CN112517049B - Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof - Google Patents

Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof Download PDF

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CN112517049B
CN112517049B CN201910886822.7A CN201910886822A CN112517049B CN 112517049 B CN112517049 B CN 112517049B CN 201910886822 A CN201910886822 A CN 201910886822A CN 112517049 B CN112517049 B CN 112517049B
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temperature
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CN112517049A (en
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亢宇
刘红梅
刘东兵
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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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
    • 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
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

The invention relates to the field of low-carbon alkane dehydrogenation catalysts, and discloses a catalyst for preparing propylene by propane dehydrogenation and a preparation method and application thereof. The method comprises the following steps: in the presence of a template agent, mixing and contacting tetraethoxysilane and a hydrochloric acid solution; obtaining a mixed solution; crystallizing the mixed solution to obtain a crystallized product, and sequentially carrying out solid-liquid separation, drying and template agent removal treatment on the crystallized product to obtain an SBA-15 molecular sieve; sequentially carrying out primary silanization ball milling treatment and twice high-temperature calcination treatment on the SBA-15 molecular sieve to obtain a modified SBA-15 molecular sieve; and introducing an active metal component by taking the modified SBA-15 molecular sieve as a carrier. The catalyst for preparing propylene by propane dehydrogenation prepared by the method can show excellent catalytic performance in propane dehydrogenation reaction under the condition of lower metal component load, and has high conversion rate of propane and high selectivity of propylene.

Description

Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof
Technical Field
The invention relates to the field of low-carbon alkane dehydrogenation catalysts, in particular to a preparation method of a catalyst for preparing propylene by propane dehydrogenation, the catalyst for preparing propylene by propane dehydrogenation prepared by the method and application of the catalyst in propane dehydrogenation reaction.
Background
Propylene is a basic raw material of petrochemical industry and is mainly used for producing polypropylene, acrylonitrile, acetone, propylene oxide, acrylic acid, butanol and octanol and the like. Half of the propylene supply comes from refinery by-products, and another about 45% comes from steam cracking and minor amounts of other alternative technologies. In recent years, the demand of propylene is increasing year by year, and the traditional propylene production can not meet the demand of the chemical industry for propylene, so that the propylene yield increase becomes a great hot point for research. Among them, the dehydrogenation of propane to produce propylene is a major technique for increasing the yield of propylene. For more than 10 years, the dehydrogenation of propane to prepare propylene has become an important process for the industrial production of propylene.
The main catalysts for propane dehydrogenation are the chromium oxide/alumina catalyst in the Catofin process from ABB Lummus and the platinum tin/alumina catalyst in the Oleflex process from UOP. The chromium catalyst has lower requirements on raw material impurities and has lower price compared with noble metals; however, the catalyst is easy to deposit carbon and deactivate, and is regenerated every 15 to 30 minutes, and the chromium in the catalyst is heavy metal, so that the environmental pollution is serious. The platinum-tin catalyst has high activity and good selectivity, the reaction period can reach several days, and the catalyst can bear harsh process conditions and is more environment-friendly; however, the noble metal platinum is expensive, so that the cost of the catalyst is high, and the catalytic activity and selectivity of the catalyst are required to be further improved.
Although the industrial production of propylene by propane dehydrogenation has been carried out for more than twenty years, and many researches on dehydrogenation catalysts have been carried out, the current catalysts still have the defects of low propane conversion rate, easy deactivation and the like, and further improvement and perfection are needed. Therefore, it is of practical significance to develop a propane dehydrogenation catalyst having excellent performance.
Much work has been done by researchers to improve the reaction performance of propane dehydrogenation catalysts. Such as: adopts a molecular sieve carrier to replace the traditional gamma-Al carrier2O3The carrier has good effect and comprises MFI type microporous molecular sieves (CN 104307555A, CN 101066532A, CN 101380587A and CN 101513613A), mesoporous MCM-41 molecular sieves (CN 102389831A), mesoporous SBA-15 molecular sieves (CN 101972664A and CN 101972664B) and the like. However, when the currently commonly used mesoporous material is used as a carrier to load an active metal component, the dispersion of the active component is not facilitated, and the catalytic effect is finally affected, for example, the conversion rate of propane and the selectivity of propylene are not high.
Disclosure of Invention
The invention aims to overcome the problems in the prior art, and provides a preparation method of a propane dehydrogenation propylene preparation catalyst, the propane dehydrogenation propylene preparation catalyst prepared by the method and an application of the propane dehydrogenation propylene preparation catalyst.
The inventor of the invention finds out in research that the carrier structure (including physical structures such as specific surface area, pore volume and pore size distribution, and chemical structures such as surface acid sites and electronic properties) of the noble metal catalyst not only has important influence on the dispersion degree of the 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. The use of a suitable support is important in order to minimize the noble metal content of the catalyst (reduce costs) and at the same time to improve the activity and stability of the catalyst. However, most of the commercially available activated alumina carriers have too much hydroxyl groups and too strong acidity on the surface, and when the alumina is used as a carrier to prepare a dehydrogenation catalyst, the surface of the catalyst is easy to deposit carbon during the reaction process, so that the catalyst is quickly deactivated. The inventor of the invention discovers that in the process of preparing and researching the propane dehydrogenation catalyst, the macroporous SBA-15 molecular sieve is prepared by hydrolyzing and crystallizing tetraethoxysilane under an acidic condition, the SBA-15 molecular sieve is modified by adopting a method of one-time silanization ball milling and two-time high-temperature calcination, and the modified SBA-15 molecular sieve is used as a carrier to load a metal component to prepare the propane dehydrogenation catalyst, so that the surface of the catalyst is not easy to deposit carbon, and the performance of the catalyst in the propane dehydrogenation reaction is excellent. The inventor guesses that in the silanization ball-milling treatment process protected by inert gas, large particles of the macroporous SBA-15 molecular sieve are uniformly crushed, and pore channels are better exposed on the outer surface, so that active metal components are better loaded; meanwhile, silane or derivative molecules thereof are bonded on the surface of the pore channel and the defect positions in the pore channel, so that the irregular position of the pore channel structure in the macroporous SBA-15 molecular sieve is made up, the structural characteristics of the surface of the macroporous SBA-15 molecular sieve material are improved, and the geometric effect and the electronic effect between the metal active component and the carrier are further improved. After silanization ball milling treatment, the macroporous SBA-15 molecular sieve is calcined twice at a higher temperature, so that water and redundant hydroxyl groups adsorbed on the surface and in a pore channel of the macroporous SBA-15 molecular sieve and redundant radicals introduced in the silanization ball milling treatment process can be removed to the maximum extent, more binding sites are provided for metal active components, and in the dehydrogenation catalyst prepared from the catalyst, the metal active components are dispersed more uniformly on the surface and in the pore channel of the modified mesoporous material with the high specific surface area, so that the adsorption of propane and the desorption of propylene are facilitated, and the conversion rate of propane and the selectivity of propylene are improved.
Based on the above findings, and in order to achieve the above object, an aspect of the present invention provides a method for preparing a catalyst for producing propylene by propane dehydrogenation, the method comprising:
(a) in the presence of a template agent, mixing and contacting tetraethoxysilane and a hydrochloric acid solution; obtaining a mixed solution;
(b) crystallizing the mixed solution to obtain a crystallized product, and sequentially carrying out solid-liquid separation, drying and template agent removal treatment on the crystallized product to obtain an SBA-15 molecular sieve;
(c) sequentially carrying out primary silanization ball milling treatment and twice high-temperature calcination treatment on the SBA-15 molecular sieve to obtain a modified SBA-15 molecular sieve;
(d) taking the modified SBA-15 molecular sieve as a carrier, introducing an active metal component, and preparing a propylene catalyst by propane dehydrogenation;
wherein, in the step (c), the silanization ball milling treatment method comprises the following steps; under the protection of inert gas, mixing the SBA-15 molecular sieve with silane or a silane derivative, and carrying out ball milling treatment on the obtained mixture to obtain the SBA-15 molecular sieve subjected to silanization ball milling treatment;
the method for the two high-temperature calcination treatments independently comprises the following steps: under the protection of inert gas, the SBA-15 molecular sieve treated by silanization ball milling is heated from the initial temperature to the end temperature and is kept at the end temperature for a period of time.
