CN110496630B - Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation - Google Patents
Isobutane dehydrogenation catalyst, preparation method thereof and method for preparing isobutene through isobutane dehydrogenation Download PDFInfo
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- 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
-
- B01J35/40—
-
- B01J35/51—
-
- 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
Abstract
The invention relates to the field of catalysts, and discloses an isobutane dehydrogenation catalyst, a preparation method thereof and a method for preparing isobutene through isobutane dehydrogenation. The method for preparing the isobutane dehydrogenation catalyst comprises the following steps: (a) preparing a mesoporous molecular sieve material; (b) preparing silica gel; (c) mixing and ball-milling the mesoporous material filter cake and the silica gel filter cake, 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 composite material carrier; (d) and (c) dipping the spherical double-mesoporous 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. The obtained isobutane dehydrogenation catalyst has better dehydrogenation activity and carbon deposition resistance.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for preparing an isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
Background
Isobutene is an important organic chemical raw material and is mainly used for preparing various organic raw materials and fine chemicals such as methyl tert-butyl ether, butyl rubber, methyl ethyl ketone, polyisobutylene, methyl methacrylate, isoprene, tert-butyl phenol, tert-butyl amine, 1, 4-butanediol, ABS resin and the like. The main sources of isobutene are the by-product C4 fraction from an apparatus for producing ethylene by steam cracking of naphtha, the by-product C4 fraction from a refinery Fluid Catalytic Cracking (FCC) apparatus, and the by-product tert-butyl alcohol (TAB) in the synthesis of propylene oxide by the Halcon method.
In recent years, with the development and utilization of downstream products of isobutene, the demand of isobutene is increased year by year, and the traditional isobutene production cannot meet the huge demand of the chemical industry on isobutene, so the research and development work of a new isobutene production technology becomes a hot spot of the chemical industry. Among the most competitive technologies, isobutane dehydrogenation, n-butene skeletal isomerization and isobutene production by a novel FCC unit are known. Among the methods, the research on the reaction for preparing isobutene by directly dehydrogenating isobutane is early, and the industrial production is realized. China has abundant C4 resources, but the chemical utilization rate of C4 fraction is low in China, most of isobutane is directly used as fuel, and the waste is serious. The reasonable utilization of C4 resource is an urgent task in the petrochemical research field. Therefore, the isobutene prepared by dehydrogenating isobutane has a great development prospect in China.
The catalysts for preparing isobutene by isobutane dehydrogenation mainly comprise two types: oxide catalysts and noble metal catalysts. The oxide catalyst mainly comprises Cr2O3、V2O5、Fe2O3、MoO3ZnO, etc., and a composite oxide thereof, such as V-Sb-O, V-Mo-O, Ni-V-O, V-Nb-O, Cr-Ce-O, molybdate, etc. Compared with noble metal catalysts, oxide catalysts are less expensive. However, the catalyst is easy to deposit carbon, and the catalytic activity, selectivity and stability are low. In addition, most oxide catalysts contain highly toxic components, which is disadvantageousIs environment-friendly. 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.
Therefore, how to improve the reaction performance of the isobutane dehydrogenation catalyst is a problem to be solved in the field of preparing isobutene by isobutane dehydrogenation.
Disclosure of Invention
The invention aims to overcome the defects of uneven dispersion of noble metal active components and poor catalytic activity and stability of the existing isobutane dehydrogenation catalyst, and provides a method for preparing the isobutane dehydrogenation catalyst, the isobutane dehydrogenation catalyst prepared by the method and a method for preparing isobutene by isobutane dehydrogenation.
In order to accomplish the above object, an aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent and butanol, contacting ethyl orthosilicate with an acid agent, crystallizing and filtering a product obtained after the contact 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 and the silica gel filter cake, 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 composite material carrier;
(d) and (c) dipping the spherical double-mesoporous composite material carrier obtained in the step (c) in a solution containing a Pt component precursor and a Zn component precursor, and then sequentially carrying out solvent removal treatment, drying and roasting.
A second aspect of the invention provides an isobutane dehydrogenation catalyst prepared by the aforementioned process.
The third aspect of the invention provides a method for preparing isobutene by dehydrogenating isobutane, which comprises the following steps: and (2) carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and hydrogen, wherein the catalyst is the isobutane dehydrogenation catalyst prepared by the method.
