CN108786800B - Supported catalyst, preparation method and application thereof, and method for preparing propylene by propane dehydrogenation - Google Patents

Supported catalyst, preparation method and application thereof, and method for preparing propylene by propane dehydrogenation Download PDF

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CN108786800B
CN108786800B CN201710313731.5A CN201710313731A CN108786800B CN 108786800 B CN108786800 B CN 108786800B CN 201710313731 A CN201710313731 A CN 201710313731A CN 108786800 B CN108786800 B CN 108786800B
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supported catalyst
propane
carrier
component
catalyst
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CN108786800A (en
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刘红梅
亢宇
张明森
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
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    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
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    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
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    • 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
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    • C07C2523/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of germanium, tin or lead
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2523/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals of the platinum group metals
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    • C07C2523/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals combined with metals, oxides or hydroxides provided for in groups C07C2523/02 - C07C2523/36
    • C07C2523/56—Platinum group metals
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Abstract

The invention relates to the field of catalysts, and discloses a supported catalyst and a preparation method thereof, application of the supported catalyst in a reaction for preparing propylene by propane dehydrogenation, and a method for preparing propylene by propane dehydrogenation. The supported catalyst comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is a hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2Per g, pore volume of 0.3-1.4cm2(ii)/g, pore diameter is 0.3-1.2 nm. The supported catalyst of the invention is used for catalyzing the reaction of propane dehydrogenation to prepare propylene, the propane conversion rate is high, and the propylene selectivity is high.

Description

Supported catalyst, preparation method and application thereof, and method for preparing propylene by propane dehydrogenation
Technical Field
The invention relates to the field of catalysts, in particular to a supported catalyst, a preparation method of the supported catalyst, application of the supported catalyst in a reaction for preparing propylene by propane dehydrogenation, and a method for preparing propylene by propane dehydrogenation.
Background
The main catalyst of propane dehydrogenation is a chromium oxide/aluminum oxide catalyst in a Catofin process of ABB L umus company and a platinum tin/aluminum oxide catalyst in an Oleflex process of UOP company for more than 10 years, the requirement of the chromium catalyst on raw material impurities is lower, the price is lower compared with that of a noble metal, the catalyst is easy to deposit carbon, the catalyst is easy to regenerate once every 15 to 30 minutes, the environmental pollution is serious due to the chromium in the catalyst, the platinum catalyst achieves high platinum activity, the catalyst has high selectivity, and the like, and has the defects of high catalytic activity, high catalytic efficiency, high catalytic activity and the like.
Much work has been done by researchers to improve the reaction performance of propane dehydrogenation catalysts. Such as: (1) adopts a molecular sieve carrier to replace the traditional gamma-Al carrier2O3The carrier has good effect and comprises MFI type microporous molecular sieves (CN104307555A, CN101066532A, CN101380587A and CN101513613A), mesoporous MCM-41 molecular sieves (CN102389831A), mesoporous SBA-15 molecular sieves (CN101972664A and CN101972664B) and the like; (2) using calcium silicate salt para-gamma-Al2O3The carrier is modified and is impregnated with various active metal components and metal assistants (CN104368364A) step by step; (3) a composite oxide of alumina and magnesia is taken as a carrier, and various active metal components and metal assistants (CN104888818A) are impregnated step by step. The above-mentioned various methods for improving propane dehydrogenation catalysts lead to more complicated catalyst preparation process, increased preparation cost, prolonged preparation period, and even use of reagents or raw materials which are not favorable for environmental resources.
Disclosure of Invention
The invention aims to overcome the defects of complex preparation process and uneven dispersion of active metal components of the existing dehydrogenation catalyst, and provides a supported catalyst and a preparation method and application thereof. The supported catalyst of the invention is used for catalyzing the reaction of propane dehydrogenation to prepare propylene, the propane conversion rate is high, and the propylene selectivity is high.
Specifically, in a first aspect, the invention provides a supported catalyst, which comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is a hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2Per g, pore volume of 0.3-1.4cm2(ii)/g, pore diameter is 0.3-1.2 nm.
