CN108927213A - A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane - Google Patents
A kind of catalyst and preparation method thereof for preparing propylene by dehydrogenating propane Download PDFInfo
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- CN108927213A CN108927213A CN201810672725.3A CN201810672725A CN108927213A CN 108927213 A CN108927213 A CN 108927213A CN 201810672725 A CN201810672725 A CN 201810672725A CN 108927213 A CN108927213 A CN 108927213A
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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
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/38—Base treatment
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Abstract
The catalyst and preparation method thereof that the present invention relates to a kind of for preparing propylene by dehydrogenating propane, when preparation, the NaZSM-5 molecular sieve of general microporous structure is first prepared, it is placed in the mixed solution of aqueous slkali and template again, it is exchanged after microwave hydrothermal crystallization with proper inorganic acid or ammonium salt solution, is fired to obtain micropore-mesopore hierarchical porous structure HZSM-5 molecular sieve；Active component and auxiliary agent are carried on multi-stage porous HZSM-5 molecular sieve again, catalyst is made.Compared with prior art, the present invention introduces meso-hole structure in ZSM-5 molecular sieve microcellular structure, solves molecule diffusion difficulty, reduces the generation of carbon distribution, extend catalyst service life；Meanwhile crystallization temperature is not only reduced by microwave secondary crystallization, shortens the time of entire synthesis technology but also moves to the non-skeleton species removed on skeleton again, improve the crystallinity of ZSM-5 molecular sieve；When carrying out preparing propylene by dehydrogenating propane reaction using the catalyst, available higher conversion of propane and Propylene Selectivity.
Description
Technical field
The present invention relates to preparing propylene by dehydrogenating propane technical fields, and in particular to a kind of catalysis for preparing propylene by dehydrogenating propane
Agent and preparation method thereof.
Background technique
In recent years, world economy is fast-developing, and chemical industry is also flown as the important component of national economy
The development of jump formula causes propylene downstream product demand constantly to increase and then propylene demand growth speed is promoted constantly to accelerate.Third
Alkene is the important Elementary Chemical Industry raw material for being only second to ethylene, and derivative mainly includes polypropylene, acrylonitrile, acetone, isopropyl downstream
Alcohol, phenol, butanol, octanol, acrylic acid etc..In particular with having the characteristics that polypropylene heat-resisting, light, that intensity is good uses extensively
In fields such as packaging, household electrical appliances, automobile and buildings, so that polyacrylic demand rapid development, the demand as raw material propylene
Also rapid growth therewith.The technique of propylene enhancing is concentrated mainly on four aspects: first is that improving the oil refining process such as FCC, excavating existing
There are device potentiality；Second is that making full use of the C of oil refining by-product4The resources such as hydrocarbon are converted into the low-carbon alkene cracking skill of ethylene, propylene
Art, olefin(e) disproportionation technology；Third is that with natural gas, coal etc. for raw material, the MTO technology of production ethylene, propylene；Fourth is that third
Alkane dehydrogenating technology.According to China's energy resource structure feature, exploitation by enriching and cheap Trends In Preparation of Propene By Catalytic Dehydrogenation of Propane technology, for
Alleviate chemicals imbalance between supply and demand, the optimization energy and chemical industry structure etc. have own strategic significance.
Currently, dehydrogenating propane technology is using the Oleflex technique of Uop Inc. and the Catofin technique of Lummus company as generation
Table, but catalytic performance is unsatisfactory, and especially hot conditions make the easy carbon distribution of catalyst, sintering, and catalyst inactivation, catalyst is caused to make
Use service life reduction.Therefore, on the basis of guaranteeing activity, selectivity, the stability for improving catalyst becomes dehydrogenating propane system third
The emphasis of alkene technology.
With Al2O3It reacts as carrier loaded active component and auxiliary agent for preparing propylene by dehydrogenating propane, has carried out both at home and abroad
The research of comparison system, has obtained many important achievements, apply relevant dehydrogenating propane patent have CN1033949A,
CN1265878C, CN106582629A, CN106582613A, CN102698750A etc..But its anti-sintering property is poor, stability
It is unsatisfactory.
