CN113145102A - Supported catalyst, preparation and application thereof - Google Patents

Supported catalyst, preparation and application thereof Download PDF

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CN113145102A
CN113145102A CN202010073771.9A CN202010073771A CN113145102A CN 113145102 A CN113145102 A CN 113145102A CN 202010073771 A CN202010073771 A CN 202010073771A CN 113145102 A CN113145102 A CN 113145102A
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solution
catalyst
oxide
precursor
zinc oxide
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邵怀启
王德龙
姜涛
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Petrochina Co Ltd
Tianjin University of Science and Technology
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Petrochina Co Ltd
Tianjin University of Science and Technology
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/26—Chromium
    • 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
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C07C5/3335—Catalytic processes with metals
    • 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 discloses a supported catalyst and preparation and application thereof. The catalyst comprises a zinc oxide doped regular mesoporous alumina carrier, and an active component and an auxiliary agent which are loaded on the carrier; the active component comprises chromium oxide, and the auxiliary agent comprises alkali metal oxide, alkaline earth metal oxide and fourth subgroup metal oxide. The catalyst has high catalytic activity, high olefin selectivity and good stability, and can improve the olefin yield and reduce carbon deposit generated in the catalyst reaction process when being applied to the reaction process of preparing propylene by propane dehydrogenation.

Description

Supported catalyst, preparation and application thereof
Technical Field
The invention belongs to the field of petrochemical industry, in particular to the technical field of catalytic dehydrogenation, and relates to a supported catalyst and preparation and application thereof.
Background
Currently, industrial propylene is mainly produced in the world through processes such as naphtha cracking, catalytic cracking, propane dehydrogenation, methanol oxidation and the like, wherein 61% of propylene yield in the world is from naphtha cracking, and 27% of propylene yield in the world is from catalytic cracking. But 90% of propylene in China comes from naphtha cracking, catalytic cracking and methanol oxidative dehydrogenation. The propylene source can show that the production of propylene is highly dependent on the oil refining industry, the traditional process for preparing propylene has the defects of high reaction temperature requirement, high energy consumption, low olefin yield and the like, and the yield of the traditional process cannot meet the requirement of the existing market for propylene along with the continuous increase of the requirement for propylene. In recent years, the demand of China for propylene is continuously rising, the yield of propylene is a gap, and the import price of propylene is also rising year by year, so that the preparation of Propylene (PDH) by propane dehydrogenation becomes an important way for increasing the yield of propylene.
Chinese patents CN 201410392504.2 and CN 201410392215.2 disclose a low-carbon hydrocarbon dehydrogenation catalyst containing framework silver and framework boron, respectively, and a preparation method thereof, wherein alumina containing silver or boron is used as a carrier, chromium oxide is used as an active component, sodium, potassium, calcium, magnesium, copper, zirconium, cerium and silver are used as auxiliaries, and the introduction of framework silver or boron improves the stability and the carbon deposition resistance of the catalyst.
Chinese patent CN 201310234194.7 discloses a preparation method of a chromium oxide/alumina catalyst, which adopts a one-step alcohol-heating method to synthesize a flaky chromium oxide/alumina catalyst with alumina as a carrier and chromium oxide as an active component. The method has the characteristics of higher propane conversion rate, good propylene selectivity and lower cost in the application of preparing olefin by dehydrogenating low-carbon alkane.
Patent application CN 103301830a discloses a preparation method of a chromium oxide/alumina catalyst and its application in the dehydrogenation of light alkanes to olefins. A hydrothermal one-step synthesis method is adopted to synthesize a catalyst active component, namely chromium oxide, uniformly dispersed on porous alumina as a carrier by using a chromium source, an aluminum source, a template agent and deionized water to prepare the high-performance catalyst for propylene by propane dehydrogenation. The method has the advantages of high activity, good stability and high yield of propylene, and has good and high economic benefits; the deactivated catalyst can be regenerated by re-calcination, and has no obvious difference in catalytic effect from the newly prepared catalyst and good reusability.
Patent application CN 104128175A discloses a low-carbon hydrocarbon dehydrogenation catalyst with good hydrothermal stability and a preparation method thereof, wherein magnesium and zinc are added into alumina to prepare a spinel-structured composite carrier, and then chromium oxide and alkali metal or alkaline earth metal oxide are loaded as an auxiliary agent, and the introduction of magnesium and zinc increases the hydrothermal stability of the catalyst and prevents the catalyst from being pulverized during regeneration.
