CN115779974A - Propane dehydrogenation-hydrogen combustion catalyst and preparation method and application thereof - Google Patents
Propane dehydrogenation-hydrogen combustion catalyst and preparation method and application thereof Download PDFInfo
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 124
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- 239000001257 hydrogen Substances 0.000 title claims abstract description 77
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 77
- 239000001294 propane Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 26
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- 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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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a propane dehydrogenation-hydrogen combustion catalyst and a preparation method and application thereof. The catalyst takes a hydrophobic molecular sieve as a carrier, the dehydrogenation active metal component is coated inside the molecular sieve, and the hydrogen burning active metal component is loaded outside the molecular sieve, so that two processes of propane dehydrogenation into propylene, hydrogen and hydrogen selective combustion can be simultaneously realized in one reactor, and the catalyst has the advantages of self-heating reaction, high propane single-pass conversion rate, hydrogen byproduct, long single-pass dehydrogenation period and the like. The catalyst is a hydrophobic molecular sieve coated catalyst, propane firstly generates propylene and hydrogen in a dehydrogenation active center coated in the molecular sieve, and then the hydrogen generates water in a hydrogen burning active center on the outer surface of the molecular sieve and releases heat. The invention synthesizes the catalyst with three functions of dehydrogenation, hydrogen burning and hydrophobic, realizes the energy-saving propane dehydrogenation-hydrogen burning integrated process, and has higher industrial application value.
Description
Technical Field
The invention relates to a propane dehydrogenation catalyst, in particular to a propane dehydrogenation-hydrogen burning catalyst and a preparation method and application thereof.
Background
Propylene is used as an important basic chemical raw material and is mainly used for producing high-added-value chemical products such as polypropylene, acrylonitrile, propylene oxide, acrylic acid and the like. With the large increase in the consumption of propylene downstream products, the demand for propylene faces a short supply. Currently, the main modes of propylene production are still catalytic cracking and steam cracking in the traditional petrochemical route. The propane dehydrogenation technology has the advantages of simple flow, high economic benefit, byproduct hydrogen gas and the like, and is a competitive propylene preparation technology.
The catalytic dehydrogenation of propane to propylene in the absence of oxygen has been commercialized using supported Pt and CrOx catalysts, mainly PtSn/Al from UOP 2 O 3 And Cr of ABB Lumus Co 2 O 3 /Al 2 O 3 。PtSn/Al 2 O 3 The catalyst has high activity, good stability and high propylene selectivity, but Pt is a noble metal, so the catalyst cost is higher; cr (chromium) component 2 O 3 /Al 2 O 3 Catalytic activity and antitoxicityGood, cheap but Cr 2 O 3 /Al 2 O 3 The use of the catalyst comprises reduction, dehydrogenation, purging, coke burning regeneration and other processes. Propane is dehydrogenated in an adiabatic bed (590-600 ℃), and as the bed temperature is reduced (560-580 ℃), the carbon deposit deposited on the catalyst needs to be removed by burning and the bed temperature is increased, the single dehydrogenation time is only about 9 minutes (CN 115073156A), and the effective production time of the reactor is obviously influenced by the single dehydrogenation period. In addition, catalytic dehydrogenation of propane has (1) equilibrium conversion limited by thermodynamics, e.g., only 50% at 600 ℃ for propane; (2) The propane and the propylene in the dehydrogenation product are separated by adopting low-temperature rectification, the separation energy consumption is high, and the lower the one-way conversion rate is, the higher the energy consumption is and the like.
The hydrogen atoms generated by the activation of propane oxidative dehydrogenation alkane and oxygen are combined into water, so that the defects of the propane catalytic dehydrogenation process can be overcome, and the method has the advantages of unlimited reaction, low energy consumption, no carbon deposition, good application prospect and the like. Researchers at home and abroad have carried out a great deal of research on oxidative dehydrogenation, disclose an alkane over-oxidation mechanism and an olefin selectivity regulation mechanism, and make progress in the aspects of novel catalytic materials, advanced synthesis methods and the like, but the key technology of the oxidative dehydrogenation of alkane is not broken through, and the olefin selectivity and the space-time yield are still the bottleneck problems of industrial application.