The 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 in the preparation process of the isobutane dehydrogenation catalyst, a composite material containing a mesoporous molecular sieve material with a three-dimensional cubic pore channel distribution structure and silicon dioxide is used as a carrier, the characteristics of high specific surface area and large pore volume of the ordered mesoporous molecular sieve and the characteristics of regular ordered mesoporous space of silica gel with the three-dimensional cubic pore channel distribution structure and the advantages of spherical morphology are combined, the advantages of large pore diameter and narrow distribution are also increased, the pore diameter distribution of the ordered mesoporous molecular sieve and the silica gel is in unique bimodal distribution, the advantages of a microsphere structure and the ordered mesoporous material with the bimodal distribution are skillfully combined, and the loading of active components is facilitated.
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) according to the isobutane dehydrogenation catalyst prepared by the method provided by the invention, as the co-impregnation method is adopted to load the active Pt component and the Zn component, the stability of the obtained Zn center with an oxidized structure under the high-temperature reduction condition is very high, the inactivation of the single Pt component loaded by the carrier can be inhibited, the carbon deposition is reduced, the 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 the geometric effect, so that the carbon deposition risk in the reaction process of preparing isobutene by anaerobic dehydrogenation of isobutane can be obviously reduced, the selectivity of a target product is improved, and the stability of the isobutane dehydrogenation catalyst is improved;
(4) the dispersity of the noble metal active component on the isobutane dehydrogenation catalyst prepared by the method provided by the invention is higher, so that the isobutane dehydrogenation catalyst is not easy to deactivate due to the agglomeration of active metal particles in the reaction process;
(5) the isobutane dehydrogenation catalyst prepared by the method provided by the invention shows good catalytic performance when used for preparing isobutene by anaerobic dehydrogenation of isobutane, and has the advantages of high isobutane conversion rate, high isobutene selectivity, good catalyst stability and low carbon deposition.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is an X-ray diffraction pattern of a spherical double mesoporous composite material carrier of example 1;
FIG. 2 is an SEM scanning electron micrograph of the spherical double mesoporous composite support of example 1;
fig. 3 is a distribution diagram of the pore size structure of the spherical dual mesoporous 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.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As previously described, a first aspect of the present invention provides a method for preparing an isobutane dehydrogenation catalyst, the method comprising the steps of:
(a) in the presence of a template agent and butanol, contacting ethyl orthosilicate with an acid agent, crystallizing and filtering a product obtained after the contact 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 and the silica gel filter cake, 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 composite material carrier;
(d) and (c) dipping the spherical double-mesoporous 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 a three-dimensional cubic pore channel distribution structure.
In the process of forming the spherical double-mesoporous composite material carrier, the pore size distribution is controlled to be bimodal distribution mainly by controlling the composition of the mesoporous material filter cake and the silica gel filter cake, the spherical double-mesoporous composite material carrier is enabled to have a double-pore distribution structure, and the micro-morphology of the spherical double-mesoporous composite material carrier is controlled to be spherical by controlling a forming method (namely, the mesoporous material filter cake and the silica gel filter cake are mixed and ball-milled firstly, then the obtained solid powder is slurried with water and then is spray-dried), so that the mesoporous molecular sieve material with a three-dimensional cubic pore channel distribution structure, silica brought by the silica gel and the advantages of the spherical carrier can be synthesized by using common and easily-obtained raw materials under simple operation conditions, and the carrier not only has the porous structure, the large specific surface area and the like of the mesoporous molecular sieve material, The isobutane dehydrogenation catalyst with no acidity on the surface, good dehydrogenation activity, high selectivity, strong stability and good carbon deposition resistance can be prepared by impregnating and loading a Pt component and a Zn component.
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, butanol, and ethyl orthosilicate may be 1: 10-100: 10-90, preferably 1: 60-90: 50-75.
According to the invention, in order to make the obtained mesoporous material filter cake have a three-dimensional cubic pore channel distribution structure, the type of the template agent is preferably 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 acidic agent may be any of various substances or mixtures (e.g., solutions) conventionally used for adjusting pH. The acid agent is preferably used in the form of an aqueous solution. Preferably, the acid agent is a hydrochloric acid solution, and the pH value of the acid agent is 1-6.
