for thermal activation treatment, and removing the hydroxyl and residual moisture of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C2.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier subjected to thermal activation treatment in the mixture solution for 5 hours at 25 ℃, then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, placing the solid product in a drying oven at 120 ℃, drying for 3 hours, then placing the dried product in a muffle furnace at 600 ℃, and roasting for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-2 (the total weight of the isobutane dehydrogenation catalyst Cat-2 is taken as a reference, the content of the Pt component in terms of the Pt element is 0.3 wt%, the content of the Zn component in terms of the Zn element is 1 wt%, and the balance is the carrier).
Table 4 shows the pore structure parameters of the three-pore hollow spherical mesoporous molecular sieve silica composite material carrier C2 and the isobutane dehydrogenation catalyst Cat-2.
TABLE 4
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector C2 | 285 | 1 | 5.3，37.5，58.2 | 27 |
| Catalyst Cat-2 | 273 | 0.9 | 5，37，56.6 | 27 |
the most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas, in order from left to right, the most probable aperture, the second most probable aperture and the third most probable aperture.
As can be seen from the data of table 4, the specific surface area and pore volume of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C2 as a carrier were reduced after loading the Pt component and the Zn component, which indicates that the Pt component and the Zn component entered the inside of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C2 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 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 with a polytetrafluoroethylene lining, crystallizing at 40 ℃ for 40h, then filtering and washing with deionized water for 4 times, and then carrying out suction filtration to obtain a hollow spherical mesoporous molecular sieve filter cake A3 with an -dimensional straight-through channel distribution structure;
mixing 15 wt% of water glass, 12 wt% of sulfuric acid solution and glycerol in a weight ratio of 6:1:1, and then the reaction mixture was subjected to a contact reaction at 20 ℃ for 3 hours, followed by adjusting the pH to 4 with sulfuric acid having a concentration of 98% by weight, and then the resulting reaction mass was subjected to suction filtration and washed with distilled water until the sodium ion content was 0.02% by weight, to obtain a silica gel cake B3.
And (2) putting 20g of the filter cake A3 and 30g of the filter cake B3 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, the ball milling tank is closed, the ball milling is carried out in the ball milling tank at the th time, the temperature is 50 ℃ and the time is 10 hours, the obtained ball milling slurry is mixed with 15g of deionized water at the 50 ℃ to prepare slurry, then the second ball milling is carried out, the temperature is 40 ℃ and the time is 5 hours, the obtained second ball milling slurry is sprayed and dried at the 250 ℃ and the rotating speed is 11000r/min, then a cyclone separation technology is adopted to carry out screening, the screened product is calcined in a muffle furnace at the 300 ℃ for 24 hours, P123 (template agent) is removed, and 53g of the three-hole hollow spherical mesoporous silica gel composite material carrier C3.
(2) Preparation of isobutane dehydrogenation catalyst
And (2) calcining the 53g of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C3 obtained in the step (1) at 400 ℃ for 10 hours under the protection of nitrogen to carry out thermal activation treatment, and removing hydroxyl and residual moisture of the three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier C3.
0.080g H2PtCl6·6H2O and 0.457g Zn (NO)3)2·6H2Dissolving O in 100ml deionized water to obtain a mixture solution, soaking the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier subjected to thermal activation treatment in the mixture solution for 5 hours at 25 ℃, evaporating solvent water in the system by using a rotary evaporator to obtain a solid product, and placing the solid product in a rotary evaporatorDrying the catalyst in a drying oven at the temperature of 120 ℃ for 3 hours, then placing the catalyst in a muffle furnace at the temperature of 600 ℃ for roasting for 6 hours 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 element is 0.3 weight percent, the content of a Zn component in terms of Zn element is 1 weight percent, and the balance is a carrier).
Table 5 shows the pore structure parameters of the three-pore hollow spherical mesoporous molecular sieve silica composite material carrier C3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 5
| Sample (I) | Specific surface area (m)2/g) | Pore volume (ml/g) | Most probable aperture*(nm) | Particle size (. mu.m) |
| Vector C3 | 273 | 0.9 | 6.3，37.3，57.8 | 24 |
| Catalyst Cat-3 | 260 | 0.8 | 5.3，35.9，57 | 24 |
the most probable aperture, the second most probable aperture and the third most probable aperture are separated by commas, in order from left to right, the most probable aperture, the second most probable aperture and the third most probable aperture.
As can be seen from the data of table 5, the specific surface area and pore volume of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C3 as a carrier were reduced after loading the Pt component and the Zn component, which indicates that the Pt component and the Zn component entered the inside of the three-hole hollow spherical mesoporous molecular sieve silica gel composite material C3 during the loading 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 6.
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 6.
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. The isobutane conversion, isobutene selectivity and carbon deposition amount of the isobutane dehydrogenation catalyst are shown in table 6.