Preferably, the silanized ball milling treatment conditions comprise: the temperature of ball milling is 20-100 ℃, the diameter of the grinding ball is 2-8mm, the rotating speed of the grinding ball is 300-600r/min, and the time is 1-30 h.
Preferably, the silane derivative is selected from one or more of dichlorodimethylsilane, hexamethyldisilane, trimethylchlorosilane, tetramethylsilane and methyltrichlorosilane.
Preferably, the two high-temperature calcination treatment steps independently comprise: under the protection of inert gas, heating the SBA-15 molecular sieve from 10-40 ℃ to 500-700 ℃ at the heating rate of 0.5-5 ℃/min, and keeping the temperature for 4-20h to carry out first high-temperature calcination treatment; then heating the SBA-15 molecular sieve subjected to the first high-temperature calcination treatment from 10-40 ℃ to 550-750 ℃ at the heating rate of 1-10 ℃/min, and keeping the temperature for 3-15h to perform second high-temperature calcination treatment.
In a second aspect, the present invention provides a catalyst for the dehydrogenation of propane to propylene, prepared by the process as described above.
In a third aspect, the present invention provides the use of the catalyst for the dehydrogenation of propane to produce propylene as described above in a propane dehydrogenation reaction.
Compared with the prior art, the catalyst for preparing propylene by propane dehydrogenation, which is prepared by the method provided by the invention, has the following advantages:
(1) the method for preparing the catalyst for preparing the propylene by propane dehydrogenation has the advantages of simple preparation process, easily controlled conditions and good product repeatability;
(2) the propane dehydrogenation propylene preparation catalyst prepared by the method provided by the invention can achieve better dehydrogenation activity and propylene selectivity under the condition of lower load of main active components (namely noble metal platinum), and can effectively reduce the preparation cost of the propane dehydrogenation propylene preparation catalyst;
(3) the metal active component on the propane dehydrogenation propylene preparation catalyst prepared by the method has high dispersity, so that the propane catalyst is not easy to inactivate due to the agglomeration of active metal particles in the reaction process;
(4) the catalyst for preparing propylene by propane dehydrogenation, which is prepared by the method provided by the invention, shows good catalytic performance when used in propane dehydrogenation reaction, and has the advantages of high propane conversion rate, high propylene selectivity and good catalyst stability.
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 macroporous SBA-15 molecular sieve A1 of example 1.
FIG. 2 is a nitrogen adsorption desorption curve for the macroporous SBA-15 molecular sieve A1 of example 1.
FIG. 3 is a schematic representation of the pore structure of macroporous SBA-15 molecular sieve A1 of example 1 (TEM transmission electron microscope).
FIG. 4 is a microscopic morphology (SEM) of macroporous SBA-15 molecular sieve A1 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.
In a first aspect, the present invention provides a method for preparing a catalyst for propane dehydrogenation to produce propylene, the method comprising:
(a) in the presence of a template agent, mixing and contacting tetraethoxysilane and a hydrochloric acid solution; obtaining a mixed solution;
(b) crystallizing the mixed solution to obtain a crystallized product, and sequentially carrying out solid-liquid separation, drying and template agent removal treatment on the crystallized product to obtain an SBA-15 molecular sieve;
(c) sequentially carrying out primary silanization ball milling treatment and twice high-temperature calcination treatment on the SBA-15 molecular sieve to obtain a modified SBA-15 molecular sieve;
(d) taking the modified SBA-15 molecular sieve as a carrier, introducing an active metal component, and preparing a propylene catalyst by propane dehydrogenation;
wherein, in the step (c), the silanization ball milling treatment method comprises the following steps; under the protection of inert gas, mixing the SBA-15 molecular sieve with silane or a silane derivative, and carrying out ball milling treatment on the obtained mixture to obtain the SBA-15 molecular sieve subjected to silanization ball milling treatment;
the method for the two high-temperature calcination treatments independently comprises the following steps: under the protection of inert gas, the SBA-15 molecular sieve treated by silanization ball milling is heated from the initial temperature to the end temperature and is kept at the end temperature for a period of time.
According to the present invention, in step (a), the conditions of the mixing contact may include: the temperature is 25-60 deg.C, and the time is 20-120 min. Among them, in order to further facilitate uniform mixing between the respective substances, the mixing contact is preferably performed under stirring conditions.
According to a preferred embodiment of the present invention, in step (a), the ratio of the template agent to the tetraethoxysilane to the hydrochloric acid solution is 1 g: 2-3g (e.g., 2g, 2.1g, 2.2g, 2.3g, 2.4g, 2.5g, 2.6g, 2.7g, 2.8g, 2.9g, 3 g): 1-5ml (1ml, 1.5ml, 2ml, 2.5ml, 3ml, 3.5ml, 4ml, 4.5ml, 5 ml).
According to the invention, the concentration of the hydrochloric acid solution may be conventional, for example, 30 to 40% by weight.
According to the present invention, in step (a), preferably, the mixing and contacting are carried out in the presence of water, preferably deionized water, and the amount of water can be selected from a wide range, as long as it can hydrolyze ethyl orthosilicate, thereby facilitating the subsequent preparation of the SBA-15 molecular sieve. Preferably, the feeding ratio of the template agent to the tetraethoxysilane to the hydrochloric acid solution to water is 1 g: 2-3 g: 1-5 ml: 30-50 ml. It is understood that the amount of water is the amount of water additionally added, excluding the water contained in the raw material, for example, hydrochloric acid.
According to the invention, the templating agent is preferably a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide EO20PO70EO20. Wherein the template agent triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20May be a product available from Aldrich under the trade name P123.
According to the present invention, in the step (a), the feeding manner of each component is not particularly limited, for example, each component may be directly and uniformly mixed, but the inventors of the present invention found that the performance of the catalyst for propylene preparation by propane dehydrogenation prepared from the prepared SBA-15 molecular sieve is better when the template agent, hydrochloric acid and water are mixed and stirred for a certain period of time, for example, until the template agent is dissolved, and then tetraethoxysilane is added to the above mixed solution and stirred for a certain period of time, for example, 40 to 80 min.
According to the present invention, in the step (b), the crystallization conditions may include: the temperature is 90-180 ℃ and the time is 10-40 h.
The crystallization is preferably carried out by a hydrothermal crystallization method, and specifically, the hydrolysate obtained in the step (a) is transferred to a hydrothermal reaction kettle with a polytetrafluoroethylene lining, and crystallized for a preset time at a preset temperature to complete the crystallization treatment.
According to the present invention, in the step (b), the solid-liquid separation may be a conventional method for separating a solid phase and a liquid phase in a system, preferably, a method combining filtration and suction filtration to achieve the solid-liquid separation, and specifically, the process may include: pre-separating the solid phase and the liquid phase of the crystallized product by filtration, washing the crystallized product for 3 to 10 times by deionized water after filtration until the pH value of the washing liquid is 6.5 to 7.0, and then carrying out suction filtration to finally obtain a solid phase material.