Therefore, the catalyst capable of realizing the dehydrogenation-hydrogen burning coupling process is developed, the self-heating, the byproduct hydrogen gas, the high single-pass conversion rate and the selectivity in the dehydrogenation process are realized, the single-pass dehydrogenation time is long, and the catalyst has important significance for improving the economy of the propane dehydrogenation process and reducing the energy consumption.
Disclosure of Invention
The invention provides a catalyst applied to a propane dehydrogenation-hydrogen burning integrated process and a preparation method thereof, aiming at the problems of external heat supply, low single-pass conversion rate, short single-pass dehydrogenation time and the like in the existing propane dehydrogenation process.
The technical scheme adopted by the invention for realizing the purpose is as follows:
a propane dehydrogenation-hydrogen burning catalyst takes a hydrophobic molecular sieve as a carrier, a dehydrogenation active metal component is coated inside the molecular sieve, and a hydrogen burning active metal component is loaded outside the molecular sieve; the dehydrogenation active metal component is one or more than two of metal oxides of V, cr, ni, ga, pt and Co, and the hydrogen burning active metal component is one or more than two of metal oxides corresponding to IIIB-VIIB elements or IIIA-VA elements.
Further, the hydrophobic molecular sieve is preferably S-1, MCM-41 or ZSM-5, and the molecular sieve has hydrophobicity and is of great importance for the catalyst, which is the key for ensuring the final realization of the propane dehydrogenation-hydrogen burning coupling process.
Further, the mass of the dehydrogenation active metal component accounts for 0.1-10% of the total mass of the propane dehydrogenation-hydrogen burning catalyst; the weight of the hydrogen burning active metal component accounts for 5-60% of the total weight of the propane dehydrogenation-hydrogen burning catalyst.
The preparation method of the propane dehydrogenation-hydrogen combustion catalyst adopts a hydrothermal crystallization method and comprises the following steps:
(1) Mixing and stirring a template agent, deionized water and a silicon source to form a uniform mixed solution;
(2) Aging the mixed solution under a stirring state;
(3) Adding a dehydrogenation active metal component into the mixed solution, and carrying out ultrasonic stirring;
(4) Transferring the mixed solution to a hydrothermal kettle for hydrothermal reaction;
(5) Filtering after the hydrothermal reaction is finished, and washing, drying and calcining the obtained solid to obtain the hydrophobic molecular sieve dehydrogenation catalyst;
(6) And loading the hydrogen burning active metal component outside the hydrophobic molecular sieve dehydrogenation catalyst to obtain the propane dehydrogenation-hydrogen burning catalyst.
Further, the template agent is tetrapropylammonium hydroxide (TPAOH), the silicon source is tetraethyl orthosilicate (TEOS), and the mass ratio of the template agent to the silicon source is 15:5-15.
Further, the aging time is 4-12 hours; the ultrasonic time is 5 to 60 minutes; the temperature of the hydrothermal reaction is 100-200 ℃, and the time of the hydrothermal reaction is 12-72 hours; the drying temperature is 60-120 ℃, and the drying time is 8-24 hours; the calcining temperature is 500-700 ℃, and the calcining time is 4-8 hours.
The propane dehydrogenation-hydrogen burning catalyst is applied to the reaction of preparing propylene by propane dehydrogenation, has three functions of dehydrogenation, hydrogen burning and hydrophobic, is coupled with the propane dehydrogenation-hydrogen burning process, realizes reaction self-heating and byproduct hydrogen gas, promotes the forward progress of the propane dehydrogenation reaction, and realizes higher propane conversion rate and propylene selectivity.