With going deep into for research, the substance with special structure and property is used to cause people's as catalyst carrier
Concern.HZSM-5 molecular sieve contains there are two types of the pore canal system intersected, and has higher shape selective catalysis performance.ZSM-5 molecular sieve is solid
The representative of body acid catalyst, the HZSM-5 molecular sieve especially after H ion exchange, surface have a large amount of B acid and L acid
Site is conducive to improve dehydrogenating propane reactivity.ZSM-5 molecular sieve can be used as substitution Al in dehydrogenating propane reaction2O3It is excellent
Good carrier: if CN101108362A is related to a kind of molecular sieve catalyst of preparing propylene by dehydrogenating propane, using the side of step impregnation
Method adds tri- component element of Pt-Sn-Na, conversion of propane 30%, Propylene Selectivity 98%；CN101066532A is related to one kind
ZSM-5 molecular sieve using skeleton containing Sn is as propane dehydrogenation catalyst, and Propylene Selectivity is up to 99%；CN101380587A is related to
And use molecular sieve of the skeleton containing rare earth elemental metals for the propane dehydrogenation catalyst of carrier to a kind of, by step impregnation alkali or
Alkaline-earth metal, Pt-Sn modifying agent, propylene conversion reach as high as 30.5%, and Propylene Selectivity is up to 97%；CN101513613A
It is related to a kind of use multicomponent hetero atom ZSM-5 molecular sieve, passes through step impregnation alkali or alkaline-earth metal, Pt-Sn modifying agent, make
For propane dehydrogenation catalyst, conversion of propane 30%, Propylene Selectivity reaches as high as 98%.
From the point of view of the patent of above-mentioned current open report, support type Pt/ZSM-5 catalyst is with metal function and acidity
The bifunctional catalyst of function connects each other between this two function, joint effect the reactivity worth of catalyst.There are also patents to adopt
With third or the 4th component modification Pt-Sn/HZSM-5 catalyst, to the modulation concern of ZSM-5 molecular sieve carrier this body structure compared with
It is few.Typical ZSM-5 molecular sieve duct is in range of micropores, and cellular structure is unfavorable for the diffusion of reactants and products, in propane
Generation carbon distribution is easy in dehydrogenation hot environment leads to catalyst inactivation.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of stability, anti-carbon
The excellent catalyst and preparation method thereof for preparing propylene by dehydrogenating propane of property.
The purpose of the present invention can be achieved through the following technical solutions: a kind of catalysis for preparing propylene by dehydrogenating propane
Agent, the catalyst include ZSM-5 molecular sieve carrier and the active component being supported in ZSM-5 molecular sieve carrier duct and auxiliary agent
Component, the ZSM-5 molecular sieve are micropore-mesopore hierarchical porous structure.The present invention is divided using the multi-stage porous ZSM-5 of micropore-mesopore
Son sieve, can enhance the mass transfer ability of ZSM-5 molecular sieve, so that making up cellular structure is unfavorable for lacking for reactants and products diffusion
It falls into.
The active component is platinum element, and the mass percent of the active component is 0.1%~0.8%.
The adjuvant component includes one or more of tin, sodium, magnesium, manganese, and the mass percent of the adjuvant component is
0.1%~2%.
A kind of preparation method for the catalyst of preparing propylene by dehydrogenating propane as described above, comprising the following steps:
(1) silicon source, silicon source, template and water are mixed, stirs to get gel mixture, it is then that the gel mixture is close
Close and be placed on baking oven and be aged, then hydrothermal crystallizing, obtain product washing, it is dry after roasted, obtain microcellular structure
NaZSM-5 molecular sieve；
(2) NaZSM-5 molecular sieve obtained by step (1) is placed in the mixed solution of aqueous slkali and template, is stirred laggard
Row is closed, and moves to progress microwave hydrothermal crystallization in microwave reactor；
(3) product that step (2) obtains is washed, dry be placed in inorganic acid solution or ammonium salt solution is stirred,
Washed dry roasting again, the product of roasting repeat operation 3 times of step (3), obtain micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
(4) mixing for micropore-mesopore hierarchical porous structure HZSM-5 molecular sieve being immersed in active component and adjuvant component is molten
It in liquid, then dries, roast up to the catalyst for being used for preparing propylene by dehydrogenating propane.