In a second aspect, the present invention provides a method for preparing the supported catalyst, comprising: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
In a third aspect, the invention provides a supported catalyst prepared by the above method.
In a fourth aspect, the invention provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
In a fifth aspect, the present invention provides a process for the dehydrogenation of propane to produce propylene, the process comprising: under the condition of preparing propylene by propane dehydrogenation, contacting propane with a catalyst, wherein the catalyst is the supported catalyst provided by the invention.
The supported catalyst and the method have the following advantages: (1) according to the invention, the catalyst is prepared by using the silicon dioxide mesoporous material carrier with macropores, large specific surface area and large pore volume, and the structural characteristics are favorable for good dispersion of metal components on the surface of the carrier, so that the prepared propane dehydrogenation catalyst has excellent performance; (2) the co-impregnation method is adopted to replace the conventional step-by-step impregnation method, the preparation process is simple, the conditions are easy to control, and the product repeatability is good; (3) the catalyst provided by the invention shows good catalytic performance when used for preparing propylene by propane dehydrogenation. High propane conversion rate, high propylene selectivity and good catalyst stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of the hexagonal mesoporous material FDU6-1 of example 1;
FIG. 2 is a nitrogen adsorption-desorption graph of the hexagonal mesoporous material FDU6-1 in example 1;
FIG. 3 is a pore size distribution diagram of the hexagonal mesoporous material FDU6-1 in example 1;
FIG. 4 is a TEM image of the hexagonal mesoporous material FDU6-1 in example 1;
FIG. 5 is a micro-topography (SEM) of the hexagonal mesoporous material FDU6-1 of example 1.
Detailed Description
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.
The invention provides a supported catalyst, which comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, wherein the carrier is a hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2Per g, pore volume of 0.3-1.4cm2(ii)/g, pore diameter is 0.3-1.2 nm.
Preferably, the specific surface area of the hexagonal mesoporous material is 570-630m2Per g, pore volume of 0.5-0.9cm2The pore diameter is 0.4-1 nm.
In the invention, the specific surface area, the pore volume and the pore diameter of the hexagonal mesoporous material can be measured according to a nitrogen adsorption method.
According to the present invention, in the supported catalyst, the contents of the platinum component, the tin component, the sodium component and the carrier may vary within a wide range, for example, the content of the platinum component may be 0.2 to 0.5% by weight, the content of the tin component may be 0.2 to 1.2% by weight, the content of the sodium component may be 0.3 to 0.8% by weight, and the content of the carrier may be 97.5 to 99.3% by weight, in terms of element, based on the total weight of the catalyst. In order to provide a dehydrogenation catalyst with better catalytic performance and reduce the preparation cost of the dehydrogenation catalyst, it is preferable that the content of the platinum component is 0.2 to 0.4 wt%, the content of the tin component is 0.3 to 1 wt%, the content of the sodium component is 0.4 to 0.7 wt%, and the content of the carrier is 97.9 to 99.1 wt%, calculated as elements, based on the total weight of the catalyst.
In the present invention, the carrier is prepared by a method comprising the steps of: mixing and contacting a template agent, potassium sulfate, an acid agent and a silicon source, filtering the obtained mixture and removing the template agent.
In the present invention, the order of mixing and contacting in the preparation process of the carrier is not particularly limited, and the template agent, the potassium sulfate, the acid agent and the silicon source may be simultaneously mixed, or any two or three of them may be mixed, and then the other components may be added and mixed uniformly. According to a preferred embodiment, the template agent, the potassium sulfate and the acid agent are mixed uniformly, and then the silicon source is added and mixed uniformly.
In the present invention, the amount of the template, potassium sulfate and silicon source may vary within a wide range, for example, the molar ratio of the template, potassium sulfate and silicon source may be 1: 100-800: 50-300, preferably 1: 150-700: 80-250, more preferably 1: 200-400: 100-200.