Chinese patent CN 201210408504.8 discloses a dehydrogenation catalyst and its preparation method, which adopts ammonia-treated alumina as carrier, chromium as active component, and potassium, manganese, cobalt, iron, nickel, copper and zinc as auxiliary agent, and has the advantages of low content of chromium oxide, high activity, good propylene selectivity, etc.
The deactivation of chromium oxide based catalysts is related to the formation of carbon deposits on the surface during the reaction of the catalyst. Reducing carbon deposit is helpful to prolong the service life of the catalyst, reduce the inactivation rate of the catalyst and improve the activity of the catalyst. Unfortunately, it is not possible to design catalysts in a targeted manner to reduce the carbon deposits produced during the reaction.
Disclosure of Invention
Based on the background technology, the invention provides a supported catalyst and preparation and application thereof. The catalyst has high catalytic activity, high olefin selectivity and good stability, and can improve the olefin yield and reduce carbon deposit generated in the catalyst reaction process when being applied to the reaction process of preparing propylene by propane dehydrogenation.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a supported catalyst, which comprises a zinc oxide doped regular mesoporous alumina carrier, and an active component and an auxiliary agent which are loaded on the carrier;
the active component comprises chromium sesquioxide, and the auxiliary agent comprises alkali metal oxide, alkaline earth metal oxide and fourth subgroup metal oxide.
In a preferable embodiment of the present invention, the content of zinc oxide is 0.5 to 2% by weight of the aluminum oxide, the loading amount of chromium sesquioxide is 5 to 20%, the loading amount of alkali metal oxide is 0.05 to 1.0%, the loading amount of alkaline earth metal oxide is 0.05 to 1.0%, and the loading amount of fourth subgroup metal oxide is 0.05 to 3.0%.
According to the catalyst of the present invention, the alkali metal is one or a combination of two or more of sodium, potassium and lithium, preferably sodium.
According to the catalyst of the invention, the alkaline earth metal is one or a combination of more than two of magnesium, calcium, strontium and barium, preferably strontium.
According to the catalyst of the invention, the fourth subgroup metal is titanium, zirconium or hafnium, preferably zirconium.
In another aspect of the present invention, there is provided a method for preparing the above supported catalyst, comprising the steps of:
dissolving a chromium sesquioxide precursor, an alkali metal, an alkaline earth metal and a fourth subgroup metal precursor into water to prepare a uniform solution, adding the uniform solution into a zinc oxide doped regular mesoporous alumina carrier, uniformly stirring, drying after molding, and calcining to obtain the catalyst.
In a preferable scheme of the invention, the zinc oxide doped regular mesoporous alumina carrier is prepared by a template method.
Preferably, the template method comprises the steps of:
dissolving a template agent in absolute ethyl alcohol to prepare a solution 1;
dissolving a zinc oxide precursor and an aluminum oxide precursor in a nitric acid water solution with the concentration of 68-70% to prepare a solution 2;
and mixing the solution 1 and the solution 2 for reaction, removing the solvent, and calcining to obtain the zinc oxide doped aluminum oxide carrier.
In a preferred embodiment of the present invention, the template method comprises the steps of:
dissolving a template agent in absolute ethyl alcohol according to the molar ratio of the template agent to aluminum oxide of 1:10-1:50 to prepare a solution 1;
dissolving a zinc oxide precursor and an aluminum oxide precursor in a nitric acid aqueous solution with the concentration of 68-70% according to the proportion that zinc oxide is 0.1-3.0% of the weight of aluminum oxide to prepare a solution 2;
and adding the solution 2 into the solution 1, stirring for 0.5-4h, heating at 30-70 ℃ for 24-72h to evaporate the solvent, heating the residue to 500-900 ℃ at the speed of 1-10 ℃/min, and carrying out heat preservation and calcination for 3-8h to obtain the zinc oxide doped aluminum oxide carrier.
In the template method, the alumina precursor is aluminum isopropoxide, aluminum nitrate or sodium aluminate, preferably aluminum isopropoxide.
In the template method, the zinc oxide precursor is zinc nitrate or zinc chloride, preferably zinc nitrate.
In the above-mentioned templating method, the templating agent is a block copolymer P123, a block copolymer F127, dodecyltrimethylaminebromide, tetradecyltrimethaminebromide or hexadecyltrimethylaminebromide, and preferably a block copolymer F127.