Preferably, the silicon source include one of silica solution, active silica, white carbon black, ethyl orthosilicate or
It is several, source of aluminium include one of aluminum oxide, boehmite, aluminium isopropoxide, aluminium hydroxide, activated alumina or
Several, the template includes one of tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, 4-propyl bromide, triethylamine
Or it is several, the silicon source, silicon source, the molar ratio of template and water are 80~120:1~10:10~20:2000~3000, step
(1) temperature of stirring described in is 10~40 DEG C, and mixing time is 2~8h.
Preferably, the Aging Temperature be 20~80 DEG C, digestion time be 6~for 24 hours；
Preferably, the temperature of hydrothermal crystallizing described in step (1) is 100~200 DEG C, time of hydrothermal crystallizing is 12~
48h；
It is washed in step (1) using deionized water, 100~120 DEG C of dry temperature, the dry time is 2~8h；
The temperature of roasting described in step (1) is 500~600 DEG C, and calcining time is 2~8h.
Preferably, the alkali solute of the aqueous slkali includes one of sodium acetate, sodium carbonate or sodium hydroxide, described
The concentration of mixed solution neutral and alkali solute is 0.1~5mol/L, and the template includes tetrapropylammonium hydroxide, tetraethyl hydrogen-oxygen
Change one or more of ammonium, 4-propyl bromide or triethylamine, in the mixed solution concentration of template be 0.1~
2mol/L, whipping temp of the NaZSM-5 molecular sieve in mixed solution are 50~90 DEG C, and mixing time is 1~5h.At alkali
It removes framework silicon and introduces meso-hole structure to the reason technology property of can choose, and being capable of regulatory molecule sieve acidity.Using inorganic base
Processing ZSM-5 molecular sieve has the characteristics that desiliconization rate is fast, pore-forming efficiency is high, but the skeleton silicon species removed easily block duct,
It is unfavorable for mass transfer；It is slow using organic base treatment effeciency, but controllability is high, is conducive to remove duct amorphous substance kind, improves and expand
Dissipate efficiency.By inorganic base and organic base mixed processing ZSM-5 molecular sieve, it can play that inorganic base desiliconization rate is fast, pore-forming efficiency
High effect, and the effect that organic base removes duct amorphous substance kind can be played.
Preferably, the temperature of the microwave hydrothermal crystallization be 100~180 DEG C, the time be 0.5~3h, power be 300~
700W.During Microwave-assisted synthesis zeolite molecular sieve, microwave changes the choosing of kinetics and reaction due to its fuel factor
Selecting property makes reaction that can foreshorten to dozens of minutes from several days, to substantially reduce the time of synthetic material.
Preferably, drying temperature described in step (3) is 100~120 DEG C, and drying time is 2~8h；
Inorganic acid solution described in step (3) includes one of hydrochloric acid, nitric acid or sulfuric acid, the inorganic acid solution it is dense
Degree is 0.1~4mol/L；
The ammonium salt solution includes ammonium nitrate solution or ammonium chloride solution, and the concentration of the ammonium salt solution is 0.1~4mol/
L；
The temperature of stirring described in step (3) is 20~80 DEG C, and the time of stirring is 2~8h；
The temperature of roasting described in step (3) is 500~600 DEG C, and the time of roasting is 2~8h.