In the present invention, the templating agent may be various templating agents that are conventional in the art. For example, the templating agent may be a triblock copolymer Polyoxyethylene (PEO) -polyoxypropylene (PPO) -Polyoxyethylene (PEO), which may be prepared by methods known to those skilled in the art or may be obtained commercially, e.g., from Fuka under the trade name Synperonic F108, PEO132-PPO50-PEO132Average molecular weight Mn14600. Wherein the number of moles of polyoxyethylene-polyoxypropylene-polyoxyethylene is calculated from the average molecular weight of polyoxyethylene-polyoxypropylene-polyoxyethylene.
In the present invention, the silicon source may be various silicon sources conventionally used in the art, and preferably the silicon source is at least one of tetraethoxysilane, methyl orthosilicate, propyl orthosilicate, sodium orthosilicate and silica sol, and more preferably tetraethoxysilane.
In the present invention, the acid agent may be various acidic aqueous solutions conventionally used in the art, and for example, may be at least one aqueous solution of hydrochloric acid, sulfuric acid, nitric acid and hydrobromic acid, preferably an aqueous hydrochloric acid solution.
The amount of the acid agent is not particularly limited, and may be varied within a wide range, and it is preferable that the pH value in the mixing contact is 1 to 7.
The conditions for the above-mentioned mixing and contacting are not particularly limited in the present invention, and may be conventionally selected in the art. For example, the conditions of the mixing contact include: the temperature can be 10-60 ℃, preferably 25-60 ℃; the time can be 10 to 72 hours, preferably 10 to 30 hours; the pH may be from 1 to 7, preferably from 3 to 6. In order to further facilitate uniform mixing between the substances, according to a preferred embodiment of the invention, the mixing contact is carried out under stirring conditions.
In the present invention, in order to remove impurities in the carrier, the preparation method of the carrier preferably further includes washing and drying processes after the filtration. The washing and drying process may be a routine choice in the art, and for example, washing may be performed at room temperature using deionized or distilled water, and drying may be performed in a drying oven at 80-110 ℃. Washing and drying to obtain the mesoporous material raw powder.
In the present invention, the conditions for removing the template agent may be conventionally selected in the art, and the removal may be achieved by washing and/or calcining, for example. The washing can be water washing and/or alcohol washing, and the washing and template agent removing conditions comprise: the temperature can be 90-120 ℃ and the time can be 10-40 hours. According to a preferred embodiment, the template agent is removed by washing the mesoporous material raw powder with ethanol and/or water under reflux conditions. The conditions for calcining to remove the template agent comprise: the temperature can be 300-600 ℃, preferably 400-600 ℃; the time may be 8 to 20 hours, preferably 10 to 24 hours. According to a preferred embodiment, the raw mesoporous material powder is calcined in a muffle furnace.
In the present invention, the supported catalyst may be prepared according to various methods conventionally used in the art as long as it can support a platinum component, a tin component and a sodium component on the carrier.
The invention also provides a preparation method of the supported catalyst, which comprises the following steps: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
Wherein the carrier is described above, and is not described herein again. In the present invention, there is no particular limitation on the selection of the water-soluble platinum compound, the water-soluble tin compound, and the inorganic sodium salt. For example, the water-soluble platinum compound is at least one of chloroplatinic acid, ammonium chloroplatinate and platinum nitrate, preferably chloroplatinic acid and/or ammonium chloroplatinate, and more preferably chloroplatinic acid; the water-soluble tin compound is tin tetrachloride; the inorganic sodium salt is sodium nitrate and/or sodium chloride.
In the present invention, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt may vary within a wide range, and for example, the amounts of the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are such that in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.5% by weight, the content of the tin component is 0.2 to 1.2% by weight, the content of the sodium component is 0.3 to 0.8% by weight and the content of the carrier is 97.5 to 99.3% by weight, in terms of elements, based on the total weight of the catalyst. Preferably, the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in such amounts that, in the prepared supported catalyst, the content of the platinum component is 0.2 to 0.4% by weight, the content of the tin component is 0.3 to 1% by weight, the content of the sodium component is 0.4 to 0.7% by weight and the content of the carrier is 97.9 to 99.1% by weight, in terms of elements, based on the total weight of the catalyst.