According to the invention, the butanol is preferably n-butanol.
According to the invention, the conditions under which the tetraethoxysilane 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 conditions for contacting the tetraethoxysilane 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 facilitate uniform mixing of the substances, the contact of the tetraethoxysilane with the acid agent is preferably carried out under stirring. The dosage of the acid agent is preferably such that the pH value of the contact reaction system of the tetraethoxysilane and the acid agent is 1-7, and more preferably 3-6.
The crystallization conditions of the present invention 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 addition, the contact mode among the template agent, the butanol, the acid agent and the ethyl orthosilicate is not particularly limited in the present invention, and for example, the four substances may be simultaneously mixed and contacted, or several of the substances may be mixed and contacted first, and then the rest of the substances may be added to the obtained mixture to continue mixing and contacting. Preferably, the contact mode is that the template agent, the butanol and the acid agent are stirred and mixed at 10-100 ℃, then the tetraethoxysilane is added and the stirring and the mixing are continued.
According to the method for preparing an isobutane dehydrogenation catalyst provided by the present invention, in the step (b), the conditions for contacting the water glass with the inorganic acid may 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.
According to the present invention, the inorganic acid may be one or more of sulfuric acid, nitric acid and hydrochloric acid. The inorganic acid may be used in a pure form or in the form of an aqueous solution thereof. The inorganic acid is preferably used in such an amount that the reaction system has a pH of 2 to 4 under the contact conditions of the water glass and the inorganic acid. Preferably, the weight ratio of the water glass to the inorganic acid is 3-6: 1.
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 amount of the mesoporous material filter cake and the silica gel filter cake may be selected according to the components of the spherical double mesoporous 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.
According to the invention, the specific operation method and conditions of the ball milling are based on that the structure of the mesoporous material is not damaged or basically not damaged and the silica gel enters the pore canal 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 specific operation method and conditions of the spray drying are preferably: adding a slurry prepared from the solid powder and water into an atomizer, and rotating at a high speed to realize spray drying. Wherein the spray drying conditions may include: 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 preferably a calcination method. The conditions for removing the template agent may include: the temperature is 300-600 ℃, preferably 350-550 ℃, and most preferably 500 ℃; the time is 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 composite material carrier can adopt an impregnation mode, the metal component enters the pore channel of the spherical double-mesoporous composite material carrier by virtue of capillary pressure of the pore channel structure of the carrier, and meanwhile, the metal component can be adsorbed on the surface of the spherical double-mesoporous composite material carrier until the metal component reaches adsorption balance on the surface of the carrier. The dipping treatment may be a co-dipping treatment or a stepwise dipping treatment. In order to save the preparation cost and simplify the experimental process, the dipping treatment is preferably co-dipping treatment; further preferably, the conditions of the co-impregnation treatment include: the spherical double-mesoporous composite material carrier is mixed and contacted with a solution containing a Pt component precursor and a Zn component precursor, the dipping temperature can be 25-50 ℃, and the dipping time can be 2-6 h.
According to the invention, the Pt component precursor is preferably H2PtCl6The Zn component precursor is preferably Zn (NO)3)2。
The concentration of the solution containing the Pt component precursor and the Zn component precursor is not particularly limited in the present invention, and may be conventionally selected in the art, for example, the concentration of the Pt component precursor may be 0.001 to 0.003mol/L, and the concentration of the Zn component precursor may be 0.015 to 0.1 mol/L.
According to the present invention, the solvent removal treatment can be carried out by a method conventional in the art, for example, a rotary evaporator can be used to remove the solvent in the system.
According to the present invention, in the step (d), the drying may be performed in a drying oven, and the firing may be performed in a muffle furnace. The drying conditions may include: the temperature is 110-150 ℃ and the time is 3-6 h; the conditions for the firing may include: the temperature is 600 ℃ and 650 ℃, and the time is 5-8 h.
According to the invention, in the step (d), the spherical dual-mesoporous 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 98-99.4 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 spherical dual-mesoporous 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 composite material carrier, the spherical double-mesoporous composite material carrier contains a mesoporous molecular sieve material with a three-dimensional cubic pore channel distribution structure and silicon dioxide, the average particle size of the spherical double-mesoporous composite material carrier is 30-60 mu m, and the specific surface area is 150-600 m-2The pore volume is 0.5-2mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 4-8nm and 20-30nm respectively.