Preferably, in the mixed solution of active component described in the step (4) and adjuvant component, active component is platinum
Salt, the adjuvant component are one or more of pink salt, sodium salt, magnesium salts or manganese salt；
The temperature of the dipping is 20~80 DEG C, and the time of dipping is 2~8h；
Dry temperature described in step (4) is 100~120 DEG C, and the dry time is 2~8h；
The temperature of roasting described in step (4) is 500~600 DEG C, and the time of roasting is 2~8h.
Compared with prior art, the beneficial effects of the present invention are embodied in following several respects:
(1) by alkaline solution treatment, meso-hole structure is introduced in ZSM-5 molecular sieve microcellular structure, solves molecule diffusion
Difficulty reduces the generation of carbon distribution, extends catalyst service life；
(2) crystallization temperature not only reduced by microwave secondary crystallization, shorten the time of entire synthesis technology but also make to take off
It removes the non-skeleton species to get off to move on skeleton again, improves the crystallinity of ZSM-5 molecular sieve；
(3) when carrying out preparing propylene by dehydrogenating propane reaction using the catalyst, available higher conversion of propane and third
Alkene selectivity.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, comprising the following steps:
(step A1) is by silica solution, boehmite, tetrapropylammonium hydroxide, deionized water according to molar ratio 120:1:
10:3000 is uniformly mixed, and is stirred 8h at 10 DEG C, is obtained a gel mixture；
The gel mixture is fitted into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE) by (step A2), after closed
It is put into baking oven, is aged 10h at 60 DEG C, crystallization is for 24 hours at 160 DEG C；
The washing of (step A3) deionized water, 100 DEG C of dry 8h, 600 DEG C of roasting 2h, obtain the NaZSM- of general microporous structure
5 molecular sieves, then be placed in the sodium hydroxide of 0.2mol/L and the mixed solution of the tetrapropylammonium hydroxide of 0.5mol/L in 90 DEG C
1h is stirred, is moved into the reaction kettle that liner is polytetrafluoroethylene (PTFE), microwave reactor is packed into after closed, in 100 DEG C of reaction 3h；
With the ammonium nitrate solution of 1mol/L in 80 DEG C of stirring 2h after the washing of (step A4) deionized water, 100 DEG C of dry 8h, then
Through deionized water washing, 100 DEG C of dry 8h, 500 DEG C of roasting 2h, alternately three times to get arrive micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Multi-stage porous HZSM-5 molecular sieve is placed in platinum acid chloride solution and the quality that mass percent is 0.1% again by (step A5)
In the mixed solution for the stannic chloride that percentage is 0.5%, in 80 DEG C of dipping 2h, 100 DEG C of dry 2h, 600 DEG C of roasting 8h, it is made and urges
Agent, in preparing propylene by dehydrogenating propane reaction.
Embodiment 2
A kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, comprising the following steps:
(step A1) is by silica solution, aluminum oxide, tetrapropylammonium hydroxide, deionized water according to molar ratio 100:1:
10:2000 is uniformly mixed, and is stirred 8h at 10 DEG C, is obtained a gel mixture；
The gel mixture is fitted into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE) by (step A2), after closed
It is put into baking oven, is aged 12h at 40 DEG C, crystallization is for 24 hours at 180 DEG C；
The washing of (step A3) deionized water, 100 DEG C of dry 8h, 600 DEG C of roasting 2h, obtain the NaZSM- of general microporous structure
5 molecular sieves, then be placed in the sodium carbonate of 0.2mol/L and the mixed solution of the tetrapropylammonium hydroxide of 0.5mol/L and stirred in 80 DEG C
1h is mixed, is moved into the reaction kettle that liner is polytetrafluoroethylene (PTFE), microwave reactor is packed into after closed, in 150 DEG C of reaction 2h；
With the ammonium nitrate solution of 1mol/L in 80 DEG C of stirring 2h after the washing of (step A4) deionized water, 120 DEG C of dry 8h, then
Through deionized water washing, 120 DEG C of dry 8h, 500 DEG C of roasting 2h, alternately three times to get arrive micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Multi-stage porous HZSM-5 molecular sieve is placed in platinum acid chloride solution and the quality that mass percent is 0.3% again by (step A5)
In the mixed solution for the sodium chloride that percentage is 0.5%, in 80 DEG C of dipping 2h, 120 DEG C of dry 2h, 600 DEG C of roasting 8h, it is made and urges
Agent, in preparing propylene by dehydrogenating propane reaction.