In the invention, the contents of the platinum component, the tin component and the sodium component in the supported catalyst are calculated according to the charge ratio of raw materials.
In the present invention, the conditions of the co-impregnation are not particularly limited, and for example, the conditions of the co-impregnation include: the temperature can be 15-60 ℃, and the time can be 1-10 hours; preferably, the temperature is 25-40 ℃ and the time is 2-8 hours.
In the present invention, the solvent water removal method is not particularly limited, and may be a method conventionally used in the art, for example, a rotary evaporator may be used.
In the present invention, the drying conditions are not particularly limited, and may be those conventional in the art. For example, the drying conditions include: the temperature can be 90-160 ℃, and preferably 100-130 ℃; the time can be 1 to 20 hours, preferably 2 to 5 hours.
In the present invention, the conditions for the calcination are not particularly limited, and may be those conventionally used in the art. For example, the conditions for the calcination include: the temperature can be 500-700 ℃, preferably 550-650 ℃; the time can be 2 to 15 hours, preferably 3 to 10 hours.
The method according to the present invention may further comprise heating the carrier at a temperature of 300-900 deg.c for 7-10 hours in the presence of an inert gas to remove hydroxyl groups on the surface of the carrier and volatile substances (e.g., water) contained in the carrier before supporting the platinum component, the tin component and the sodium component.
In the present invention, the inert gas is a gas which does not react with the raw materials and the product, and may be, for example, nitrogen gas or at least one of group zero element gases in the periodic table, preferably nitrogen gas, which is conventional in the art.
The invention also provides a supported metallocene catalyst prepared by the method. The supported catalyst prepared by the method has large specific surface area and pore volume, and the dispersion condition of the metal component on the carrier is good, so that the catalyst shows excellent catalytic performance in catalytic dehydrogenation reaction.
The invention also provides the application of the supported catalyst in the reaction of preparing propylene by propane dehydrogenation.
The invention also provides a method for preparing propylene by propane dehydrogenation, which comprises the following steps: under the condition of preparing propylene by propane dehydrogenation, propane is contacted with a catalyst, and the catalyst is the supported catalyst provided by the invention.
In the present invention, the catalyst provided by the present invention can be used for propane dehydrogenation to prepare propylene by using the conditions conventionally used in the art, and preferably, the method further comprises adding a diluent gas, wherein the diluent gas is usually hydrogen. The contacting of the propane with the catalyst may be carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene include: the molar ratio of propane to hydrogen may be from 0.5 to 5: 1, the reaction temperature can be 500-650 ℃, the pressure can be 0.05-0.15MPa, and the mass space velocity of the propane can be 1-10h-1. The pressures of the present invention are gage pressures.
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples, polyoxyethylene-polyoxypropylene-polyoxyethylene was obtained from Fuka under the trade name
Figure BDA0001287864100000081
F108, molecular formula EO132PO60EO132Abbreviated as F108, and an average molecular weight Mn of 14600.
The rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the drying box is produced by Shanghai-Hengchun scientific instruments Co., Ltd, and is of a type DHG-9030A;
the muffle furnace is manufactured by CARBO L ITE company, model CWF 1100.
X-ray diffraction analysis was performed on an X-ray diffractometer model D8Advance, available from Bruker AXS, Germany; n of the sample2The adsorption-desorption experiments were carried out on an adsorption apparatus model ASAP2020-M + C manufactured by Micromeritics, USA, and BET method was used for the calculation of the specific surface area and pore volume of the sample.
Scanning Electron Microscope (SEM) analysis was performed on a model X L-30 scanning electron microscope available from FEI, USA, and the pore structure of the sample was observed using a FEI Tecnai 20 high-resolution transmission electron microscope.
The content of each component in the prepared dehydrogenation catalyst is determined by calculating the raw material feeding during preparation;
propane conversion and selectivity were analyzed by gas chromatography and calculated as follows:
the propane conversion was × 100% based on the amount of propane consumed by the reaction/initial amount of propane;
the propylene selectivity was calculated as follows:
propylene selectivity is × 100% of the amount of propane consumed to form propylene/total propane consumption;
the propylene yield was calculated as follows:
the propylene yield was × 100% based on the actual yield of propylene/theoretical yield of propylene.