According to the present invention, in the step (b), the drying conditions may include: the temperature is 100 ℃ and 150 ℃, and the time is 3-20 h. The drying can be carried out in a constant-temperature drying oven to obtain a dry material, namely, macroporous SBA-15 molecular sieve raw powder.
According to the present invention, the method for removing the template from the raw powder of the macroporous SBA-15 molecular sieve in step (b) can be a method conventional in the art, and preferably, the dried material is washed with alcohol at 90-120 ℃ for 10-40 h. Among them, the alcohol is preferably ethanol.
According to the invention, the SBA-15 molecular sieve can be finally obtained through the step (b), wherein the SBA-15 molecular sieve has a two-dimensional hexagonal pore channel structure and the specific surface area is 250-2Per g, pore volume of 0.8-1.3mL/g, average pore diameter of 10-13.5 nm.
According to the invention, the silane can be monosilane SiH4Or disilane Si2H6。
According to the invention, the silane derivative is preferably monosilane in which 2 to 4 hydrogen atoms are substituted by substituents or disilane in which 2 to 6 hydrogen atoms are substituted by substituents, preferably the substituents are preferably halogen and/or C1-C4 alkyl, further preferably the halogen is chlorine, and the C1-C4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl.
According to a preferred embodiment of the present invention, silane derivatives selected from one or more of dichlorodimethylsilane, hexamethyldisilane, trimethylchlorosilane, tetramethylsilane, methyltrichlorosilane are mixed with the SBA-15 molecular sieve. Within this preferred range, the performance of the catalyst prepared from the resulting modified SBA-15 molecular sieve can be further improved.
According to the invention, the weight ratio of the silane or silane derivative to the SBA-15 molecular sieve may vary within wide limits, preferably the weight ratio of the silane or silane derivative to the SBA-15 molecular sieve is from 0.03 to 0.2:1, e.g., 0.03:1, 0.06:1, 0.08:1, 0.1:1, 0.12:1, 0.14:1, 0.16:1, 0.18:1, 0.2: 1.
According to the present invention, the inert gas used in the silanized ball milling process may be nitrogen, helium or argon, preferably nitrogen.
According to the invention, the ball-milling treatment can be carried out in conventional equipment, for example in a ball mill. The number of balls in the ball mill may be appropriately selected depending on the size of the ball mill pot provided in the ball mill, and for example, 20 to 80 balls may be generally used for a ball mill pot having a size of 50 to 150 mL. The material of the grinding ball can be agate, polytetrafluoroethylene and the like, and agate is preferred.
According to the present invention, preferably, the silanized ball milling process conditions include: the temperature of the ball mill is 20-100 deg.C (for example, 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C, 100 deg.C), the diameter of the ball mill is 2-8mm (for example, 2mm, 3mm, 4mm, 5mm, 6mm, 7mm, 8mm), the rotation speed of the ball mill is 300-600r/min (for example, 300r/min, 350r/min, 400r/min, 450r/min, 500r/min, 650r/min, 600r/min), and the time is 1-30h (for example, 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30 h). By controlling the conditions of the silanization ball milling within the preferable range, the performance of the prepared catalyst can be further improved.
According to a preferred embodiment of the present invention, the two high-temperature calcination treatments comprise: heating SBA-15 molecular sieve from 10-40 deg.C (e.g., 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C) to 500 deg.C (e.g., 500 deg.C, 550 deg.C, 600 deg.C, 650 deg.C, 700 deg.C) at a heating rate of 0.5-5 deg.C/min (e.g., 0.5 deg.C/min, 1 deg.C/min, 1.5 deg.C/min, 2 deg.C/min, 2.5 deg.C/min, 3 deg.C/min, 3.C/min, 4 deg.C/min, 4.C/min, 5 deg.C/min), and maintaining at the temperature for 4-20h (e.g., 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h) to perform a first high temperature calcination treatment; then, the SBA-15 molecular sieve after the first high-temperature calcination treatment is heated from 10 to 40 ℃ (for example, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃) to 1 to 10 ℃/min (for example, 1 ℃/min, 1.5 ℃/min, 2 ℃/min, 2.5 ℃/min, 3 ℃/min, 3.5 ℃/min, 4 ℃/min, 4.5 ℃/min, 5 ℃/min, 5.5 ℃/min, 6 ℃/min, 6.5 ℃/min, 7 ℃/min, 7.5 ℃/min, 8 ℃/min, 8.5 ℃/min, 9 ℃/min, 9.5 ℃/min, 10 ℃/min) at a heating rate of 1 to 10 ℃/min (for example, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃) and is kept at the temperature for 3 to 15 hours (for example, and may be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h) to perform the second high-temperature calcination treatment. The modification of the prepared SBA-15 molecular sieve under the preferable conditions can further improve the performance of the finally prepared propane dehydrogenation propylene catalyst.
According to the present invention, the method may further comprise, after the first high-temperature calcination treatment, stopping the heating and naturally lowering the temperature of the material, for example, to the starting temperature or room temperature of the second high-temperature calcination treatment, and then starting the operation of performing the second heating treatment. It can be understood that the process of stopping heating and naturally cooling is also carried out under the protection of inert gas.
According to the present invention, the starting temperature, the temperature increase rate, the end temperature, and the time maintained at the end temperature of the first high-temperature calcination process and the starting temperature, the temperature increase rate, the end temperature, and the time maintained at the end temperature of the second high-temperature calcination process are the same or different.
According to the present invention, the inert gas used in the two high-temperature calcination processes may be one or more of nitrogen, argon or helium, and is preferably nitrogen.
According to the present invention, the two high-temperature calcination processes may be performed in a muffle furnace.
According to the invention, the specific surface area, the pore volume and the average pore diameter of the SBA-15 molecular sieve can be further improved through the calcining treatment and the ball milling treatment of the invention, but the 2D hexagonal pore channel structure of the mesoporous material is not changed. Preferably, the modified SBA-15 molecular sieve has a 2D hexagonal pore channel structure and a specific surface area of 300-500m2Per g, pore volume of 1.0-1.5mL/g, average pore diameter of 10.0-13.5 nm. When the structural parameters of the modified SBA-15 molecular sieve are preferably controlled within the range, the catalyst for preparing propylene by propane dehydrogenation, which is prepared by taking the modified macroporous SBA-15 molecular sieve as a carrier, can be ensured to keep good catalytic effect in the process of propane dehydrogenation. In the present invention, it is to be noted that the modificationThe SBA-15 molecular sieve and SBA-15 molecular sieve are crossed within the parameters as above, but this does not alter the fact that the specific surface area, pore volume and average pore diameter of the SBA-15 molecular sieve can be increased by the silanized ball milling and high temperature calcination treatment of the present invention.
According to the present invention, in step (d), the metal active ingredient may be incorporated into the support by a conventional method, and according to a preferred embodiment of the present invention, the method of incorporating the active ingredient comprises: and (3) dipping the carrier into a solution containing the active metal component precursor, and sequentially carrying out solvent removal treatment, drying treatment and roasting treatment after dipping.
According to the present invention, the active metal component may be a conventional active metal component for propylene production by propane dehydrogenation, and preferably, the active metal component is one or more of platinum, tin, zinc, magnesium, calcium and gallium, preferably one or more of platinum, tin, magnesium and calcium, and more preferably contains platinum (the precursor may be H)2PtCl6) And contains tin (the precursor can be SnCl)4·5H2O, magnesium (the precursor can be Mg (NO)3)2) And calcium (the precursor may be Ca (NO)3)2) At least 1 kind of (1). The method can improve the catalyst for preparing propylene by propane dehydrogenation and reduce the using amount of the active metal component, so that the method provides an economic basis for selecting the active metal component as a noble metal.