According to the preparation method of the supported catalyst, the chromic oxide precursor is chromium nitrate, chromic acid, chromium trioxide, chromium acetylacetonate, chromium acetate or chromium oxalate, preferably chromium trioxide or chromium acetate, and more preferably chromium trioxide.
The catalyst forming machine is a tablet machine, a roller type granulator, a pelleting machine, a strip extruding machine and the like, and the formed shape is spherical, flaky, cylindrical, star-shaped or trilobal.
According to the preparation method of the supported catalyst, the drying conditions comprise room temperature drying for 12-24 hours and 100 ℃ drying for 2-18 hours; the calcining condition comprises calcining for 2-8 h at the temperature of 500-900 ℃.
The invention further provides the application of the supported catalyst in the preparation of propylene by propane dehydrogenation.
Preferably, the catalyst of the present invention is used in propane removalWhen the propylene is prepared by hydrogen, the reaction temperature is 550--1。
When the supported catalyst is applied to preparing propylene by propane dehydrogenation, the initial conversion rate of propane is more than 54 percent, the selectivity of the propylene is higher than 87 percent, and the carbon deposition resistance of the catalyst is obviously enhanced.
The invention has the advantages and beneficial effects that:
1) the zinc oxide is added in the process of forming the alumina framework structure, so that the zinc oxide can be fully doped in the alumina framework, the acid structure of the alumina is effectively adjusted, the generation of carbon deposition is inhibited, and the high-temperature stability is good.
2) The invention can fully utilize the uniform pore channel structure of the carrier, improve the dispersion degree of the chromium sesquioxide on the carrier, and simultaneously reduce the mass transfer resistance of the propane and the propylene, thereby improving the catalytic activity.
3) The alkaline earth metal and the fourth subgroup metal are added into the formula of the catalyst, so that the selectivity of the catalyst can be effectively increased, and carbon deposition on the catalyst is reduced.
Drawings
FIG. 1 is an SEM photograph of catalyst A obtained in example 1 of the present invention.
FIG. 2 is an XRD pattern of catalyst A, catalyst B and catalyst C obtained in the example of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
This example prepares catalyst A
1) Preparation of Zn-doped alumina carrier:
weighing 75.00g of template agent F127, dissolving in 1000mL of absolute ethyl alcohol, stirring until the template agent F127 is completely dissolved, adding 0.56g of zinc nitrate hexahydrate, and continuing stirring for 3 hours to prepare a solution 1;
weighing 122.55g of aluminum isopropoxide, weighing 750mL of absolute ethyl alcohol, placing the mixture into a three-neck flask, violently stirring for 30min, adding 80mL of concentrated nitric acid, and continuously stirring for 5h until the solution is completely dissolved to obtain a solution 2;
solution 2 was added dropwise to solution 1 over 30min and stirred for 8h to mix thoroughly.
And slowly heating the solution to 60 ℃, keeping the temperature and heating for 48h, evaporating the solvent to obtain white powder, heating to 700 ℃ at the speed of 2 ℃/min, and calcining for 4h to obtain 30.75g of the 0.5% Zn-doped alumina carrier.
2) Loading a catalyst:
dissolving 6.04g of chromium trioxide, 0.42g of sodium nitrate, 0.31g of strontium nitrate and 0.86g of zirconium nitrate in 100mL of water, adding 30.75g of the 3% Zn-doped alumina carrier, stirring for 30min, drying at room temperature for 18h, drying at 100 ℃ for 12h, calcining at 750 ℃ for 6h, and pressing into sheets by using a tablet press to obtain the catalyst A.
Based on the weight of the alumina, the loading of chromium oxide is 15.0%, the loading of sodium oxide is 0.5%, the loading of strontium oxide is 0.5%, and the loading of zirconium oxide is 1.0%.
Example 2
This example prepares catalyst B
1) Preparation of Zn-doped alumina carrier:
weighing 75.00g of template agent F127, dissolving in 1000mL of absolute ethyl alcohol, stirring until the template agent F127 is completely dissolved, adding 1.12g of zinc nitrate hexahydrate, and continuing stirring for 3 hours to prepare a solution 1;
weighing 122.55g of aluminum isopropoxide, weighing 750mL of absolute ethyl alcohol, placing the mixture into a three-neck flask, violently stirring for 30min, adding 80mL of concentrated nitric acid, and continuously stirring for 5h until the solution is completely dissolved to obtain a solution 2;
solution 2 was added dropwise to solution 1 over 30min and stirred for 8h to mix thoroughly.