Embodiment 3
A kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, comprising the following steps:
(step A1) mixes silica solution, aluminum oxide, triethylamine, deionized water according to molar ratio 100:2:10:2500
It closes uniformly, stirs 6h at 20 DEG C, obtain a gel mixture；
The gel mixture is fitted into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE) by (step A2), after closed
It is put into baking oven, is aged 12h at 40 DEG C, crystallization is for 24 hours at 180 DEG C；
The washing of (step A3) deionized water, 120 DEG C of DEG C of dry 8h, 550 DEG C of roasting 2h, obtain general microporous structure
NaZSM-5 molecular sieve, then be placed in the sodium acetate of 0.5mol/L and the mixed solution of the tetrapropylammonium hydroxide of 0.5mol/L in
80 DEG C of stirring 1h are moved into the reaction kettle that liner is polytetrafluoroethylene (PTFE), microwave reactor are packed into after closed, in 150 DEG C of reaction 2h；
With the hydrochloric acid solution of 1mol/L in 80 DEG C of stirring 2h after the washing of (step A4) deionized water, 120 DEG C of dry 8h, then pass through
Deionized water washing, 120 DEG C of dry 8h, 500 DEG C of roasting 2h, alternately three times to get arrive micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Multi-stage porous HZSM-5 molecular sieve is placed in platinum acid chloride solution and the quality that mass percent is 0.2% again by (step A5)
In the mixed solution for the magnesium chloride that percentage is 0.3%, in 80 DEG C of dipping 2h, 120 DEG C of dry 2h, 600 DEG C of roasting 8h, it is made and urges
Agent, in preparing propylene by dehydrogenating propane reaction.
Comparative example 1
A collection of HZSM-5 molecular sieve (SiO is had purchased from conventional molecular sieve producer2/Al2O3Molar ratio is 100), by purchase
HZSM-5 molecular sieve is placed in the mixed of the platinum acid chloride solution that mass percent is 0.3% and the sodium chloride that mass percent is 0.5%
It closes in solution, in 80 DEG C of dipping 2h, 120 DEG C of dry 2h, 600 DEG C of roasting 8h, CAT-2A catalyst is made, is used for dehydrogenating propane system
In propylene reaction.
Comparative example 2
A collection of HZSM-5 molecular sieve (SiO is had purchased from conventional molecular sieve producer2/Al2O3Molar ratio is 100), by purchase
HZSM-5 molecular sieve is placed in the mixed of the platinum acid chloride solution that mass percent is 0.2% and the magnesium chloride that mass percent is 0.3%
It closes in solution, in 80 DEG C of dipping 2h, 120 DEG C of dry 2h, 600 DEG C of roasting 8h, CAT-3A catalyst is made, is used for dehydrogenating propane system
In propylene reaction.