It is worth to be noted that the relative positions of the dehydrogenation active component and the hydrogen burning component and the carrier molecular sieve are very important, and if the dehydrogenation active component and the hydrogen burning component are coated inside the molecular sieve or loaded outside the molecular sieve together, the propane dehydrogenation-hydrogen burning coupling effect is poor. Meanwhile, the hydrophobicity is extremely important for the performance of the coupling catalyst, and the good hydrophobic performance is endowed to the catalyst besides the functions of composite dehydrogenation and hydrogen burning, which is also the core of the invention. If the coupling function is only the coupling dehydrogenation function and the coupling hydrogen burning function, and the importance of the hydrophobic function is neglected, the coupling effect is poor, and the actual requirement cannot be met.
The invention has the beneficial results that:
the catalyst has the functions of dehydrogenation and hydrogen burning, has hydrophobic performance, can couple the propane dehydrogenation and hydrogen burning processes, and simultaneously realizes two processes of propane dehydrogenation into propylene, hydrogen and hydrogen selective combustion in one reactor. Propane first generates propylene and hydrogen at dehydrogenation sites coated inside the molecular sieve, and then hydrogen generates water at the hydrogen-burning sites on the outer surface of the molecular sieve, and heat is released. By burning part of hydrogen generated in the reaction process, the self-heating of the reaction is realized, the forward progress of the dehydrogenation reaction is promoted, and the method has the advantages of high conversion rate of propane per pass, hydrogen byproduct, long single dehydrogenation period, energy saving and the like. The catalyst of the invention has excellent catalytic activity and stability, high propane conversion rate and propylene selectivity and higher industrial application value.
Drawings
FIG. 1 is a schematic diagram of a catalyst in which dehydrogenation active centers and hydrogen-burning active centers are jointly supported on a hydrophobic molecular sieve.
FIG. 2 is a schematic diagram of a catalyst in which a dehydrogenation active center and a hydrogen burning active center are jointly coated in a hydrophobic molecular sieve.
Fig. 3 is a schematic diagram of a catalyst in which a dehydrogenation active center is coated inside a hydrophobic molecular sieve and a hydrogen-burning active center is loaded outside the hydrophobic molecular sieve (i.e., a schematic diagram of a propane dehydrogenation-hydrogen burning catalyst of the present invention).
Detailed Description
The present invention is further illustrated with reference to examples, but the invention includes, but is not limited to, the scope of the examples. Modifications and adaptations made based on the contents and spirit of the present invention are within the scope of the present invention.
The performance test of the hydrophobic propane dehydrogenation-hydrogen burning catalyst is carried out on a fixed bed reactor, and the method comprises the following specific steps:
filling 3g of dehydrogenation-hydrogen combustion catalyst tablets into a reaction tube, filling quartz sand at two ends of the reaction tube for maintaining the height of a bed layer, adding quartz cotton for isolating the quartz sand and the catalyst, and assembling to obtain a fixed bed reactor;
introducing propane mixed gas into the reaction tube for reaction, collecting products obtained by the reaction through an air bag, and performing gas chromatography on-line analysis;
reaction conditions are as follows: and (3) introducing propane gas (60 ml/min), wherein the reaction temperature is 600 ℃, the reaction pressure is 0.1MPa, and the reaction time is 1h.
Example 1
In 2 O 3 /Ga 2 O 3 Preparation of @ S-1 hydrophobic dehydrogenation-hydrogen combustion catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen combustion catalyst comprises the following specific synthesis steps: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate to obtain a mixed solution, and aging for 6 hours at room temperature; adding 0.14g of gallium nitrate hydrate into 6g of deionized water, adding 1ml of ethylenediamine, carrying out ultrasonic treatment for 5min, and stirring for 60min to obtain a gallium nitrate solution; adding the gallium nitrate solution into the mixed solution, and stirring for 30min; finally, the mixed solution is transferred into a hydrothermal kettle and crystallized for 72 hours at 180 ℃. Filtering and washing after the crystallization process is finished, then drying at 80 ℃ for 12h, and roasting the dried solid in a muffle furnace at 600 ℃ for 6h to obtain the high-hydrophobicity Ga 2 O 3 @ S-1 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g of Ga was added 2 O 3 @ S-1 dehydrogenation catalyst, stirring for 10h at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /Ga 2 O 3 @ S-1 dehydrogenation-hydrogen-burning catalyst.