TABLE 6
As can be seen from table 6, when the isobutane dehydrogenation catalyst prepared by using the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier of the present invention is used in the reaction for preparing isobutene through isobutane dehydrogenation, a higher isobutane conversion rate and isobutene selectivity can be 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 (12)
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 hollow spherical mesoporous molecular sieve filter cake with an -dimensional through-channel distribution structure;
(b) mixing the filter cake of the hollow spherical mesoporous molecular sieve with the -dimensional through channel structure with silica gel, performing ball milling at , mixing the obtained -th ball-milling slurry with water for pulping, performing second ball milling to obtain second ball-milling slurry, performing spray drying on the second ball-milling slurry, screening by adopting a cyclone separation technology, and removing a template agent in the screened product to obtain a three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier;
(c) and (c) carrying out thermal activation on the three-hole hollow spherical mesoporous molecular sieve silica gel composite material carrier obtained in the step (b), then carrying out immersion treatment 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 polyethylene glycol-polyglycerol-polyethylene glycol, 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 of claim 1, wherein, in step (b), the silica gel is formed by a method comprising: contacting water glass, inorganic acid and glycerol;
preferably, the conditions of the contacting include: the temperature is 10-60 ℃, the time is 1-5h, the pH value is 2-4, and the weight ratio of the water glass, the inorganic acid and the glycerol can be 3-6:1: 1;
more preferably, the inorganic acid solution is at least aqueous solutions of sulfuric acid, nitric acid, and hydrochloric acid.
4. The method as claimed in claim 1, wherein, in the step (b), the th ball milling and the second ball milling are performed under the same or different conditions, and the th ball milling and the second ball milling are performed under the conditions of 200 r/min, 15-100 ℃ of temperature in the ball milling tank and 0.1-100 hours of ball milling time, respectively;
preferably, the weight ratio of the th ball milling slurry to the water is 1: 0.1-5, and the temperature for mixing the th ball milling slurry with the water for pulping is 25-60 ℃;
preferably, the conditions of the spray drying include: the temperature is 150-;
preferably, the screening process of the second ball-milling slurry by using the cyclone separation technology after the spray drying comprises the following steps: and performing cyclone separation on the gas containing the powder particles discharged by the second ball-milling slurry through spray drying to collect the powder particles.
5. The method according to claim 1, wherein, in the step (b), the weight ratio of the filter cake of the mesoporous molecular sieve having dimensional through channel structure to the silica gel is 1: 0.5-1.5.
6. The method according to claim 1, wherein, in the step (c), the three-hole hollow spherical mesoporous molecular sieve silica gel composite 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 three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier, 0.1-0.5 wt% of the Pt component calculated as Pt element and 0.5-1.5 wt% of the Zn component calculated as Zn element, based on the total weight of the isobutane dehydrogenation catalyst;
preferably, the conditions of thermal activation include: the temperature is 300-900 ℃ and the time is 7-10 h; the conditions of the impregnation treatment include: the temperature is 25-50 ℃ and the time is 2-6 h.
7. An isobutane dehydrogenation catalyst produced by the process of any of claims of claims 1-6.
8. The isobutane dehydrogenation catalyst according to claim 7, 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 three-hole hollow spherical mesoporous molecular sieve silica gel composite carrier comprising silica gel and a hollow spherical mesoporous molecular sieve having a -dimensional through-channel distribution structure, and the three-hole hollow sphere comprises a hollow sphere and a mesoporous molecular sieve having a three-hole hollow sphere and a three-hole straight-through channel distribution structureThe average particle diameter of the mesoporous molecular sieve silica gel composite material carrier is 20-30 mu m, and the specific surface area is 200-400m2The pore volume is 0.5-1.5mL/g, the pore size distribution is trimodal, and the most probable pore sizes corresponding to the trimodal are 3-10nm, 30-50nm and 50-70nm, respectively.
9. An isobutane dehydrogenation catalyst according to claim 8, 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 22-28 mu m, and the specific surface area is 220-320m2The pore volume is 0.5-1.2mL/g, the pore size distribution is trimodal, and the most probable pore sizes corresponding to the trimodal are 5-8nm, 30-40nm and 55-65nm respectively.
10. The isobutane dehydrogenation catalyst according to claim 8, wherein the content of the hollow spherical mesoporous molecular sieve having an -dimensional through channel distribution structure and the silica gel is in a weight ratio of 1: 0.5-1.5.
11. Use of the isobutane dehydrogenation catalyst according to any of claims 7-10 in the preparation of isobutene by the dehydrogenation of isobutane, wherein the method for preparing isobutene by the dehydrogenation of isobutane comprises dehydrogenating isobutane in the presence of a catalyst and hydrogen.
12. Use according to claim 11, 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 is 2-5h-1。
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Application publication date: 20200131 |