According to the invention, in the impregnation process, active metal ions in the impregnation solution can enter the pore channels of the modified SBA-15 molecular sieve by means of the capillary pressure of the pore channels of the modified SBA-15 molecular sieve, and the metal ions can be adsorbed on the surface of the modified SBA-15 molecular sieve until the adsorption is balanced.
The impregnation method is not particularly limited, and when the number of the active metal components is at least 2, a conventional stepwise impregnation method may be used, however, the inventors of the present invention have found that the method of the present invention may use a co-impregnation method and the same effect can be achieved, that is, the method of the present invention also saves an impregnation step.
Preferably, the impregnation conditions include: and mixing and contacting the modified SBA-15 molecular sieve with a solution containing a metal component precursor, wherein the impregnation temperature can be 20-90 ℃, and the impregnation time can be 2-16 h.
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 or a vacuum oven can be used to remove the solvent in the system.
According to the present invention, the drying may be performed in a drying oven, and the drying conditions may include: the temperature is 70-150 ℃ and the time is 3-16 h.
According to the invention, the firing may be carried out in a muffle furnace, and the firing conditions may include: the temperature is 500-650 ℃, and the time is 3-12 h.
According to a preferred embodiment of the invention, the active metal components are Pt and other metal components, and during the impregnation process, the modified SBA-15 molecular sieve and the precursor of the active metal components are used in such amounts that the modified SBA-15 molecular sieve is contained in the prepared propane dehydrogenation propylene preparation catalyst in an amount of 98.0 to 99.0 wt%, the main active component Pt is contained in an amount of 0.2 to 0.5 wt% calculated as Pt element, and the other metal components are contained in an amount of 0.8 to 1.8 wt% calculated as metal elements, based on the total weight of the propane dehydrogenation propylene preparation catalyst. Thus being beneficial to exerting the synergistic effect between each component and the carrier to the maximum extent and obtaining the optimal catalytic activity.
According to a preferred embodiment of the present invention, a method for preparing a catalyst for producing propylene by propane dehydrogenation comprises:
(1) at 25-60 ℃, mixing and stirring a template agent triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene, a hydrochloric acid solution and water until the template agent is dissolved, then adding tetraethoxysilane into the mixed solution, and continuously stirring for a period of time, for example, 40-80min to obtain a hydrolysate; wherein, relative to each gram of the template agent, the dosage of the tetraethoxysilane is 2-3g, the dosage of the hydrochloric acid is 1-5ml, and the dosage of the water is 30-50 ml;
crystallizing the mixed solution at 90-180 ℃ for 10-40h to obtain a crystallized product, sequentially carrying out solid-liquid separation and drying on the crystallized product to obtain SBA-15 molecular sieve raw powder, and washing the SBA-15 molecular sieve raw powder with ethanol at 90-120 ℃ for 10-40h to obtain the SBA-15 molecular sieve.
The SBA-15 molecular sieve has a two-dimensional hexagonal pore channel structure, and the specific surface area is 250-450m2Per g, pore volume of 0.8-1.3mL/g, average pore diameter of 10-13.5 nm.
(2) Mixing the SBA-15 molecular sieve with one or more silane derivatives selected from dichlorodimethylsilane, hexamethyldisilane, trimethylchlorosilane, tetramethylsilane and methyltrichlorosilane according to the weight ratio of 0.03-0.2: 1, and under the protection of inert gas, performing ball milling treatment under the conditions that the diameter of a grinding ball is 2-8mm, the rotating speed of the grinding ball is 300-600r/min, the ball milling temperature is 20-100 ℃, and the ball milling time is 1-30 h;
then, under the protection of inert gas, sequentially carrying out first high-temperature calcination treatment and second high-temperature calcination treatment on the SBA-15 molecular sieve subjected to silanization ball milling treatment; the initial temperature of the first high-temperature calcination treatment is 10-40 ℃, the heating rate is 0.5-5 ℃/min, the end temperature is 500-; the initial temperature of the second high-temperature calcination treatment is 10-40 ℃, the heating rate is 1-10 ℃/min, the end temperature is 550-.
The modified SBA-15 molecular sieve has a two-dimensional hexagonal pore channel structure, and the specific surface area is 300-500m2Per g, pore volume of 1.0-1.5mL/g, average pore diameter of 12.0-14.5 nm. The pore structure of the SBA-15 molecular sieve is not changed by silanization ball milling and calcination.
(3) Impregnating the modified SBA-15 molecular sieve in a catalyst containing H2PtCl6·6H2O、SnCl4·5H2O and Ca (NO)3)2Soaking the mixed solution for 2 to 16 hours at the temperature of between 20 and 90 ℃, and then evaporating water in the system by using a rotary evaporator to obtain a solid product; placing the solid product in a drying oven at 70-150 deg.CAnd drying for 3-16 h. And then roasting the mixture in a muffle furnace at 650 ℃ for 3-12h at 500-650 ℃ to obtain the propylene catalyst prepared by propane dehydrogenation, wherein the using amount of each component is that based on the total weight of the propylene catalyst prepared by propane dehydrogenation, the content of the modified SBA-15 molecular sieve is 98.0-99.0 wt%, the content of the main active component Pt calculated by Pt element is 0.2-0.5 wt%, the content of Sn calculated by element is 0.4-1.0 wt%, and the content of Zn calculated by Zn element is 0.4-0.8 wt%.
In the present invention, the specific surface area, the pore volume and the average pore diameter as described above are measured according to the nitrogen adsorption method.
In the invention, the content of each element in the catalyst for preparing propylene by propane dehydrogenation can be measured by adopting an X-ray fluorescence spectrum analysis method.
In a second aspect, the present invention provides a catalyst for the dehydrogenation of propane to propylene prepared by the above process.
In a third aspect, the invention provides the use of the catalyst for producing propylene by propane dehydrogenation in propane dehydrogenation reaction.
According to the present invention, the propane dehydrogenation may be carried out according to a method conventional in the art, for example, the method of propane dehydrogenation reaction includes: propane is subjected to a dehydrogenation reaction in the presence of a catalyst and hydrogen.
When the catalyst for preparing propylene by propane dehydrogenation, which is prepared by the method provided by the invention, is used for catalyzing propane dehydrogenation reaction, the conversion rate of propane and the selectivity of propylene can be greatly improved.
According to the present invention, in order to improve the propane conversion and prevent coking of the catalyst, it is preferable that the molar ratio of the amount of propane to the amount of hydrogen is 1: 0.2-5.0.
The conditions for the propane 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 0.05-0.30MPa, and the mass space velocity of propane is 1.0-15.0h-1。
The present invention will be described in detail below by way of examples.
In the following examples and comparative examples:
x-ray diffraction analysis was performed on an X-ray diffractometer model D8Advance, available from Bruker AXS, Germany;
pore structure parameter analysis was performed on an adsorption apparatus model ASAP2020-M + C, available from Micromeritics, USA;
the specific surface area and the pore volume of the sample are calculated by a BET method;
the rotary evaporator is produced by German IKA company, and the model is RV10 digital;
the content of the metal component of the catalyst for preparing propylene by propane dehydrogenation is measured on a wavelength dispersion X-ray fluorescence spectrometer which is purchased from Parnaco, Netherlands and has the model of Axios-Advanced;
analysis of the reaction product composition was performed on a gas chromatograph available from Agilent under model 7890A;
triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20Is a product available from Aldrich under the trade name P123 and has an average molecular weight of 5800; other reagents are purchased from chemical reagents of national medicine group, Inc., and the purity is analytical purity. (ii) a
Conversion (%) of propane, the amount of propane consumed by the reaction/initial amount of propane × 100%;
the selectivity (%) of propylene means the amount of propane consumed to produce propylene/the total amount of propane consumed × 100%.