Example 2
In 2 O 3 /Ga 2 O 3 Preparation of a/@ S-1 Hydrophobically dehydrogenating-hydrogenating catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen burning catalyst comprises the following specific synthetic steps: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate to obtain a mixed solution, and aging for 6 hours at room temperature; then transferring the mixture into a hydrothermal kettle, and crystallizing for 72 hours at 180 ℃; and after the crystallization process is finished, filtering, washing, drying at 80 ℃ for 12 hours, then putting the solid into a muffle furnace, and calcining at 600 ℃ for 6 hours to obtain S-1. Adding 50ml of TPAOH into a 100ml beaker, adding calcined S-1 for etching for 8 hours, and centrifuging to obtain etched S-1; adding 6g of deionized water and 0.14g of gallium nitrate hydrate into a 50ml beaker, adding etched S-1, performing ultrasonic treatment for 5min, stirring for 10h at room temperature, heating and evaporating to dryness to obtain Ga 2 O 3 (ii) an/S-1 dehydrogenation catalyst; ga is mixed with 2 O 3 Adding the/S-1 into TPAOH used for etching, transferring the TPAOH into a hydrothermal kettle, crystallizing the TPAOH at 180 ℃ for 72 hours, filtering the TPAOH, drying the TPAOH at 80 ℃ for 12 hours, putting the TPAOH into a muffle furnace, and calcining the dried TPAOH at 600 ℃ for 6 hours to obtain hydrophobic Ga 2 O 3 /@ S-1 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g Ga was added 2 O 3 /@ S-1 dehydrogenation catalyst, stirring at room temperature for 10h; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /Ga 2 O 3 /@ S-1 dehydrogenation-hydrogenation catalyst.
Example 3
In 2 O 3 /Ga 2 O 3 @ ZSM-5 hydrophobic dehydrogenation-calcinationPreparation of Hydrogen catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen combustion catalyst comprises the following specific synthesis steps: sodium metaaluminate, tetrapropylammonium hydroxide, tetraethyl orthosilicate and deionized water in a molar ratio of 0.18:10:25:480, adding 0.14g of gallium nitrate hydrate, adjusting the pH value to 10 by using NaOH, stirring for 4 hours, transferring the mixed solution into a hydrothermal kettle, and crystallizing for 18 hours at 180 ℃; filtering and washing after the crystallization process is finished, then drying at 80 ℃ for 12h, and roasting the dried solid in a muffle furnace at 600 ℃ for 6h to obtain hydrophobic Ga 2 O 3 @ ZSM-5 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g Ga was added 2 O 3 @ ZSM-5 dehydrogenation catalyst, stirring for 10h at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /Ga 2 O 3 The catalyst of @ ZSM-5 dehydrogenation-hydrogen burning.
Example 4
In 2 O 3 /Ga 2 O 3 Preparation of @ MCM-41 hydrophobic dehydrogenation-hydrogen burning catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen burning catalyst comprises the following specific synthetic steps: mixing 65mL of water with 50mL of ammonia water, adding 0.5g of hexadecyl trimethyl ammonium bromide, adding 0.084g of gallium nitrate hydrate, stirring at 60 ℃ until the mixture is completely dissolved, and slowly dropwise adding 5mL of ethyl orthosilicate during stirring to generate white floccules. Stirring at 60 deg.C for 2 hr, filtering, washing, drying at 80 deg.C for 12 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain hydrophobic Ga 2 O 3 @ MCM-41 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g Ga was added 2 O 3 The catalyst is stirred for 10 hours at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /Ga 2 O 3 @ MCM-41 dehydrogenation-hydrogen combustion catalyst.