According to the invention, in the isobutane dehydrogenation catalyst, the spherical double-mesoporous composite material carrier has a special three-dimensional cubic channel distribution structure, the average particle size of particles is measured by adopting 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. In the present invention, the particle size refers to the particle size of the raw material particles, and is expressed by the diameter of the sphere when the raw material particles are spherical, by the side length of the cube when the raw material particles are cubic, and by the mesh size of the screen that can sieve out the raw material particles when the raw material particles are irregularly shaped.
According to the invention, the spherical double-mesoporous composite material carrier can ensure that the spherical double-mesoporous composite material carrier is not easy to agglomerate by controlling the particle size of the spherical double-mesoporous composite material carrier within the range, and the conversion rate of reaction raw materials in the reaction process of preparing isobutene by isobutane dehydrogenation can be improved by using the supported catalyst prepared by using the spherical double-mesoporous composite material carrier as the carrier. When the specific surface area of the spherical double mesoporous 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 composite material carrier is more than 600m2G and/or pore volumeWhen the concentration is more than 2mL/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 reaction raw materials in the reaction process of preparing isobutene by isobutane dehydrogenation is influenced.
Preferably, the average particle diameter of the spherical double mesoporous composite material carrier is 20-55 μm, and the specific surface area is 180-600m2The pore volume is 0.8-1.4mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 4.5-7.5nm and 21-29nm 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.
In the invention, the content of each element in the isobutane dehydrogenation catalyst component can be measured by adopting an X-ray fluorescence spectrum analysis method.
Further preferably, the average particle diameter of the isobutane dehydrogenation catalyst is 30-60 μm, and the specific surface area is 100-500m2The pore volume is 0.4-1.8mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 4-8nm and 20-30nm respectively. .
According to the present invention, in the spherical double mesoporous composite material support, the weight of the silica is 1 to 200 parts by weight, preferably 50 to 150 parts by weight, based on 100 parts by weight of the mesoporous molecular sieve material having a three-dimensional cubic pore channel distribution structure.
According to the invention, the silicon dioxide contained in the spherical double-mesoporous composite material carrier is introduced through silica gel. The term "silica introduced through silica gel" refers to a silica component which is brought into the finally prepared spherical double-mesoporous composite material carrier by using silica gel as a preparation raw material during the preparation process of the spherical double-mesoporous composite material carrier. In the spherical double mesoporous composite material support, the content of the silica introduced through the 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 three-dimensional cubic pore channel distribution structure.
According to the present invention, the mesoporous molecular sieve material having a three-dimensional cubic pore channel distribution structure may be a mesoporous molecular sieve material conventionally used in the art, and may be prepared according to the aforementioned method.
As described above, the third aspect of the present invention provides a method for producing isobutene by dehydrogenating isobutane, including: and (2) carrying out dehydrogenation reaction on the isobutane in the presence of a catalyst and hydrogen, wherein the catalyst is the isobutane dehydrogenation catalyst prepared by the method.
When the isobutane dehydrogenation catalyst prepared by the method provided by the invention is used for catalyzing isobutane to dehydrogenate to prepare isobutene, the conversion rate of isobutane and the selectivity of isobutene can be greatly improved.
According to the present invention, in order to increase the isobutane conversion rate and prevent the catalyst from coking, it is preferable that the molar ratio of the amount of isobutane to the amount of hydrogen is 0.5 to 1.5: 1.
the conditions for the dehydrogenation reaction in the present invention are not particularly limited and may be conventionally selected in the art, and for example, the conditions for the dehydrogenation reaction may include: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, the 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; pore structure parameter analysis was performed on an ASAP2020-M + C type adsorber, available from Micromeritics, USA, and BET method was used for the specific surface area and pore volume calculation of the sample; the particle size distribution of the sample is carried out on a Malvern laser particle sizer; the rotary evaporator is produced by German IKA company, and the model is RV10 digital; the active component loading of the isobutane dehydrogenation catalyst was measured on a wavelength dispersive X-ray fluorescence spectrometer, available from parnacco, netherlands, model No. Axios-Advanced; analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A.