Example 1
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
1.46g (0.0001mol) of template F108 and 5.24g (0.03mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;
adding 4.2g (0.02mol) of ethyl orthosilicate into the solution, stirring for 15 minutes at 38 ℃, and standing for 24 hours at 38 ℃;
then 100g of deionized water is added for dilution, filtration, washing and drying to obtain the original powder mesoporous material. Calcining the raw powder mesoporous material at 400 ℃ for 10 hours to remove the template agent, and obtaining the hexagonal mesoporous material FDU 6-1.
And characterizing the hexagonal mesoporous material FDU6-1 by using an X-ray diffraction instrument, a transmission electron microscope, a scanning electron microscope and a nitrogen adsorption instrument.
Fig. 1 is an X-ray diffraction pattern having an abscissa of 2 θ in units °, and it is understood from the pattern that 1 diffraction peak (2 θ ═ 0.6 °) of the (110) plane and a diffraction shoulder (2 θ ═ 1.2 °) of the (200) plane corresponding to the cube center Im3m appear in the small angle region in sample FDU 6-1. (110) The intensity of the diffraction peak of the surface is high, the peak shape is narrow, and the hexagonal mesoporous material FDU6-1 is proved to have a good long-range ordered structure. In addition, the position of the diffraction shoulder (2 θ ═ 1.2 °) of the (200) plane is completely different from that of the hexagonal unit cell or the layered structure.
FIG. 2 is a nitrogen adsorption-desorption graph (abscissa is relative pressure, unit is p/p) of hexagonal mesoporous material FDU6-10) FIG. 2 shows that the hexagonal mesoporous material FDU6-1 is a typical IUPAC-defined class IV adsorption-desorption isotherm, and the sample has H2The type hysteresis loop proves that the hexagonal mesoporous material FDU6-1 has a mesoporous structure with a peculiar cubic cage structure reported in the literature. The desorption branch between 0.4 and 0.5 relative partial pressure also indicates that the material has a cage-like cavity structure.
FIG. 3 is a graph showing a distribution of pore sizes (0.1 nm on the abscissa) of a hexagonal mesoporous material FDU 6-1. According to the pore size distribution diagram, the hexagonal mesoporous material FDU6-1 has narrow pore size distribution and very uniform pore channels.
Fig. 2 and 3 show that: the specific surface area of the hexagonal mesoporous material FDU6-1 is 598m2Per g, pore volume 0.7cm3Per g, pore size 0.7 nm.
FIG. 4 is a Transmission Electron Micrograph (TEM) of sample hexagonal mesoporous material FDU 6-1. From FIG. 4, the shape of the pores in the (100) plane of the hexagonal mesoporous material FDU6-1 of the samples can be clearly seen, and the samples all have a cubic-centered Im3m structure.
FIG. 5 is a micro-topography (SEM) of hexagonal mesoporous material FDU 6-1. According to the figure, the micro-topography of the hexagonal mesoporous material FDU6-1 is hexagonal, and the particle size is in the micron level.
(2) Preparation of Supported catalysts
In the presence of nitrogen, the hexagonal mesoporous material FDU6-1 is calcined at 400 ℃ for 10 hours to be thermally activated, and hydroxyl and residual moisture are removed, so that the thermally activated hexagonal mesoporous material FDU6-1 is obtained.
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolved in 100ml of deionized water and then dissolved in water,the resulting mixture was mixed with 10g of the hexagonal mesoporous FDU6-1 prepared above, and the mixture was continuously stirred at room temperature for 5 hours. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. And then placing the product in a muffle furnace, and roasting for 6 hours at the temperature of 600 ℃ to obtain the supported catalyst A1.
The specific gravity of each component of the supported catalyst A1 is as follows: 0.3 percent of platinum component calculated by platinum element, 0.7 percent of tin component calculated by tin element, 0.5 percent of sodium component calculated by sodium element, and the balance of hexagonal mesoporous material carrier.