Example 5
In 2 O 3 /(Pt+Ga 2 O 3 ) Preparation of @ S-1 hydrophobic dehydrogenation-hydrogen combustion catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen combustion catalyst comprises the following specific synthesis steps: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate to obtain a mixed solution, and aging for 6 hours at room temperature; adding 0.14g of gallium nitrate hydrate and 0.1g of chloroplatinic acid hydrate into 6g of deionized water, adding 2ml of ethylenediamine, carrying out ultrasonic treatment for 5min, and stirring for 60min to obtain a metal mixed solution; adding the metal mixed solution into the mixed solution, and stirring for 30min; finally, the mixed solution is transferred into a hydrothermal kettle and crystallized for 72 hours at 180 ℃. Filtering, washing, drying at 80 deg.C for 12 hr, and calcining at 600 deg.C in muffle furnace for 6 hr to obtain hydrophobic (Pt + Ga) 2 O 3 ) @ S-1 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g of (Pt + Ga) was added 2 O 3 ) @ S-1 dehydrogenation catalyst, stirring for 10h at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace for calcining for 6 hours at the temperature of 600 ℃ to obtain hydrophobic In 2 O 3 /(Pt+Ga 2 O 3 ) @ S-1 dehydrogenation-hydrogen-burning catalyst.
Example 6
In 2 O 3 /(Pt+Ga 2 O 3 ) Preparation of/@ S-1 hydrophobic dehydrogenation-hydrogen-burning catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen burning catalyst comprises the following specific synthetic steps: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate to obtain a mixed solution, and aging for 6 hours at room temperature; then transferring the mixture into a hydrothermal kettle, and crystallizing the mixture for 72 hours at 180 ℃; and after the crystallization process is finished, filtering, washing, drying at 80 ℃ for 12 hours, then putting the solid into a muffle furnace, and calcining at 600 ℃ for 6 hours to obtain S-1. Adding 50ml of TPAOH into a 100ml beaker, adding calcined S-1 for etching for 8 hours, and centrifuging to obtain etched S-1; adding 6g deionized water, 0.14g gallium nitrate hydrate and 0.1g chloroplatinic acid hydrate into a 50ml beaker, adding etched S-1, performing ultrasonic treatment for 5min, stirring at room temperature for 10h, heating and steamingDrying to obtain (Pt + Ga) 2 O 3 ) (ii) an/S-1 dehydrogenation catalyst; mixing (Pt + Ga) 2 O 3 ) adding/S-1 into etched and used TPAOH, transferring into a hydrothermal kettle, crystallizing at 180 deg.C for 72 hr, filtering, drying at 80 deg.C for 12 hr, placing into a muffle furnace, calcining at 600 deg.C for 6 hr to obtain hydrophobic (Pt + Ga) 2 O 3 ) /@ S-1 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g of (Pt + Ga) was added 2 O 3 ) The catalyst is stirred for 10 hours at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /(Pt+Ga 2 O 3 ) /@ S-1 dehydrogenation-hydrogen-burning catalyst.
Example 7
In 2 O 3 /(Pt+Ga 2 O 3 ) Preparation of @ ZSM-5 hydrophobic dehydrogenation-hydrogen burning catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen combustion catalyst comprises the following specific synthesis steps: sodium metaaluminate, tetrapropylammonium hydroxide, tetraethyl orthosilicate and deionized water are mixed according to a molar ratio of 0.18:10:25:480, adding 0.14g of gallium nitrate hydrate and 0.1g of hydrated chloroplatinic acid, adjusting the pH to 10 by using NaOH, stirring for 4 hours, transferring the mixed solution into a hydrothermal kettle, and crystallizing for 18 hours at 180 ℃; filtering, washing, drying at 80 deg.C for 12 hr, and calcining at 600 deg.C in muffle furnace for 6 hr to obtain hydrophobic (Pt + Ga) 2 O 3 ) @ ZSM-5 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g of (Pt + Ga) was added 2 O 3 ) @ ZSM-5 dehydrogenation catalyst, stirring for 10h at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /(Pt+Ga 2 O 3 ) @ ZSM-5 dehydrogenation-hydrogen burning catalyst.