Example 1
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
(1) Preparation of macroporous SBA-15 molecular sieve
40g of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20(P123), 164mL of hydrochloric acid (37% by weight) and 1280g of deionized water, and stirring at 40 ℃ until P123 is completely dissolved; then 88.6g of tetraethoxysilane is slowly added into the solution, stirred for 60min at 40 ℃, and then the obtained solution is transferred into a reaction kettle with a polytetrafluoroethylene liningCrystallizing at 150 ℃ for 20h, filtering, washing with deionized water for 5 times, performing suction filtration and drying to obtain macroporous SBA-15 molecular sieve raw powder; and (3) mixing 20g of the macroporous SBA-15 molecular sieve raw powder with 200mL of ethanol, refluxing and washing at 100 ℃ for 24h, and removing the template agent to obtain the macroporous SBA-15 molecular sieve A1.
The macroporous SBA-15 molecular sieve A1 is characterized by using an ASAP2020-M + C type adsorption apparatus, and the specific surface area of the macroporous SBA-15 molecular sieve A1 is 351M2Pore volume 1.0ml/g, average pore diameter 12.0 nm.
FIG. 1 is an X-ray diffraction pattern of a macroporous SBA-15 molecular sieve. The XRD spectrogram proves that the macroporous SBA-15 molecular sieve has an ordered two-dimensional hexagonal pore structure which is peculiar to an SBA-15 mesoporous molecular sieve.
Figure 2 is an adsorption-desorption isotherm for a macroporous SBA-15 molecular sieve. It can be seen that this sample has a type IV adsorption-desorption isotherm with a typical hysteresis loop of type H1, while producing a jump in the amount of adsorption at p/p0 of 0.7 to 0.8. The characteristics prove that the macroporous SBA-15 molecular sieve is a mesoporous molecular sieve with a uniform pore channel structure.
FIGS. 3 and 4 are a schematic representation of the pore structure (TEM transmission electron microscope) and a microscopic morphology image (SEM scanning electron microscope) of the macroporous SBA-15 molecular sieve. As can be seen from the figure, the macroporous SBA-15 maintains the two-dimensional ordered hexagonal mesoporous channel structure which is peculiar to the mesoporous material SBA-15, and the result is consistent with the result of XRD.
(2) Preparation of modified macroporous SBA-15 molecular sieve
And (3) putting 10g of the macroporous SBA-15 molecular sieve A1 and 1.0g of dichlorodimethylsilane into a 100ml ball milling tank, and carrying out ball milling treatment under the protection of nitrogen to obtain the macroporous SBA-15 molecular sieve B1. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 4mm, the number of the grinding balls is 50, the rotating speed of each grinding ball is 450r/min, the temperature in the ball milling tank is 50 ℃, and the ball milling time is 15 hours.
And (3) putting the macroporous SBA-15 molecular sieve B1 subjected to silanization ball milling treatment into a muffle furnace, introducing nitrogen for protection, and performing first high-temperature calcination treatment. The temperature is raised from 25 ℃ to 550 ℃ at a heating rate of 1 ℃/min and kept at 550 ℃ for 8 h. And stopping heating after the first high-temperature calcination treatment is finished, and carrying out second high-temperature calcination treatment after the sample temperature is cooled to the room temperature under the protection of nitrogen. The second high-temperature calcination treatment is carried out at a heating rate of 2 ℃/min, the temperature is increased from 30 ℃ to 600 ℃ and kept at 600 ℃ for 10 h. And after the second high-temperature calcination treatment, cooling the sample to room temperature under the protection of nitrogen to obtain the modified macroporous SBA-15 molecular sieve C1.
The modified macroporous SBA-15 molecular sieve C1 is characterized by an ASAP2020-M + C type adsorption apparatus to obtain the modified macroporous SBA-15 molecular sieve C1 with the specific surface area of 409M2Pore volume 1.2ml/g, average pore diameter 12.8 nm.
The X-ray diffraction pattern of the modified macroporous SBA-15 molecular sieve C1 is completely the same as that in figure 1, which shows that the modified macroporous SBA-15 molecular sieve C1 and the unmodified macroporous SBA-15 molecular sieve A1 have the completely same SBA-15 pore channel structure, and the modification process of one-time silanization ball milling treatment and two-time high-temperature calcination treatment does not cause the change of the ordered structure of the macroporous SBA-15 molecular sieve.
(3) Preparation of catalyst for preparing propylene by propane dehydrogenation
0.040g H2PtCl6·6H2O、0.118g SnCl4·5H2O and 0.103g Ca (NO)3)2Dissolving the mixed solution in 50mL of deionized water in a round-bottom flask to obtain a mixed solution; adding 5g of the modified macroporous SBA-15 molecular sieve C1 obtained in the step (2) into the mixed solution, carrying out co-impregnation treatment, continuously stirring and reacting for 5 hours under the water bath condition of 60 ℃, and then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product; the solid product was placed in a drying oven at 110 ℃ and dried for 6 h. And then roasting the mixture in a muffle furnace at the temperature of 550 ℃ for 8 hours to obtain a propane dehydrogenation propylene preparation catalyst Cat-1, wherein in the propane dehydrogenation propylene preparation catalyst Cat-1, the content of a platinum component in terms of platinum element is 0.3 wt%, the content of a tin component in terms of tin element is 0.8 wt%, and the content of a calcium component in terms of calcium element is 0.5 wt% based on the total weight of the propane dehydrogenation propylene preparation catalyst Cat-1.
Example 2
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
(1) Preparation of macroporous SBA-15 molecular sieve
40g of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20(P123), 107mL of hydrochloric acid (37 wt.%), and 1160g of deionized water, and stirring at 50 ℃ until P123 is completely dissolved; then, slowly adding 103.4g of tetraethoxysilane into the solution, stirring for 40min at 50 ℃, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 30h at 130 ℃, then filtering, washing for 4 times by using deionized water, and then carrying out suction filtration and drying to obtain macroporous SBA-15 molecular sieve raw powder; and (3) mixing 20g of the macroporous SBA-15 molecular sieve raw powder with 200mL of ethanol, refluxing and washing at 110 ℃ for 15h, and removing the template agent to obtain the macroporous SBA-15 molecular sieve A2.
The specific surface area of the macroporous SBA-15 molecular sieve A2 is 378m2Pore volume 1.1ml/g, average pore diameter 12.8 nm.
(2) Preparation of modified macroporous SBA-15 molecular sieve
And (3) putting 10g of the macroporous SBA-15 molecular sieve A2 and 1.5g of trimethylchlorosilane into a 100ml ball milling tank, and carrying out ball milling treatment under the protection of nitrogen to obtain the macroporous SBA-15 molecular sieve B2. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 3mm, the number of the grinding balls is 60, the rotating speed of each grinding ball is 400r/min, the temperature in the ball milling tank is 60 ℃, and the ball milling time is 20 hours.
And (3) putting the macroporous SBA-15 molecular sieve B2 subjected to silanization ball milling treatment into a muffle furnace, introducing nitrogen for protection, and performing first high-temperature calcination treatment. The temperature is raised from 30 ℃ to 600 ℃ at the temperature raising rate of 2.5 ℃/min and kept at 600 ℃ for 8 h. And stopping heating after the first high-temperature calcination treatment is finished, and carrying out second high-temperature calcination treatment after the sample temperature is cooled to the room temperature under the protection of nitrogen. The second high-temperature calcination treatment is carried out at a heating rate of 2.5 ℃/min, the temperature is raised from 20 ℃ to 600 ℃ and kept at 600 ℃ for 12 h. And after the second high-temperature calcination treatment, cooling the sample to room temperature under the protection of nitrogen to obtain the modified macroporous SBA-15 molecular sieve C2.