(3) Dehydrogenation of propane to propylene
0.5g of the supported catalyst A1 was charged into a fixed bed quartz reactor, the reaction temperature was controlled at 610 ℃, the reaction pressure was 0.1MPa, the molar ratio of propane: the molar ratio of hydrogen is 1:1, and the mass space velocity of propane is 3.0h-1The reaction time is 50 h. The reaction results are shown in Table 1.
Example 2
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
1.46g (0.0001mol) of template F108 and 6.96g (0.04mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;
adding 3.1g (0.015mol) of tetraethoxysilane into the solution, stirring for 15min at 45 ℃, and standing for 30 hours at 45 ℃;
then 100g of deionized water is added for dilution, filtration, washing and drying to obtain the original powder mesoporous material. Calcining the raw powder mesoporous material at 600 ℃ for 15 hours to remove the template agent, and obtaining the hexagonal mesoporous material FDU 6-2.
Specific surface area 569m of hexagonal mesoporous material FDU6-22Per g, pore volume 0.6cm3Per g, pore size 0.5 nm.
(2) Preparation of Supported catalysts
In the presence of nitrogen, the hexagonal mesoporous material FDU6-2 is calcined at 400 ℃ for 10 hours to be thermally activated, and hydroxyl and residual moisture are removed, so that the thermally activated hexagonal mesoporous material FDU6-2 is obtained.
0.053g of H2PtCl6·6H2O, 0.09g of SnCl4·5H2O and 0.127g of NaCl are dissolved in 50ml of deionized water, and the mixture is mixed with 10g of the thermally activated hexagonal mesoporous material FDU6-2 prepared in the above manner, and the mixture is continuously stirred and reacted for 2 hours at the temperature of 40 ℃. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then calcined in a muffle furnace at 650 ℃ for 3 hours to obtain the supported catalyst A2.
The specific gravity of each component of the supported catalyst A2 is as follows: 0.2 wt% of platinum component calculated by platinum element, 0.3 wt% of tin component calculated by tin element, 0.4 wt% of sodium component calculated by sodium element, and the balance of hexagonal mesoporous material FDU 6-2.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst a2 was used in place of the supported catalyst a1 in example 1. The reaction results are shown in Table 1.
Example 3
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
1.46g (0.0001mol) of template F108 and 3.48g (0.02mol) of K2SO4Stirring with 60g hydrochloric acid solution with 2(2N) equivalent concentration at 38 deg.C until F108 is completely dissolved;
adding 2.1g (0.01mol) of tetraethoxysilane into the solution, stirring at 35 ℃ for 15min, and standing at 35 ℃ for 20 hours;
then 100g of deionized water is added for dilution, filtration, washing and drying to obtain the mesoporous material raw powder. Washing the mesoporous material raw powder with ethanol for 24 hours at 100 ℃ under reflux to remove the template agent, thus obtaining the hexagonal mesoporous material FDU 6-3.
Preparation of hexagonal mesoporous material FDU6-3Specific surface area of 624m2Per g, pore volume 0.9cm3Per g, pore size 0.8 nm.
(2) Preparation of Supported catalysts
In the presence of nitrogen, the hexagonal mesoporous material FDU6-3 is calcined at 400 ℃ for 10 hours to be thermally activated, and hydroxyl and residual moisture are removed, so that the thermally activated hexagonal mesoporous material FDU6-3 is obtained.
0.11g of H2PtCl6·6H2O, 0.296g of SnCl4·5H2O and 0.259g NaNO3Dissolving in 200ml deionized water, mixing with 10g of the thermally activated hexagonal mesoporous material FDU6-3 prepared above, and continuously stirring and reacting at 30 ℃ for 8 hours. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 100 ℃ for 5 hours. Then, the catalyst was calcined in a muffle furnace at 550 ℃ for 10 hours to obtain a supported catalyst A3.
The specific gravity of each component of the supported catalyst A3 is as follows: 0.4 wt% of platinum component calculated by platinum element, 1 wt% of tin component calculated by tin element, 0.7 wt% of sodium component calculated by sodium element, and the balance of hexagonal mesoporous material FDU 6-3.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst A3 was used in place of the supported catalyst a1 in example 1. The reaction results are shown in Table 1.