Example 8
In 2 O 3 /(Pt+Ga 2 O 3 ) Preparation of @ MCM-41 hydrophobic dehydrogenation-hydrogen combustion catalyst
A preparation method of a hydrophobic propane dehydrogenation-hydrogen combustion catalyst comprises the following specific synthesis steps: mixing 65mL of water with 50mL of ammonia water, adding 0.5g of hexadecyl trimethyl ammonium bromide, adding 0.084g of gallium nitrate hydrate and 0.06g of hydrated chloroplatinic acid, stirring at 60 ℃ until the mixture is completely dissolved, and slowly dropwise adding 5mL of tetraethoxysilane while stirring to generate white floccules. Stirring at 60 deg.C for 2 hr, filtering, washing, drying at 80 deg.C for 12 hr, transferring into muffle furnace, and calcining at 600 deg.C for 6 hr to obtain hydrophobic (Pt + Ga) 2 O 3 ) An @ MCM-41 dehydrogenation catalyst. Adding 6g of deionized water into a 50ml beaker, adding 0.28g of indium nitrate hydrate, and carrying out ultrasonic treatment for 5min; after completion of sonication, 1g of (Pt + Ga) was added 2 O 3 ) The catalyst is stirred for 10 hours at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace, and calcining for 6 hours at 600 ℃ to obtain the hydrophobic In 2 O 3 /(Pt+Ga 2 O 3 ) An @ MCM-41 dehydrogenation-hydrogen-combustion catalyst.
Comparative example 1
In 2 O 3 /Ga 2 O 3 Preparation of dehydrogenation-hydrogen combustion catalyst (without hydrophobic Properties)
The specific synthesis steps are as follows: adding 6ml of deionized water into a 50ml beaker, adding 0.14g of gallium nitrate hydrate and 0.28g of indium nitrate hydrate, carrying out ultrasonic treatment for 5min, and stirring for 10h at room temperature; after stirring, heating and evaporating to dryness, transferring to a muffle furnace, and calcining for 6h at 600 ℃ to obtain In 2 O 3 /Ga 2 O 3 A dehydrogenation-hydrogen combustion catalyst.
Comparative example 2
(In 2 O 3 +Ga 2 O 3 ) Preparation of/S-1 dehydrogenation-hydrogen combustion catalyst (dehydrogenation active component and hydrogen combustion active component are loaded outside the molecular sieve together)
The specific synthesis steps are as follows: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate, and aging for 6 hours at room temperature; transferring the mixed solution into a hydrothermal kettle, and crystallizing for 72 hours at 180 ℃. And after the crystallization process is finished, filtering and washing, drying at 80 ℃ for 12 hours, and roasting the dried solid in a muffle furnace at 600 ℃ for 6 hours to obtain the S-1 carrier. 6g of deionized water was added to a 50ml beaker followed by 0.Carrying out ultrasonic treatment on 14g of gallium nitrate hydrate and 0.28g of indium nitrate hydrate for 5min; after the ultrasonic treatment is finished, 1g of S-1 is added, and the mixture is stirred for 10 hours at room temperature; after stirring, heating and evaporating to dryness, putting the mixture into a muffle furnace at 600 ℃, and calcining for 6h to obtain (Ga) 2 O 3 +In 2 O 3 ) S-1 supported dehydrogenation-hydrogen burning catalyst.
Comparative example 3
(In 2 O 3 +Ga 2 O 3 ) Preparation of @ S-1 dehydrogenation-hydrogen burning catalyst (dehydrogenation active component and hydrogen burning active component are jointly coated in the molecular sieve)
The specific synthesis steps are as follows: mixing and stirring 15g of deionized water, 13g of TPAOH and 8g of tetraethyl orthosilicate to obtain a mixed solution, and aging for 6 hours at room temperature; adding 0.14g of gallium nitrate hydrate and 0.28g of indium nitrate hydrate into 6g of deionized water, adding 2ml of ethylenediamine, carrying out ultrasonic treatment for 5min, and stirring for 60min to obtain a metal mixed solution; adding the metal mixed solution into the mixed solution, and stirring for 30min; finally, the mixed solution is transferred into a hydrothermal kettle and crystallized for 72 hours at 180 ℃. Filtering, washing, drying at 80 deg.C for 12 hr, and calcining at 600 deg.C In muffle furnace for 6 hr to obtain (In) 2 O 3 +Ga 2 O 3 ) @ S-1 dehydrogenation-hydrogen-burning catalyst.