And slowly heating the solution to 60 ℃, keeping the temperature and heating for 48h, evaporating the solvent to obtain white powder, heating to 700 ℃ at the speed of 2 ℃/min, and calcining for 4h to obtain 30.91g of the 1% Zn-doped alumina carrier.
2) Loading a catalyst:
dissolving 6.04g of chromium trioxide, 0.42g of sodium nitrate, 0.31g of strontium nitrate and 0.86g of zirconium nitrate in 100mL of water, adding 30.91g of the 1% Zn-doped alumina carrier, stirring for 30min, drying at room temperature for 18h, drying at 100 ℃ for 12h, calcining at 750 ℃ for 6h, and pressing into a sheet by a tablet press to obtain the catalyst B.
Based on the weight of the alumina, the loading of chromium oxide is 15.0%, the loading of sodium oxide is 0.5%, the loading of strontium oxide is 0.5%, and the loading of zirconium oxide is 1.0%.
Example 3
This example prepares catalyst C
1) Preparation of Zn-doped alumina carrier:
weighing 75.00g F127 and dissolving in 1000mL of absolute ethyl alcohol, stirring until the solution is completely dissolved, adding 2.24g of zinc nitrate hexahydrate, and stirring for 3 hours to obtain a solution 1;
weighing 122.55g of aluminum isopropoxide, weighing 750mL of absolute ethyl alcohol, placing the mixture into a three-neck flask, violently stirring for 30min, adding 80mL of concentrated nitric acid, and continuously stirring for 5h until the solution is completely dissolved to obtain a solution 2;
solution 2 was added dropwise to solution 1 over 30min and stirred for 8h to mix thoroughly. The solution was slowly heated to 60 ℃ and kept at that temperature for 48h, the solvent was evaporated to give a white powder, which was then heated at a rate of 2 ℃/min to 700 ℃ and calcined for 4h to give 31.21g of a 2% Zn-doped alumina support.
2) Loading a catalyst:
dissolving 6.04g of chromium trioxide, 0.42g of sodium nitrate, 0.31g of strontium nitrate and 0.86g of zirconium nitrate in 100mL of water, adding 31.21g of the 2% Zn-doped alumina carrier, stirring for 30min, drying at room temperature for 18h, drying at 100 ℃ for 12h, calcining at 750 ℃ for 6h, and pressing into sheets by using a tablet press to obtain the catalyst C.
Based on the weight of the alumina, the loading of chromium oxide is 15.0%, the loading of sodium oxide is 0.5%, the loading of strontium oxide is 0.5%, and the loading of zirconium oxide is 1.0%.
Example 4
This example preparation of catalyst D
1) Preparation of Zn-doped alumina carrier:
weighing 75.00g of template agent F127, dissolving in 1000mL of absolute ethyl alcohol, stirring until the template agent F127 is completely dissolved, adding 3.36g of zinc nitrate hexahydrate, and continuing stirring for 3 hours to prepare a solution 1;
weighing 122.55g of aluminum isopropoxide, weighing 750mL of absolute ethyl alcohol, placing the mixture into a three-neck flask, violently stirring for 30min, adding 80mL of concentrated nitric acid, and continuously stirring for 5h until the solution is completely dissolved to obtain a solution 2;
solution 2 was added dropwise to solution 1 over 30min and stirred for 8h to mix thoroughly.
The solution was slowly heated to 60 ℃ and kept at that temperature for 48h, the solvent was evaporated to give a white powder, which was then heated at a rate of 2 ℃/min to 700 ℃ and calcined for 4h to give 31.52g of 3% Zn-doped alumina support.
2) Loading a catalyst:
dissolving 6.04g of chromium trioxide, 0.42g of sodium nitrate, 0.31g of strontium nitrate and 0.86g of zirconium nitrate in 100mL of water, adding 31.52g of the 3% Zn-doped alumina carrier, stirring for 30min, drying at room temperature for 18h, drying at 100 ℃ for 12h, calcining at 750 ℃ for 6h, and pressing into a sheet by a tablet press to obtain the catalyst D.
Based on the weight of the alumina, the loading of chromium oxide is 15.0%, the loading of sodium oxide is 0.5%, the loading of strontium oxide is 0.5%, and the loading of zirconium oxide is 1.0%.