Modified macroporous SBA-15 molecular sieve C2 has a specific surface area of 421m2Pore volume 1.3ml/g, average pore diameter 13.5 nm.
(3) Preparation of catalyst for preparing propylene by propane dehydrogenation
0.053g H2PtCl6·6H2O、0.074g SnCl4·5H2O、0.123g Mg(NO3)2And 0.124g Ca (NO)3)2Dissolving the mixed solution in 50mL of deionized water in a round-bottom flask to obtain a mixed solution; adding 5g of the modified macroporous SBA-15 molecular sieve C2 obtained in the step (2) into the mixed solution, carrying out impregnation treatment, continuously stirring and reacting for 10 hours under the condition of water bath at 40 ℃, and then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product; the solid product was placed in a drying cabinet at 120 ℃ and dried for 5 h. And then roasting the mixture in a muffle furnace at the temperature of 550 ℃ for 6 hours to obtain a propane dehydrogenation propylene preparation catalyst Cat-2, wherein in the propane dehydrogenation propylene preparation catalyst Cat-2, the content of a platinum component in terms of platinum element is 0.4 wt%, the content of a tin component in terms of tin element is 0.5 wt%, the content of a magnesium component in terms of magnesium element is 0.4 wt%, and the content of a calcium component in terms of calcium element is 0.6 wt%, based on the total weight of the propane dehydrogenation propylene preparation catalyst Cat-2.
Example 3
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
(1) Preparation of macroporous SBA-15 molecular sieve
40g of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20(P123), 64mL of hydrochloric acid (37 wt.%), and 1390g of deionized water, stirred at 25 ℃ until P123 is completely dissolved; then slowly adding 110.8g of tetraethoxysilane into the solution, stirring for 120min at 25 ℃, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 10h at 180 ℃, then filtering, washing for 8 times by using deionized water, then carrying out suction filtration and drying to obtain macroporous SBA-15 molecular sieve raw powder; mixing 20g of the macroporous SBA-15 molecular sieve raw powder with 200mL of ethanol, refluxing and washing at 120 ℃ for 10h, and removingRemoving the template agent to obtain the macroporous SBA-15 molecular sieve A3.
The specific surface area of the macroporous SBA-15 molecular sieve A3 is 345m2Pore volume 0.9ml/g, average pore diameter 11.2 nm.
(2) Preparation of modified macroporous SBA-15 molecular sieve
And (3) putting 10g of the macroporous SBA-15 molecular sieve A3 and 2.0g of methyltrichlorosilane into a 100ml ball milling tank, and carrying out ball milling treatment under the protection of nitrogen to obtain the macroporous SBA-15 molecular sieve B3. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 2mm, the number of the grinding balls is 80, the rotating speed of each grinding ball is 300r/min, the temperature in the ball milling tank is 100 ℃, and the ball milling time is 1 hour.
And (3) putting the macroporous SBA-15 molecular sieve B3 subjected to silanization ball milling treatment into a muffle furnace, introducing nitrogen for protection, and performing first high-temperature calcination treatment. The temperature is raised from 10 ℃ to 700 ℃ at a temperature raising rate of 5 ℃/min and kept at 700 ℃ for 4 h. And stopping heating after the first high-temperature calcination treatment is finished, and carrying out second high-temperature calcination treatment after the sample temperature is cooled to the room temperature under the protection of nitrogen. The second high-temperature calcination treatment is carried out at a heating rate of 10 ℃/min, the temperature is increased from 10 ℃ to 750 ℃ and is kept at 750 ℃ for 3 h. And after the second high-temperature calcination treatment, cooling the sample to room temperature under the protection of nitrogen to obtain the modified macroporous SBA-15 molecular sieve C3.
The specific surface area of the modified macroporous SBA-15 molecular sieve C3 is 396m2Pore volume 1.1ml/g, average pore diameter 12.2 nm.
(3) Preparation of catalyst for preparing propylene by propane dehydrogenation
0.066g H2PtCl6·6H2O、0.104g SnCl4·5H2O、0.185g Mg(NO3)2And 0.145g Ca (NO)3)2Dissolving the mixed solution in 50mL of deionized water in a round-bottom flask to obtain a mixed solution; adding 5g of the modified macroporous SBA-15 molecular sieve C3 obtained in the step (2) into the mixed solution, carrying out impregnation treatment, continuously stirring and reacting for 2 hours under the condition of a water bath at 90 ℃, and then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product; placing the solid product in a drying oven at 70 deg.C, and dryingAnd (4) 16 h. And then roasting the mixture in a muffle furnace at the temperature of 500 ℃ for 12 hours to obtain a propane dehydrogenation propylene preparation catalyst Cat-3, wherein in the propane dehydrogenation propylene preparation catalyst Cat-3, the content of a platinum component in terms of platinum element is 0.5 wt%, the content of a tin component in terms of tin element is 0.7 wt%, the content of a magnesium component in terms of magnesium element is 0.6 wt%, and the content of a calcium component in terms of calcium element is 0.7 wt% based on the total weight of the propane dehydrogenation propylene preparation catalyst Cat-3.
Example 4
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
(1) Preparation of macroporous SBA-15 molecular sieve
40g of triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20(P123), 158mL of hydrochloric acid (37 wt.%), and 1890g of deionized water, stirred at 60 ℃ until P123 is completely dissolved; then, slowly adding 118.1g of tetraethoxysilane into the solution, stirring for 20min at 65 ℃, then transferring the obtained solution into a reaction kettle with a polytetrafluoroethylene lining, crystallizing for 40h at 90 ℃, then filtering, washing for 4 times by using deionized water, and then carrying out suction filtration and drying to obtain macroporous SBA-15 molecular sieve raw powder; and (3) mixing 20g of the macroporous SBA-15 molecular sieve raw powder with 200mL of ethanol, refluxing and washing at 90 ℃ for 40h, and removing the template agent to obtain the macroporous SBA-15 molecular sieve A4.
The specific surface area of the macroporous SBA-15 molecular sieve A4 is 383m2Pore volume 1.2ml/g, average pore diameter 13.1 nm.
(2) Preparation of modified macroporous SBA-15 molecular sieve
And (3) putting 10g of the macroporous SBA-15 molecular sieve A4 and 0.3g of tetramethylsilane into a 100ml ball milling tank, and carrying out ball milling treatment under the protection of nitrogen to obtain the macroporous SBA-15 molecular sieve B4. Wherein the ball milling tank is made of polytetrafluoroethylene, the grinding balls are made of agate, the diameter of each grinding ball is 8mm, the number of the grinding balls is 20, the rotating speed of each grinding ball is 600r/min, the temperature in the ball milling tank is 20 ℃, and the ball milling time is 30 hours.
And (3) putting the macroporous SBA-15 molecular sieve B4 subjected to silanization ball milling treatment into a muffle furnace, introducing nitrogen for protection, and performing first high-temperature calcination treatment. The temperature is raised from 40 ℃ to 500 ℃ at a heating rate of 0.5 ℃/min and kept at 500 ℃ for 20 h. And stopping heating after the first high-temperature calcination treatment is finished, and carrying out second high-temperature calcination treatment after the sample temperature is cooled to the room temperature under the protection of nitrogen. The second high-temperature calcination treatment is carried out at a heating rate of 1 ℃/min, the temperature is increased from 40 ℃ to 550 ℃, and the temperature is kept at 550 ℃ for 15 h. And after the second high-temperature calcination treatment, cooling the sample to room temperature under the protection of nitrogen to obtain the modified macroporous SBA-15 molecular sieve C4.