Embodiment 4
A kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, comprising the following steps:
(step A1) mixes silica solution, boehmite, triethylamine, deionized water according to molar ratio 100:2:10:2500
It closes uniformly, stirs 6h at 20 DEG C, obtain a gel mixture；
The gel mixture is fitted into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE) by (step A2), after closed
It is put into baking oven, is aged 12h at 40 DEG C, the crystallization 36h at 180 DEG C；
The washing of (step A3) deionized water, 120 DEG C of dry 8h, 600 DEG C of roasting 2h, obtain the NaZSM- of general microporous structure
5 molecular sieves, then be placed in the mixed solution of the sodium acetate of 0.5mol/L and the triethylamine of 0.5mol/L in 80 DEG C of stirring 2h, it moves into
Liner is microwave reactor to be packed into after closed, in 120 DEG C of reaction 1.5h in the reaction kettle of polytetrafluoroethylene (PTFE)；
With the hydrochloric acid solution of 1mol/L in 80 DEG C of stirring 2h after the washing of (step A4) deionized water, 120 DEG C of dry 8h, then pass through
Deionized water washing, 120 DEG C of dry 8h, 500 DEG C of roasting 2h, alternately three times to get arrive micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Multi-stage porous HZSM-5 molecular sieve is placed in platinum acid chloride solution and the quality that mass percent is 0.1% again by (step A5)
In the mixed solution for the sodium chloride that percentage is 0.2%, in 80 DEG C of dipping 2h, 100 DEG C of dry 5h, 600 DEG C of roasting 8h, it is made and urges
Agent, in preparing propylene by dehydrogenating propane reaction.
Embodiment 5
A kind of preparation method of the catalyst for preparing propylene by dehydrogenating propane, comprising the following steps:
(step A1) mixes silica solution, boehmite, triethylamine, deionized water according to molar ratio 100:2:15:2800
It closes uniformly, stirs 4h at 20 DEG C, obtain a gel mixture；
The gel mixture is fitted into the stainless steel autoclave that liner is polytetrafluoroethylene (PTFE) by (step A2), after closed
It is put into baking oven, is aged 20h at 40 DEG C, the crystallization 36h at 180 DEG C；
The washing of (step A3) deionized water, 120 DEG C of dry 8h, 600 DEG C of roasting 2h, obtain the NaZSM- of general microporous structure
5 molecular sieves, then be placed in the mixed solution of the sodium acetate of 0.5mol/L and the triethylamine of 0.5mol/L in 80 DEG C of stirring 2h, it moves into
Liner is microwave reactor to be packed into after closed, in 120 DEG C of reaction 1.5h in the reaction kettle of polytetrafluoroethylene (PTFE)；
With the nitric acid solution of 1mol/L in 80 DEG C of stirring 2h after the washing of (step A4) deionized water, 120 DEG C of dry 8h, then pass through
Deionized water washing, 120 DEG C of dry 8h, 500 DEG C of roasting 2h, alternately three times to get arrive micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Multi-stage porous HZSM-5 molecular sieve is placed in platinum acid chloride solution and the quality that mass percent is 0.5% again by (step A5)
In the mixed solution for the sodium chloride that percentage is 0.2%, in 80 DEG C of dipping 2h, 130 DEG C of dry 5h, 600 DEG C of roasting 8h, it is made and urges
Agent, in preparing propylene by dehydrogenating propane reaction.
The catalyst of above-described embodiment 1~5 and comparative example is used for dehydrogenating propane, its activity is tested, as a result such as 1 institute of table
Show.
Each catalyst reaction expression activitiy of table 1
From table 1 it follows that according to the CAT-2A and CAT-3A of tradition preparation compared with catalyst prepared by the present invention,
Conversion ratio, selectivity and the stability of its dehydrogenating propane are below catalyst prepared by the present invention.
Claims (10)
1. a kind of catalyst for preparing propylene by dehydrogenating propane, which includes ZSM-5 molecular sieve carrier and is supported on
Active component and adjuvant component in ZSM-5 molecular sieve carrier duct, which is characterized in that the ZSM-5 molecular sieve is micropore-Jie
Hole hierarchical porous structure.
2. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 1, which is characterized in that the activity
Group is divided into platinum element, and the mass percent of the active component is 0.1%~0.8%.
3. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 1, which is characterized in that the auxiliary agent group
Dividing includes one or more of tin, sodium, magnesium, manganese, and the mass percent of the adjuvant component is 0.1%~2%.