Comparative example 1
Preparation of catalyst E of this comparative example
1) Preparing an alumina carrier:
weighing 75.00g F127, dissolving in 1000mL of absolute ethyl alcohol, and stirring until the solution is completely dissolved to obtain a solution 1;
weighing 122.55g of aluminum isopropoxide, weighing 750mL of absolute ethyl alcohol, placing the mixture into a three-neck flask, violently stirring for 30min, adding 80mL of concentrated nitric acid, and continuously stirring for 5h until the solution is completely dissolved to obtain a solution 2;
solution 2 was added dropwise to solution 1 over 30min and stirred for 8h to mix thoroughly. Slowly heating the solution to 60 ℃, keeping the temperature and heating for 48h, evaporating the solvent to obtain white powder, heating to 700 ℃ at the speed of 2 ℃/min, and calcining for 4h to obtain 30.60g of the alumina carrier.
2) Loading a catalyst:
adding 30.60g of the alumina carrier into 6.04g of chromium trioxide, 0.42g of sodium nitrate, 0.31g of strontium nitrate and 0.86g of zirconium nitrate, stirring for 30min, drying at room temperature for 18h, drying at 100 ℃ for 12h, calcining at 750 ℃ for 6h, and pressing into a sheet by a tablet press to obtain the catalyst E.
Based on the weight of the alumina, the loading of chromium oxide is 15.0%, the loading of sodium oxide is 0.5%, the loading of strontium oxide is 0.5%, and the loading of zirconium oxide is 1.0%.
FIG. 1 is an SEM image of catalyst A. FIG. 2 is an XRD pattern for catalyst A, catalyst B, catalyst C, catalyst D and catalyst E; wherein only gamma-alumina and Cr are found2O3The crystal diffraction peak of (2) shows no diffraction peak related to Zn, which indicates that the structure of alumina is not changed by adding Zn, and the structure of zinc-aluminum composite oxide is not formed.
Example 5
In this example, the catalyst obtained above was applied to the production of propylene by dehydrogenation of propane.
Carrying out propane dehydrogenation reaction on the catalyst A, the catalyst B, the catalyst C and the catalyst D obtained in the examples 1 to 4 and the catalyst E obtained in the comparative example 1 in a normal-pressure micro-reaction device, wherein a fixed bed reactor is adopted, the inner diameter of the reactor is 20mm, the loading amount of the catalyst is 10g, the reaction temperature is 610 ℃, the reaction pressure is 0.05MPa, and the space velocity of propane gas is 300h-1The propane conversion and propylene selectivity are shown in Table 1, and the amount of carbon deposited after the reaction is shown in Table 2.
TABLE 1 reaction Performance of the catalyst for the catalytic dehydrogenation of propane in the examples
Figure BDA0002377944860000081
From the results in table 1, it can be seen that after the experiment is performed for 180min, the activity and selectivity of the catalyst of the present invention are not significantly reduced, which indicates that the catalyst has good stability and long service life.
When the supported catalyst is applied to preparing propylene by propane dehydrogenation, the initial conversion rate of propane is more than 54 percent, the selectivity of the propylene is higher than 87 percent, and the carbon deposition resistance is obviously enhanced.
TABLE 2 amount of carbon deposition after the reaction of the catalyst catalyzed propane dehydrogenation in the examples
Figure BDA0002377944860000082
Figure BDA0002377944860000091
From the results in table 2, it can be seen that the carbon deposition amount of the catalyst after the reaction of the present invention is significantly reduced after the experiment is performed for 180min, which indicates that the catalyst has a better carbon deposition resistance.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.

Claims (18)

1. A supported catalyst is characterized by comprising a zinc oxide doped regular mesoporous alumina carrier, and an active component and an auxiliary agent which are loaded on the carrier;
the active component comprises chromium sesquioxide, and the auxiliary agent comprises alkali metal oxide, alkaline earth metal oxide and fourth subgroup metal oxide.
2. The supported catalyst according to claim 1, wherein the zinc oxide is contained in an amount of 0.5 to 2%, the chromium oxide is contained in an amount of 5 to 20%, the alkali metal oxide is contained in an amount of 0.05 to 1.0%, the alkaline earth metal oxide is contained in an amount of 0.05 to 1.0%, and the fourth subgroup metal oxide is contained in an amount of 0.05 to 3.0% based on the weight of the alumina.
3. The supported catalyst of claim 1, wherein the alkali metal is one or a combination of two or more of sodium, potassium, and lithium.
4. The supported catalyst of claim 1, wherein the alkaline earth metal is one or a combination of two or more of magnesium, calcium, strontium, and barium.