Example 4
This example illustrates the supported catalyst, the preparation method thereof, and the method for preparing propylene by propane dehydrogenation provided by the present invention
(1) Preparation of the support
The support was prepared according to the method of example 1.
(2) Preparation of Supported catalysts
The procedure of example 1 was followed except that the contents of the platinum component, the tin component and the sodium component were varied. In particular, H2PtCl6·6H2The dosage of O is 0.133g, SnCl4·5H2O is used in an amount of0.355g，NaNO3The amount of (2) was 0.111g, and the rest was the same as in example 1, to obtain a supported catalyst A4.
The specific gravity of each component of the supported catalyst A4 is as follows: 0.5 wt% of platinum component calculated by platinum element, 1.2 wt% of tin component calculated by tin element, 0.3 wt% of sodium component calculated by sodium element, and the balance of hexagonal mesoporous material FDU 6-1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene by following the procedure of example 1 except that a supported catalyst a4 was used in place of the supported catalyst a1 in example 1. The reaction results are shown in Table 1.
Comparative example 1
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
0.080g of H2PtCl6·6H2O, 0.207g SnCl4·5H2O and 0.185g NaNO3Dissolved in 100ml of deionized water, 10g of commercially available gamma-Al were added2O3Carrier (Qingdao Seawa silica gel desiccant company brand is a commercial product of industrial grade low specific surface area activated alumina, and the specific surface area is 162m2Per g, pore volume 0.82cm3And/g) are mixed and the reaction is continued for 5 hours at room temperature with stirring. And (4) evaporating the solvent water in the system by using a rotary evaporator to obtain a solid product. The solid product was dried in a drying oven at 120 ℃ for 3 hours. Then the catalyst was calcined in a muffle furnace at 600 ℃ for 6 hours to obtain the supported catalyst DA 1.
The specific gravity of each component of the supported catalyst DA1 is as follows: 0.3 wt% of platinum component calculated by platinum element, 0.7 wt% of tin component calculated by tin element, 0.5 wt% of sodium component calculated by sodium element, and the balance of gamma-Al2O3And (3) a carrier.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene in accordance with the procedure of example 1, except that a supported catalyst DA1 was used in place of the supported catalyst A1 in example 1. The reaction results are shown in Table 1.
Comparative example 2
This comparative example serves to illustrate a reference supported catalyst and a process for the dehydrogenation of propane to propylene
A support and a supported catalyst were prepared by following the procedure of example 1, except that the supported catalyst was prepared by a stepwise impregnation method instead of a co-impregnation method. Specifically, the thermally activated carrier FDU6-1 was first immersed in an aqueous chloroplatinic acid solution for 5 hours, the immersed carrier FDU6-1 was dried and calcined under the conditions of example 1, and then immersed in an aqueous solution of tin tetrachloride and sodium nitrate for 5 hours, and then dried and calcined under the conditions of example 1, to obtain the supported catalyst DA 2.
The specific gravity of each component of the supported catalyst DA2 is as follows: 0.3 weight percent of platinum component calculated by platinum element, 0.7 weight percent of tin component calculated by tin element, 0.5 weight percent of sodium component calculated by sodium element, and the balance of hexagonal mesoporous material carrier FDU 6-1.
(3) Dehydrogenation of propane to propylene
Propane dehydrogenation was carried out to produce propylene in accordance with the procedure of example 1, except that a supported catalyst DA2 was used in place of the supported catalyst A1 in example 1. The reaction results are shown in Table 1.
TABLE 1
Figure BDA0001287864100000151
As can be seen from the results in Table 1, examples 1-4 using the supported catalyst of the present invention for the reaction of propane dehydrogenation to produce propylene have significantly better catalytic performance than the commercially available gamma-Al2O3The catalyst prepared by the carrier (comparative example 1) has obviously improved average conversion rate of propane, average selectivity of propylene and average yield of propylene. The preparation method of the dehydrogenation catalyst provided by the invention can realize the effect of improving the catalytic performance of the dehydrogenation catalyst. Compared with the catalyst prepared by adopting the step-by-step impregnation method in the comparative example 2, the catalyst disclosed by the invention is simple in preparation process and good in catalytic effect. The effects are clearly most optimal with examples 1-3 in the preferred range.