The specific surface area of the modified macroporous SBA-15 molecular sieve C4 is 429m2Pore volume 1.4ml/g, average pore diameter 14.3 nm.
(3) Preparation of catalyst for preparing propylene by propane dehydrogenation
0.026g H2PtCl6·6H2O、0.059g SnCl4·5H2O and 0.123g Mg (NO)3)2Dissolving the mixed solution in 50mL of deionized water in a round-bottom flask to obtain a mixed solution; adding 5g of the modified macroporous SBA-15 molecular sieve C4 obtained in the step (2) into the mixed solution, carrying out impregnation treatment, continuously stirring and reacting for 16 hours under the water bath condition of 20 ℃, and then evaporating solvent water in the system by using a rotary evaporator to obtain a solid product; the solid product was placed in a drying oven at 150 ℃ and dried for 3 h. And then roasting the mixture in a muffle furnace at the temperature of 650 ℃ for 3 hours to obtain a propane dehydrogenation propylene preparation catalyst Cat-4, wherein in the propane dehydrogenation propylene preparation catalyst Cat-4, the content of a platinum component in terms of platinum element is 0.2 wt%, the content of a tin component in terms of tin element is 0.4 wt%, and the content of a magnesium component in terms of magnesium element is 0.4 wt% based on the total weight of the propane dehydrogenation propylene preparation catalyst Cat-4.
Example 5
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
The preparation of the catalyst for the dehydrogenation of propane to propene and its use in the dehydrogenation of propane were carried out as described in example 1, except that dichlorodimethylsilane was replaced by the same amount of monosilane. The ASAP2020-M + C type adsorption apparatus is used for characterizing the modified macroporous SBA-15 molecular sieve C5, and the structural parameters of the obtained modified macroporous SBA-15 molecular sieve C5 are within the scope of the invention.
Example 6
This example is provided to illustrate the preparation of a catalyst for propane dehydrogenation to propylene and its use in propane dehydrogenation reactions.
The preparation method of the catalyst for preparing propylene by propane dehydrogenation and the application of the catalyst in propane dehydrogenation reaction are carried out according to the method in the embodiment 1, except that the preparation method of the macroporous SBA-15 molecular sieve A5 is carried out, specifically, a template agent, tetraethoxysilane, 37 weight percent of hydrochloric acid and sub-water are directly mixed at the temperature of 40 ℃, and the mixture is stirred for 90 min. The ASAP2020-M + C type adsorption apparatus is used for characterizing the modified macroporous SBA-15 molecular sieve C6, and the structural parameters of the obtained modified macroporous SBA-15 molecular sieve C6 are within the scope of the invention.
Comparative example 1
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The catalyst Cat-D-1 for propane dehydrogenation to propylene was prepared according to the method of example 1, except that the step (2) was omitted and the catalyst for propane dehydrogenation to propylene was prepared directly by using unmodified macroporous SBA-15 molecular sieve a1 as a supported metal component, and the preparation process of the catalyst was the same as that of the step (3) of example 1. Based on the total weight of the catalyst Cat-D-1, the content of the platinum component calculated by platinum element is 0.3 wt%, the content of the tin component calculated by tin element is 0.8 wt%, the content of the calcium component calculated by calcium element is 0.5 wt%, and the balance is carrier.
Comparative example 2
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The method for preparing the propylene catalyst Cat-D-2 by propane dehydrogenation is as in example 1, except that the silanization ball milling treatment process in the step (2) is eliminated, the macroporous SBA-15 molecular sieve a1 is subjected to two high-temperature calcination treatments to obtain the modified macroporous SBA-15 molecular sieve D1, and the propane dehydrogenation catalyst is prepared by taking the modified macroporous SBA-15 molecular sieve D1 as a carrier supported metal component, wherein the catalyst preparation process is the same as that in the step (3) in example 1. Based on the total weight of the catalyst Cat-D-2, the content of the platinum component calculated by platinum element is 0.3 wt%, the content of the tin component calculated by tin element is 0.8 wt%, the content of the calcium component calculated by calcium element is 0.5 wt%, and the balance is carrier.
Comparative example 3
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The method of example 1 was used to prepare the catalyst Cat-D-3 for propylene production by propane dehydrogenation, except that the two high-temperature calcination processes in step (2) were omitted, the macroporous SBA-15 molecular sieve a1 was ball-milled to obtain the modified macroporous SBA-15 molecular sieve D2, and the catalyst for propylene production by propane dehydrogenation was prepared using the modified macroporous SBA-15 molecular sieve D2 as the carrier-supported metal component, and the catalyst preparation process was the same as in step (3) of example 1. Based on the total weight of the catalyst Cat-D-3, the content of the platinum component calculated by platinum element is 0.3 wt%, the content of the tin component calculated by tin element is 0.8 wt%, the content of the calcium component calculated by calcium element is 0.5 wt%, and the balance is carrier.
Comparative example 4
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The propylene preparation catalyst Cat-D-4 from propane dehydrogenation was prepared according to the method of example 2. Except that the process of the step (2) is as follows:
10g of macroporous SBA-15 molecular sieve A2 and 0.1g of tetramethylsilane are put into a 100ml ball milling tank and ball milling treatment is carried out under the protection of nitrogen. The diameter of the grinding balls is 8mm, the number of the grinding balls is 10, the rotating speed of the grinding balls is 400r/min, the temperature in the ball milling tank is 40 ℃, and the ball milling time is 0.5 hour. And (3) putting the sample subjected to silanization ball milling treatment into a muffle furnace, cancelling nitrogen protection, and performing first high-temperature calcination treatment. The temperature is raised from 30 ℃ to 900 ℃ at a heating rate of 1 ℃/min and kept at 900 ℃ for 15 h. And stopping heating after the first high-temperature calcination treatment is finished, and carrying out second high-temperature calcination treatment after the sample is cooled to room temperature under the protection of nitrogen. The second high-temperature calcination treatment is carried out at a heating rate of 3 ℃/min, the temperature is raised from 25 ℃ to 1000 ℃ and kept at 1000 ℃ for 15 h. And after the second high-temperature calcination treatment, cooling the sample to room temperature under the protection of nitrogen to obtain the modified macroporous SBA-15 molecular sieve D3.
The modified macroporous SBA-15 molecular sieve D3 is used as a carrier to load a metal component to prepare the propylene catalyst by propane dehydrogenation, and the preparation process of the catalyst is the same as that of the step (3) in the example 2. Based on the total weight of the catalyst Cat-D-4, the content of the platinum component calculated by platinum element is 0.4 wt%, the content of the tin component calculated by tin element is 0.5 wt%, the content of the magnesium component calculated by magnesium element is 0.4 wt%, the content of the calcium component calculated by calcium element is 0.6 wt%, and the balance is a carrier.
Comparative example 5
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The preparation of the catalyst for the dehydrogenation of propane to propene and its use in the dehydrogenation of propane were carried out as in example 1, except that dichlorodimethylsilane was not used in the ball milling.
Comparative example 6
The method for preparing the reference catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are explained.
The preparation method of the catalyst for preparing propylene by propane dehydrogenation and the application thereof in the propane dehydrogenation reaction are carried out according to the method in the embodiment 1, except that the first high-temperature roasting treatment is carried out, then the silanization ball milling treatment is carried out, and finally the second high-temperature roasting treatment is carried out.