In the following experimental examples and experimental comparative examples, the conversion (%) of isobutane was equal to the amount of isobutane consumed by the reaction/initial amount of isobutane × 100%;
the selectivity (%) of isobutylene was defined as the amount of isobutane consumed for producing isobutylene/total consumption of isobutane × 100%.
Example 1
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of spherical double-mesoporous composite material carrier
6g (0.001mol) of a triblock copolymer surfactant P123 was dissolved in 10ml of a hydrochloric acid aqueous solution having a pH value of 4 and 220ml of a deionized water solution, stirred for 4 hours until the P123 was dissolved to form a transparent solution, 6g (0.08mol) of n-butanol was added to the transparent solution and stirred for 1 hour, then placed in a water bath at 40 ℃, 12.9g (0.062mol) of ethyl orthosilicate was slowly added dropwise to the solution, stirred for 24 hours while maintaining the temperature at about 40 ℃ and a pH value of 4.5, then subjected to hydrothermal treatment at 100 ℃ for 24 hours, followed by filtration and washing with deionized water 4 times, and then suction-filtered to obtain a cake A1 of a mesoporous molecular sieve material having three-dimensional cubic pore channels.
Mixing 15 wt% water glass and 12 wt% sulfuric acid solution in a weight ratio of 5:1, reacting at 30 deg.c for 2 hr, regulating the pH to 3 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 B1.
And putting 10g of the prepared filter cake A1 and 10g of the prepared filter cake B1 into a 100ml ball milling tank together, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 400 r/min. Sealing the ball milling tank, and carrying out ball milling for 1 hour in the ball milling tank at the temperature of 60 ℃ to obtain 30g of solid powder; dissolving the solid powder in 30g of deionized water, and spray-drying at 200 ℃ at a rotating speed of 12000 r/min; calcining the spray-dried product in a muffle furnace at 500 ℃ for 24 hours, and removing the template agent to obtain 30g of spherical double-mesoporous composite material carrier C1 with a three-dimensional cubic 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 composite material carrier C1 prepared in the step (1) 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 drying oven at 120 ℃ for drying for 3 hours. And then roasting the mixture in a muffle furnace at the temperature of 600 ℃ for 6 hours to obtain the isobutane dehydrogenation catalyst Cat-1 (based on the total weight of the isobutane dehydrogenation catalyst Cat-1, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
The spherical double mesoporous 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, wherein the curve in the pattern is an XRD pattern of spherical double mesoporous composite carrier C1, the abscissa is 2 θ, and the ordinate is intensity, and the XRD pattern of spherical double mesoporous composite carrier C1 has a 2D hexagonal channel structure specific to mesoporous materials, as can be seen from the small angle peaks appearing in the XRD pattern;
FIG. 2 is an SEM (scanning electron microscope) image, which shows that the microscopic morphology of the spherical double mesoporous composite material carrier C1 is mesoporous spheres with the granularity of 30-60 μm;
fig. 3 is a pore size distribution graph, and it can be seen from the graph that the pore size distribution of the spherical double mesoporous composite material carrier C1 is bimodal, and the channels are very uniform.
Table 1 shows the pore structure parameters of the spherical double mesoporous 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 | 271 | 1.7 | 7.2，25 | 30-60 |
| Catalyst Cat-1 | 243 | 1.5 | 7，23.3 | 30-60 |
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data of table 1, the specific surface area and the pore volume of the spherical dual mesoporous composite support are reduced after the Pt component and the Zn component are loaded, which indicates that the Pt component and the Zn component enter the interior of the spherical dual mesoporous composite support during the loading reaction.
Comparative example 1
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
The carrier and the isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that in the preparation of the isobutane dehydrogenation catalyst, the spherical dual-mesoporous composite carrier was replaced with the same weight of alumina carrier, thereby preparing the carrier D1 and the isobutane dehydrogenation catalyst Cat-D-1, respectively.
Comparative example 2
This comparative example serves to illustrate a reference isobutane dehydrogenation catalyst and a process for its preparation.
A support and an isobutane dehydrogenation catalyst were prepared according to the method of example 1, except that there was no spray-drying step in the preparation of the isobutane dehydrogenation catalyst, and a Pt component and a Zn component were supported on the support only by the impregnation method, thereby preparing a support D2 and an isobutane dehydrogenation catalyst Cat-D-2, respectively.