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 (15)

1. A supported catalyst comprises a carrier and a platinum component, a tin component and a sodium component which are loaded on the carrier, and is characterized in that the carrier is a hexagonal mesoporous material, and the specific surface area of the hexagonal mesoporous material is 550-650m2Per g, pore volume of 0.3-1.4cm2Per gram, the aperture is 0.3-1.2 nm;
wherein, by taking the total weight of the catalyst as a reference, the content of the platinum component is 0.2-0.5 wt%, the content of the tin component is 0.2-1.2 wt%, the content of the sodium component is 0.3-0.8 wt%, and the content of the carrier is 97.5-99.3 wt% calculated by elements;
wherein the preparation method of the supported catalyst comprises the following steps: the carrier is co-impregnated with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then the solvent water is removed, dried and calcined.
2. The supported catalyst as claimed in claim 1, wherein the hexagonal mesoporous material has a specific surface area of 570-630m2Per g, pore volume of 0.5-0.9cm2The pore diameter is 0.4-1 nm.
3. The supported catalyst of claim 1, wherein the support is prepared by a process comprising: mixing and contacting a template agent, potassium sulfate, an acid agent and a silicon source, filtering the obtained mixture and removing the template agent.
4. The supported catalyst of claim 3, wherein the molar ratio of the templating agent, potassium sulfate, and silicon source is 1: 100-800: 50-300.
5. The supported catalyst of claim 3, wherein the conditions of the mixed contacting comprise: the temperature is 25-60 deg.C, the time is 10-72 hr, and the pH value is 1-7.
6. The supported catalyst of claim 3, wherein the conditions for removing the template agent comprise: the temperature is 300 ℃ and 600 ℃, and the time is 8-20 hours.
7. A process for preparing a supported catalyst according to any one of claims 1 to 6, comprising: co-impregnating a carrier with a mixed aqueous solution containing a water-soluble platinum compound, a water-soluble tin compound and an inorganic sodium salt, then removing solvent water, drying and roasting;
wherein, the water-soluble platinum compound, the water-soluble tin compound and the inorganic sodium salt are used in such amounts that in the prepared supported catalyst, the content of the platinum component is 0.2-0.5 wt%, the content of the tin component is 0.2-1.2 wt%, the content of the sodium component is 0.3-0.8 wt%, and the content of the carrier is 97.5-99.3 wt% calculated by elements based on the total weight of the catalyst.
8. The method of claim 7, wherein the co-impregnating conditions comprise: the temperature is 15-60 ℃ and the time is 1-10 hours.
9. The method of claim 7, wherein the firing conditions include: the temperature is 500 ℃ and 700 ℃ and the time is 2-15 hours.
10. The process as claimed in claim 7, wherein the process further comprises heating the support at a temperature of 300-900 ℃ for 7-10 hours in the presence of an inert gas prior to co-impregnation.
11. A supported catalyst prepared by the process of any one of claims 7-10.
12. Use of a supported catalyst according to any one of claims 1 to 6 and 11 in the dehydrogenation of propane to produce propylene.
13. A method for preparing propylene by propane dehydrogenation is characterized by comprising the following steps: contacting propane with a catalyst under conditions for the dehydrogenation of propane to propylene, characterized in that the catalyst is a supported catalyst according to any one of claims 1-6 and 11.
14. The method of claim 13, further comprising adding a diluent gas, hydrogen.
15. The process of claim 13, wherein the contacting of the propane with the catalyst is carried out in a fixed bed quartz reactor, and the conditions for the dehydrogenation of propane to produce propylene comprise: the molar ratio of propane to hydrogen is 0.5-5: 1, the reaction temperature is 500-650 ℃, the pressure is 0.05-0.15MPa, and the mass space velocity of propane is 1-10h-1。
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