Test example 1:
and (3) testing the performance of the catalyst for preparing propylene by propane dehydrogenation in the propane dehydrogenation reaction.
1.0g of a catalyst for preparing propylene by propane dehydrogenation is loaded into a fixed bed quartz reactor, the reaction temperature is controlled to be 610 ℃, the reaction pressure is 0.1MPa, and the reaction pressure is as follows: the molar ratio of hydrogen is 1:1, the reaction time is 50h, and the mass space velocity of propane is 7.2h-1. By Al2O3The reaction product separated by the S molecular sieve column directly enters a hydrogen flameAn Agilent 7890A gas chromatograph of a detector (FID) is used for on-line analysis to obtain the propane conversion rate and the propylene selectivity. The test results are shown in Table 1.
TABLE 1
Figure BDA0002207553710000251
Figure BDA0002207553710000261
As can be seen from Table 1, the dehydrogenation catalyst prepared by the method of the present invention has excellent performance when used in the reaction of propane dehydrogenation to produce propylene. The experimental results of the catalyst Cat-1 and the catalysts Cat-D-1, Cat-D-2, Cat-D-3, Cat-D-4, Cat-D-5 and Cat-D-6 are compared, and it can be found that compared with the macroporous SBA-15 molecular sieve which is not modified according to the method, the macroporous SBA-15 molecular sieve which is subjected to one-time silanization ball milling treatment and two-time high-temperature calcination treatment is more suitable to be used as a carrier of a propane dehydrogenation reaction catalyst, and can effectively improve the propane conversion rate and the propylene selectivity.
Obviously, the method for silanization ball milling and high-temperature calcination modification of the macroporous SBA-15 molecular sieve provided by the invention can effectively improve the pore channel structure of the mesoporous material, including improving the average pore diameter, specific surface area and pore volume of the material. The modified macroporous SBA-15 molecular sieve is used as a carrier, and a metal component is loaded to obtain the catalyst for preparing the propylene by propane dehydrogenation. When the catalyst is used for propane dehydrogenation reaction, the catalytic effect with excellent propane conversion rate and propylene selectivity can be obtained.
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 (21)

1. A preparation method of a catalyst for preparing propylene by propane dehydrogenation is characterized by comprising the following steps:
(a) in the presence of a template agent, mixing and contacting tetraethoxysilane and a hydrochloric acid solution; obtaining a mixed solution;
(b) crystallizing the mixed solution to obtain a crystallized product, and sequentially carrying out solid-liquid separation, drying and template agent removal treatment on the crystallized product to obtain an SBA-15 molecular sieve;
(c) sequentially carrying out primary silanization ball milling treatment and twice high-temperature calcination treatment on the SBA-15 molecular sieve to obtain a modified SBA-15 molecular sieve;
(d) taking the modified SBA-15 molecular sieve as a carrier, introducing an active metal component, and preparing a propylene catalyst by propane dehydrogenation;
wherein, in the step (c), the silanization ball milling treatment method comprises the following steps; under the protection of inert gas, mixing the SBA-15 molecular sieve with silane or a silane derivative, and carrying out ball milling treatment on the obtained mixture to obtain the SBA-15 molecular sieve subjected to silanization ball milling treatment;
the method for the two high-temperature calcination treatments independently comprises the following steps: under the protection of inert gas, the SBA-15 molecular sieve treated by silanization ball milling is heated from the initial temperature to the end temperature and is kept at the end temperature for a period of time.
2. The method of claim 1, wherein the conditions of the silanized ball milling process comprise: the ball milling temperature is 20-100 ℃, the diameter of the grinding ball is 2-8mm, the rotation speed of the grinding ball is 300-600r/min, and the time is 1-30 h.
3. The method of claim 1, wherein the silane is monosilane SiH4Or disilane Si2H6The silane derivative is monosilane in which 2 to 4 hydrogen atoms are substituted with a substituent or disilane in which 2 to 6 hydrogen atoms are substituted with a substituent.
4. The method of claim 3, wherein the substituents are halogen and/or C1-C4 alkyl.
5. The method of claim 1, wherein the silane derivative is selected from one or more of dichlorodimethylsilane, hexamethyldisilane, trimethylchlorosilane, tetramethylsilane, methyltrichlorosilane.
6. The method of claim 1, wherein the weight ratio of silane or silane derivative to SBA-15 molecular sieve is from 0.03 to 0.2: 1.
7. the method of claim 1, wherein the two high temperature calcination treatments each independently comprise: under the protection of inert gas, heating the SBA-15 molecular sieve from 10-40 ℃ to 500-700 ℃ at the heating rate of 0.5-5 ℃/min, and keeping the temperature for 4-20h to carry out first high-temperature calcination treatment; then heating the SBA-15 molecular sieve subjected to the first high-temperature calcination treatment from 10-40 ℃ to 550-750 ℃ at the heating rate of 1-10 ℃/min, and keeping the temperature for 3-15h to perform second high-temperature calcination treatment.
8. The process of any one of claims 1-7, wherein in step (a), the conditions of the mixing contact comprise: the temperature is 25-60 deg.C, and the time is 20-120 min.
9. The method of claim 1, wherein,
the feeding ratio of the template agent to the tetraethoxysilane to the hydrochloric acid solution is 1 g: 2-3 g: 1-5 mL.
10. The method of claim 9, wherein,
the template agent is triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene EO20PO70EO20。
11. The method of any one of claims 1-7, wherein in step (b), the crystallization conditions comprise: the temperature is 90-180 ℃ and the time is 10-40 h.
12. The method of claim 1, wherein,
the method for removing the template comprises the following steps: washing the dried material with alcohol at 90-120 deg.C for 10-40 h.
13. The method as claimed in claim 1, wherein the obtained SBA-15 molecular sieve has a two-dimensional hexagonal pore structure with a specific surface area of 250-450m2Per g, pore volume of 0.8-1.3mL/g, average pore diameter of 10-13.5 nm.
14. The method as claimed in any one of claims 1 to 7, wherein the modified SBA-15 molecular sieve has a two-dimensional hexagonal channel structure with a specific surface area of 300-500m2Per g, pore volume of 1-1.5mL/g, average pore diameter of 12-14.5 nm.
15. The method of claim 1, wherein the method of introducing the reactive metal component comprises: and (2) soaking the modified SBA-15 molecular sieve in a solution containing an active metal component precursor, and sequentially carrying out solvent removal treatment, drying treatment and roasting treatment after soaking.
16. The method of claim 15, wherein,
the impregnation conditions include: the temperature is 20-90 ℃ and the time is 2-16 h; and/or
The conditions of the drying treatment include: the temperature is 70-150 ℃, and the time is 3-16 h; and/or
The roasting treatment conditions comprise: the temperature is 500-650 ℃, and the time is 3-12 h.
17. The method of claim 15, wherein the active metal component is one or more of platinum, tin, zinc, magnesium, calcium, and gallium.
18. The method of claim 17, wherein,
the active metal component is one or more of platinum, tin, magnesium and calcium.
19. A catalyst for the dehydrogenation of propane to produce propylene prepared by the process of any one of claims 1 to 18.
20. Use of the catalyst for propane dehydrogenation to propylene of claim 19 in a propane dehydrogenation reaction.
21. Use according to claim 20, wherein the conditions of the propane dehydrogenation reaction comprise: the reaction temperature is 550-650 ℃, the reaction pressure is 0.02-0.3MPa, and the molar ratio of propane to hydrogen in the raw materials is 1: 0.2 to 5, and the mass space velocity of the propane is 1 to 15 hours-1。
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