Comparative example 3
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 0.080gH2PtCl6·6H2O, only loading a single Pt component on a spherical double-mesoporous composite material carrier by a co-impregnation method to prepare the isobutane dehydrogenation catalyst Cat-D-3, taking the total weight of the isobutane dehydrogenation catalyst Cat-D-3 as a reference,the content of the Pt component was 0.3 wt% in terms of Pt element, and the balance was the support).
Example 2
This example is illustrative of an isobutane dehydrogenation catalyst and a method for preparing the same.
(1) Preparation of spherical double-mesoporous composite material carrier
Dissolving 6g (0.001mol) of triblock copolymer surfactant P123 in 10ml of hydrochloric acid aqueous solution with the pH value of 4 and 220ml of deionized water solution, stirring for 4h until the P123 is dissolved to form a transparent solution, adding 6.7g (0.09mol) of n-butyl alcohol into the transparent solution, stirring for 1h, then placing the transparent solution in a water bath at 40 ℃, slowly dripping 10.4g (0.05mol) of ethyl orthosilicate into the solution, stirring for 24h under the condition that the temperature is kept at about 40 ℃ and the pH value is 5, then carrying out hydrothermal treatment for 36h at 90 ℃, then carrying out filtration and washing for 4 times by using deionized water, and then carrying out suction filtration to obtain a filter cake A2 of a mesoporous material with three-dimensional cubic pore molecular sieves;
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.
And (3) putting 20g of the prepared filter cake A2 and 10g of the prepared filter cake B2 into a 100ml ball milling tank together, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 300 r/min. Sealing the ball milling tank, and carrying out ball milling for 0.5 hour in the ball milling tank at the temperature of 80 ℃ to obtain 38g of solid powder; dissolving the solid powder in 12g of deionized water, and spray-drying at 250 ℃ at the rotating speed of 11000 r/min; calcining the spray-dried product in a muffle furnace at 500 ℃ for 15 hours, and removing the template agent to obtain 35g of spherical double-mesoporous composite material carrier C2 with a three-dimensional cubic pore channel distribution structure.
(2) Preparation of isobutane dehydrogenation catalyst
0.080g H2PtCl6·6H2O and 0.457g Zn(NO3)2·6H2Dissolving O in 100ml of deionized water to obtain a mixture solution, soaking 10g of the spherical double-mesoporous composite material carrier C2 prepared in the step (1) 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 drying oven at 120 ℃ for drying for 3 hours. 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 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 | 260 | 1.5 | 7.5，24 | 35-55 |
| Catalyst Cat-2 | 235 | 1.4 | 7.4，22.9 | 35-55 |
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data of table 2, the specific surface area and the pore volume of the spherical dual mesoporous composite support are reduced after the Pt component and the Zn component are loaded, which indicates that the Pt component and the Zn component enter the interior of the spherical dual mesoporous composite support 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 spherical double-mesoporous composite material carrier
Dissolving 6g (0.001mol) of triblock copolymer surfactant P123 in 10ml of hydrochloric acid aqueous solution with the pH value of 4 and 220ml of deionized water solution, stirring for 4h until the P123 is dissolved to form a transparent solution, adding 5.2g (0.07mol) of n-butyl alcohol into the transparent solution, stirring for 1h, then placing the transparent solution in a water bath at 40 ℃, slowly dripping 12.5g (0.06mol) of tetraethoxysilane into the solution, stirring for 24h under the condition that the temperature is kept at about 40 ℃ and the pH value is 5, then carrying out hydrothermal treatment for 36h at 100 ℃, then carrying out filtration and washing for 4 times by using deionized water, and then carrying out suction filtration to obtain a filter cake A3 of a mesoporous material with three-dimensional cubic pore molecular sieves;
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.