The catalysts obtained in the above examples 1 to 8 and comparative examples 1 to 3 were applied to propane dehydrogenation reactions, and the reaction results are shown in table 1.
TABLE 1 dehydrogenation of propane-hydrogen combustion test results
As can be seen from table 1, according to the present invention, the dehydrogenation active component is coated inside the molecular sieve and the hydrogen-burning active component is loaded outside the molecular sieve, and the high hydrophobic property of the molecular sieve is ensured, such that the obtained catalyst has good dehydrogenation, hydrogen-burning and hydrophobic properties, and when applied to the propane dehydrogenation reaction, the propane conversion rate and the propylene selectivity are significantly improved.
Claims (9)
1. A propane dehydrogenation-hydrogen burning catalyst is characterized in that a hydrophobic molecular sieve is used as a carrier, a dehydrogenation active metal component is coated inside the molecular sieve, and a hydrogen burning active metal component is loaded outside the molecular sieve; the dehydrogenation active metal component is one or more than two of metal oxides of V, cr, ni, ga, pt and Co, and the hydrogen burning active metal component is one or more than two of metal oxides corresponding to IIIB-VIIB elements or IIIA-VA elements.
2. The propane dehydrogenation-dehydrogenation catalyst of claim 1, wherein the hydrophobic molecular sieve is S-1, MCM-41, or ZSM-5.
3. The propane dehydrogenation-dehydrogenation catalyst according to claim 1, wherein the mass of the dehydrogenation active metal component is 0.1-10% of the total mass of the propane dehydrogenation-dehydrogenation catalyst; the weight of the hydrogen burning active metal component accounts for 5-60% of the total weight of the propane dehydrogenation-hydrogen burning catalyst.
4. A process for the preparation of a propane dehydrogenation-hydrogenation catalyst according to any one of claims 1 to 3, characterized by the fact that it is prepared by hydrothermal crystallization, comprising the steps of:
(1) Mixing and stirring a template agent, deionized water and a silicon source to form a uniform mixed solution;
(2) Aging the mixed solution under a stirring state;
(3) Adding a dehydrogenation active metal component into the mixed solution, and carrying out ultrasonic stirring;
(4) Transferring the mixed solution to a hydrothermal kettle for hydrothermal reaction;
(5) After the hydrothermal reaction is finished, filtering, washing, drying and calcining the obtained solid to obtain the hydrophobic molecular sieve dehydrogenation catalyst;
(6) And loading the hydrogen burning active metal component outside the hydrophobic molecular sieve dehydrogenation catalyst to obtain the propane dehydrogenation-hydrogen burning catalyst.
5. The preparation method according to claim 4, wherein the template agent is tetrapropylammonium hydroxide, the silicon source is tetraethyl orthosilicate, and the mass ratio of the template agent to the silicon source is 15:5-15.
6. The method of claim 4, wherein the aging time is 4 to 12 hours; the ultrasonic time is 5 to 60 minutes.
7. The method according to claim 4, wherein the hydrothermal reaction is carried out at a temperature of 100 to 200 ℃ for 12 to 72 hours.
8. The method according to claim 4, wherein the drying temperature is 60 to 120 ℃ and the drying time is 8 to 24 hours; the calcining temperature is 500-700 ℃, and the calcining time is 4-8 hours.
9. Use of the propane dehydrogenation-dehydrogenation catalyst of claim 1 in the dehydrogenation of propane to produce propylene.
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