5. The supported catalyst of claim 1, wherein the fourth subgroup metal is titanium, zirconium or hafnium.
6. A process for the preparation of a supported catalyst according to any one of claims 1 to 5, comprising the steps of:
dissolving a chromium sesquioxide precursor, an alkali metal, an alkaline earth metal and a fourth subgroup metal precursor into water to prepare a uniform solution, adding the uniform solution into a zinc oxide doped regular mesoporous alumina carrier, uniformly stirring, drying after molding, and calcining to obtain the catalyst.
7. The preparation method of claim 6, wherein the zinc oxide doped regular mesoporous alumina support is prepared by a template method.
8. The method of claim 7, wherein the template method comprises the steps of:
dissolving a template agent in absolute ethyl alcohol to prepare a solution 1;
dissolving a zinc oxide precursor and an aluminum oxide precursor in a nitric acid water solution to prepare a solution 2;
and mixing the solution 1 and the solution 2 for reaction, removing the solvent, and calcining to obtain the zinc oxide doped aluminum oxide carrier.
9. The method of claim 7, wherein the template method comprises the steps of:
dissolving a template agent in absolute ethyl alcohol according to the molar ratio of the template agent to aluminum oxide of 1:10-1:50 to prepare a solution 1;
dissolving a zinc oxide precursor and an aluminum oxide precursor in a nitric acid aqueous solution with the concentration of 68-70% according to the proportion that zinc oxide is 0.1-3.0% of the weight of aluminum oxide to prepare a solution 2;
and adding the solution 2 into the solution 1, stirring for 0.5-4h, heating at 30-70 ℃ for 24-72h to evaporate the solvent, heating the residue to 500-900 ℃ at the speed of 1-10 ℃/min, and carrying out heat preservation and calcination for 3-8h to obtain the zinc oxide doped aluminum oxide carrier.
10. The method according to claim 8 or 9, wherein the alumina precursor is aluminum isopropoxide, aluminum nitrate or sodium aluminate.
11. The method according to claim 8 or 9, wherein the zinc oxide precursor is zinc nitrate or zinc chloride.
12. The method according to claim 8 or 9, wherein the template is a block copolymer P123, a block copolymer F127, dodecyltrimethylaminium bromide, tetradecyltrimethaminium bromide or hexadecyltrimethylaminium bromide.
13. The method of claim 6, wherein the chromic oxide precursor is chromic nitrate, chromic acid, chromic trioxide, chromic acetylacetonate, chromic acetate, or chromic oxalate.
14. The method of claim 13, wherein the chromium trioxide precursor is chromium trioxide or chromium acetate.
15. The method according to claim 6, wherein the machine for forming the catalyst is a tablet press, a roll granulator, a pellet mill or a plodder; the shape after molding is spherical, flaky, cylindrical, star-shaped or trilobal.
16. The preparation method according to claim 6, wherein the drying conditions comprise room temperature drying for 12-24 h, 100 ℃ drying for 2-18 h; the calcining condition comprises calcining for 2-8 h at the temperature of 500-900 ℃.
17. Use of a supported catalyst according to any one of claims 1 to 5 for the dehydrogenation of propane to propylene.
18. The use as claimed in claim 17, wherein the reaction temperature is 550-650 ℃, the reaction pressure is 0.01-1MPa, and the propane space velocity is 150-1000h-1。
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138361A (en) * 2022-07-04 2022-10-04 黄河三角洲京博化工研究院有限公司 Ordered mesoporous low-carbon alkane dehydrogenation catalyst, preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106040271A (en) * 2016-05-30 2016-10-26 天津科技大学 Catalyst for propylene preparation using propane dehydrogenation and preparation method of catalyst
CN109289831A (en) * 2018-10-09 2019-02-01 天津科技大学 The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon
CN109331810A (en) * 2018-08-22 2019-02-15 天津科技大学 A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106040271A (en) * 2016-05-30 2016-10-26 天津科技大学 Catalyst for propylene preparation using propane dehydrogenation and preparation method of catalyst
CN109331810A (en) * 2018-08-22 2019-02-15 天津科技大学 A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane
CN109289831A (en) * 2018-10-09 2019-02-01 天津科技大学 The catalyst of preparing propylene by dehydrogenating propane and preparation method thereof with high anti-carbon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
马占华等: "助剂Zn 对PtSn/Al2O3催化剂丙烷脱氢性能的影响", 《化工进展》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115138361A (en) * 2022-07-04 2022-10-04 黄河三角洲京博化工研究院有限公司 Ordered mesoporous low-carbon alkane dehydrogenation catalyst, preparation method and application

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Application publication date: 20210723