And (3) putting 20g of the prepared filter cake A3 and 30g of the prepared filter cake B3 into a 100ml ball milling tank together, wherein the ball milling tank is made of polytetrafluoroethylene, grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 1, and the rotating speed is 550 r/min. Sealing the ball milling tank, and carrying out ball milling for 10 hours in the ball milling tank at the temperature of 40 ℃ to obtain 55g of solid powder; dissolving the solid powder in 30g of deionized water, and spray-drying at 150 ℃ at the rotating speed of 13000 r/min; calcining the spray-dried product in a muffle furnace at 450 ℃ for 70 hours, and removing the template agent to obtain 53g of spherical double-mesoporous composite material carrier C3 with a three-dimensional cubic 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 composite material carrier C3 prepared in the step (1) 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 drying oven at 120 ℃ for drying for 3 hours. And then roasting the mixture for 6 hours in a muffle furnace at the temperature of 600 ℃ to obtain the isobutane dehydrogenation catalyst Cat-3 (based on the total weight of the isobutane dehydrogenation catalyst Cat-3, the content of a Pt component in terms of Pt is 0.3 wt%, the content of a Zn component in terms of Zn is 1 wt%, and the balance is a carrier).
Table 3 shows the pore structure parameters of the spherical double mesoporous composite material carrier C3 and the isobutane dehydrogenation catalyst Cat-3.
TABLE 3
*: the first most probable aperture and the second most probable aperture are separated by a comma: the first most probable aperture and the second most probable aperture are arranged in the order from left to right.
As can be seen from the data of table 3, the specific surface area and the pore volume of the spherical dual mesoporous composite support are reduced after the Pt component and the Zn component are supported, which indicates that the Pt component and the Zn component enter the interior of the spherical dual mesoporous composite support 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
| Dehydrogenation catalyst | Isobutane conversion rate | Selectivity to isobutene | Carbon deposition amount of catalyst | |
| Experimental example 1 | Cat-1 | 24％ | 92％ | 1.3wt％ |
| Experimental example 2 | Cat-2 | 23.5％ | 91.8％ | 1.2wt％ |
| Experimental example 3 | Cat-3 | 23.4％ | 91.5％ | 1.4wt％ |
| Experimental comparative example 1 | Cat-D-1 | 12.1％ | 71.3％ | 5.3wt％ |
| Experimental comparative example 2 | Cat-D-2 | 18.7％ | 85.2％ | 2.2wt％ |
| Experimental comparative example 3 | Cat-D-3 | 6.5％ | 56.3％ | 6.8wt％ |
As can be seen from table 4, when the isobutane dehydrogenation catalyst prepared by using the spherical dual-mesoporous 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 (14)
1. A method for preparing an isobutane dehydrogenation catalyst, characterized in that the method comprises the following steps:
(a) in the presence of a template agent and butanol, contacting ethyl orthosilicate with an acid agent, crystallizing and filtering a product obtained after the contact 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 and the silica gel filter cake, 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 composite material carrier;
(d) dipping the spherical double-mesoporous 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;
wherein the carrier is a spherical double-mesoporous composite material carrier, the spherical double-mesoporous composite material carrier contains a mesoporous molecular sieve material with a three-dimensional cubic pore channel distribution structure and silicon dioxide, the average particle size of the spherical double-mesoporous composite material carrier is 30-60 mu m, and the specific surface area is 150-600 m-2The pore volume is 0.5-2mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 4-8nm and 20-30nm respectively;
in the step (d), the spherical dual-mesoporous 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 spherical dual-mesoporous composite material carrier is 98-99.4 wt%, the content of the Pt component calculated by the Pt element is 0.1-0.5 wt%, and the content of the Zn component calculated by the Zn element is 0.5-1.5 wt%.
2. The method of claim 1, wherein in step (a), the molar ratio of the templating agent, butanol, and ethyl orthosilicate is 1: 10-100: 10-90.
3. The method according to claim 1, wherein, in step (a), the template agent is a triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, the acid agent is hydrochloric acid having a pH of 1-6, and the butanol is n-butanol.
4. The method of claim 1, wherein in step (a), the conditions under which the tetraethoxysilane is contacted with the acid agent comprise: the temperature is 10-60 ℃, the time is 10-72 hours, and the pH value is 1-7; the crystallization conditions include: the temperature is 30-150 ℃ and the time is 10-72 hours.
5. The method of claim 1, wherein in step (b), the conditions under which the water glass is contacted with the mineral acid comprise: the temperature is 10-60 ℃, the time is 1-5 hours, and the pH value is 2-4; the inorganic acid is one or more of sulfuric acid, nitric acid and hydrochloric acid.
6. The method according to claim 1, wherein, in the step (c), the silica gel cake is used in an amount of 1 to 200 parts by weight based on 100 parts by weight of the mesoporous material cake.