4. a kind of preparation method as described in claims 1 to 3 is any for the catalyst of preparing propylene by dehydrogenating propane, feature exist
In, comprising the following steps:
Step (1): silicon source, silicon source, template and water are mixed, gel mixture is stirred to get, then by the gel mixture
The closed baking oven that is placed on is aged, then hydrothermal crystallizing, is roasted after obtaining product washing, drying, obtains microcellular structure
NaZSM-5 molecular sieve；
Step (2): NaZSM-5 molecular sieve obtained by step (1) is placed in the mixed solution of aqueous slkali and template, is stirred laggard
Row is closed, and moves to progress microwave hydrothermal crystallization in microwave reactor；
Step (3): the product that step (2) obtains is washed, dry be placed in inorganic acid solution or ammonium salt solution is stirred,
Washed dry roasting again, the product of roasting repeat operation 3 times of step (3), obtain micropore-mesopore hierarchical porous structure
HZSM-5 molecular sieve；
Step (4): the mixing that micropore-mesopore hierarchical porous structure HZSM-5 molecular sieve is immersed in active component and adjuvant component is molten
It in liquid, then dries, roast up to the catalyst for being used for preparing propylene by dehydrogenating propane.
5. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that the silicon source
Including one or more of silica solution, active silica, white carbon black, ethyl orthosilicate, source of aluminium includes three oxidations two
One or more of aluminium, boehmite, aluminium isopropoxide, aluminium hydroxide, activated alumina, the template include tetrapropyl
One or more of ammonium hydroxide, tetraethyl ammonium hydroxide, 4-propyl bromide, triethylamine, the silicon source, silicon source, template
The molar ratio of agent and water is 80~120:1~10:10~20:2000~3000, the temperature of stirring described in step (1) is 10~
40 DEG C, mixing time is 2~8h.
6. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that the ageing
Temperature be 20~80 DEG C, digestion time be 6~for 24 hours；
The temperature of hydrothermal crystallizing described in step (1) is 100~200 DEG C, and the time of hydrothermal crystallizing is 12~48h；
It is washed in step (1) using deionized water, 100~120 DEG C of dry temperature, the dry time is 2~8h；
The temperature of roasting described in step (1) is 500~600 DEG C, and calcining time is 2~8h.
7. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that the alkali soluble
The alkali solute of liquid includes one of sodium acetate, sodium carbonate or sodium hydroxide, the concentration of the mixed solution neutral and alkali solute
For 0.1~5mol/L, the template includes tetrapropylammonium hydroxide, tetraethyl ammonium hydroxide, 4-propyl bromide or three second
One or more of amine, the concentration of template is 0.1~2mol/L in the mixed solution, and the NaZSM-5 molecular sieve exists
Whipping temp in mixed solution is 50~90 DEG C, and mixing time is 1~5h.
8. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that the microwave
The temperature of hydrothermal crystallizing is 100~180 DEG C, and the time is 0.5~3h, and power is 300~700W.
9. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that in step (3)
The drying temperature is 100~120 DEG C, and drying time is 2~8h；
Inorganic acid solution described in step (3) includes one of hydrochloric acid, nitric acid or sulfuric acid, and the concentration of the inorganic acid solution is
0.1~4mol/L；
The ammonium salt solution includes ammonium nitrate solution or ammonium chloride solution, and the concentration of the ammonium salt solution is 0.1~4mol/L；
The temperature of stirring described in step (3) is 20~80 DEG C, and the time of stirring is 2~8h；
The temperature of roasting described in step (3) is 500~600 DEG C, and the time of roasting is 2~8h.
10. a kind of catalyst for preparing propylene by dehydrogenating propane according to claim 4, which is characterized in that the step
Suddenly in the mixed solution of active component described in (4) and adjuvant component, active component is platinum salt, the adjuvant component be pink salt,
One or more of sodium salt, magnesium salts or manganese salt；
The temperature of the dipping is 20~80 DEG C, and the time of dipping is 2~8h；
Dry temperature described in step (4) is 100~120 DEG C, and the dry time is 2~8h；
The temperature of roasting described in step (4) is 500~600 DEG C, and the time of roasting is 2~8h.
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