7. The method according to claim 6, wherein, in the step (c), the silica gel cake is used in an amount of 50 to 150 parts by weight based on 100 parts by weight of the mesoporous material cake.
8. An isobutane dehydrogenation catalyst produced by the process of any one of claims 1-7.
9. The isobutane dehydrogenation catalyst according to claim 8, wherein the average particle diameter of the isobutane dehydrogenation catalyst is 30-60 μm, and the specific surface area is 100-500m2The pore volume is 0.4-1.8mL/g, the pore size distribution is bimodal, and the most probable pore sizes corresponding to the bimodal are 4-8nm and 20-30nm respectively.
10. The isobutane dehydrogenation catalyst according to claim 8, wherein the weight of the silica is 1-200 parts by weight based on 100 parts by weight of the mesoporous molecular sieve material having a three-dimensional cubic channel distribution structure.
11. The isobutane dehydrogenation catalyst according to claim 10, wherein the weight of the silica is 50-150 parts by weight based on 100 parts by weight of the mesoporous molecular sieve material having a three-dimensional cubic channel distribution structure.
12. A method for preparing isobutene by dehydrogenating isobutane, comprising the following steps: isobutane is subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen, characterized in that said catalyst is an isobutane dehydrogenation catalyst according to any of the claims 8-11.
13. The process according to claim 12, wherein the molar ratio of the amount of isobutane to the amount of hydrogen is between 0.5 and 1.5: 1.
14. the method of claim 12, wherein the dehydrogenation reaction conditions comprise: the reaction temperature is 550-650 ℃, the reaction pressure is 0.05-0.2MPa, the reaction time is 20-40h, and the mass space velocity of isobutane is 2-5h-1。
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248981A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate |
| CN104258855A (en) * | 2014-08-20 | 2015-01-07 | 南京沃来德能源科技有限公司 | Preparation method and use of difunctional low-carbon alkane dehydrogenation catalyst |
| WO2016017994A1 (en) * | 2014-07-28 | 2016-02-04 | 롯데케미칼 주식회사 | Dehydrogenation catalyst, and preparation method therefor |
| CN106140218A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of loaded catalyst with meso-hole structure and its preparation method and application |
| CN107417826A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and loaded catalyst and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734987B (en) * | 2008-11-07 | 2012-11-21 | 中国石油化工股份有限公司 | Method for preparing ethylene and propylene from C4 hydrocarbons |
| CN106563452A (en) * | 2016-10-09 | 2017-04-19 | 华南理工大学 | Iron catalyst for isobutylene preparation through catalytic dehydrogenation of isobutane, preparation method and applications thereof |
-
2018
- 2018-05-17 CN CN201810475361.XA patent/CN110496630B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104248981A (en) * | 2013-06-28 | 2014-12-31 | 中国石油化工股份有限公司 | Spherical composite carrier of three dimensional cube tunnel and catalyst, preparation method and application thereof, and preparation method of ethyl acetate |
| WO2016017994A1 (en) * | 2014-07-28 | 2016-02-04 | 롯데케미칼 주식회사 | Dehydrogenation catalyst, and preparation method therefor |
| CN104258855A (en) * | 2014-08-20 | 2015-01-07 | 南京沃来德能源科技有限公司 | Preparation method and use of difunctional low-carbon alkane dehydrogenation catalyst |
| CN106140218A (en) * | 2015-03-27 | 2016-11-23 | 中国石油化工股份有限公司 | A kind of loaded catalyst with meso-hole structure and its preparation method and application |
| CN107417826A (en) * | 2016-05-24 | 2017-12-01 | 中国石油化工股份有限公司 | Spherical zeolite mesoporous composite material and loaded catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Preparation and characterization of Pt/ZnO-Cr2O3 catalyst for low-temperature dehydrogenation of isobutane;Ohta, M et al;《APPLIED CATALYSIS A-GENERAL》;20000220;第258卷(第2期);第153-158页 * |
| Zn-modified MCM-41 as support for Pt catalysts;Silvestre-Albero, J. et al;《APPLIED CATALYSIS A-GENERAL》;20080829;第351卷(第1期);第17、22页 * |
| 铂系异丁烷脱氢催化剂研究;刘丽花;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20150215(第2期);全文 * |
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