CN108658093A - A kind of preparation method and applications of multi-stage porous ZSM-5 molecular sieve - Google Patents
A kind of preparation method and applications of multi-stage porous ZSM-5 molecular sieve Download PDFInfo
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- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
The present invention provides a kind of preparation methods of 5 molecular sieves of multi-stage porous ZSM, specifically related to by the synthetic system of silicon source, silicon source, Organic structure directing agent and deionized water, proper amount of cationic surfactant cetyl trimethylammonium bromide is added as soft template, it is thoroughly mixed and is formed uniformly Zeolite synthesis collosol and gel, then above-mentioned gel is dried to obtain dry glue, the method for recycling dry gel conversion method to prepare 5 molecular sieves of multi-stage porous ZSM.Provide a kind of mild preparation condition, simple and effective, without synthesis discharging of waste liquid, 5 molecular sieve preparation methods of multi-stage porous ZSM that are environmental-friendly and can realizing industrialized production embody good catalytic performance in the reaction of normal octane preparing low-carbon olefin by catalytically cracking.Therefore, the preparation method of 5 molecular sieves of multi-stage porous ZSM provided by the invention has significant environmental benefit and economic benefit, industrial production prospect good.
Description
Technical field
The invention belongs to zeolite molecular sieve synthetic technology fields, and in particular to a kind of synthesis of multi-stage porous ZSM-5 molecular sieve
Method, and using prepared multistage porous molecular sieve as hydrocarbon catalytic cracking producing light olefins catalyst.
Background technology
The low-carbon alkenes such as ethylene, propylene are the most basic raw material of chemical industry.With the quick hair of Chinese national economy
Exhibition, low-carbon alkene market demand is growing, therefore researches and develops new and effective low-carbon alkene technology of preparing and increasingly closed
Note.Currently, the production technology of low-carbon alkene mainly has steam thermal cracking, catalytic pyrolysis, methanol-to-olefins, olefin(e) disproportionation, propane
Dehydrogenation and F- T synthesis etc..In above-mentioned technique, catalytic pyrolysis is researched and developed on conventional vapor pyrolysis technology basis, tool
Have that plant energy consumption is low, CO2Discharge capacity is low, raw material range is wide, yield of light olefins is high and product distribution is flexible and coking is few etc.
Feature has a good application prospect in low-carbon alkene prepares industry.However, hydrocarbon catalytic cracking producing light olefins technology
Core is catalysis material.
ZSM-5 molecular sieve due to excellent duct shape selectivity, flexibly can modulation Acidity and good heat and water
The features such as thermal stability, becomes the excellent catalyst material of comprehensive catalytic.But since conventional ZSM-5 molecular sieve only contains micropore
Duct, mass transfer diffusivity is limited, does not only result in yield of light olefins reduction, can also form coke and block duct, cause to urge
Agent inactivates.Therefore, people have been devoted to improve the diffusion mass transfer performance of ZSM-5 molecular sieve.Patent CN103447076A reports
Road is with foramen magnum-mesoporous SiO2Multi-stage porous ZSM-5/SiO is prepared for carrier2Catalyst effectively prevents using binder plugging hole
Road, in normal octane catalytic cracking reaction, ethylene and propylene maximum yield respectively reach 42.5% and 35.7%.Patent
CN103071522A has synthesized multi-stage porous ZSM-5 molecular sieve by adding two kinds of organic formwork agents, and it is mixed to be applied to C4-C6
The reaction of hydrocarbon preparing low-carbon olefin by catalytically cracking is closed, prepared multi-stage porous ZSM-5 molecular sieve has catalytic activity good, diene high income
And the advantage of catalyst life length.The studies above the result shows that：Multi-stage porous ZSM-5 molecular sieve can significantly improve catalytic performance.But
The synthetic method of multi-stage porous ZSM-5 molecular sieve is relative complex, high temperature and pressure preparation condition is harsh, one-pot combined coefficient is low and discharge
The technological deficiencies such as a large amount of synthesis waste liquids, this greatly limits multi-stage porous ZSM-5 molecular sieve industrialized production and applications.Therefore,
It is significant to develop the sustainable Zeolite synthesis technique study of novel greenization.
Xu Wen Yang are reported in nineteen ninety and are successfully synthesized ZSM-5 molecular sieve (Xu W, et using dry gel conversion method for the first time
al.Journal of the Chemical Society Chemical Communications,1990,10(10):755-
756).Dry gum method refers to that Solid raw materials and liquid phase separation are utilized vapor transport or steam assist conversion under the high temperature conditions
Method prepares the synthetic method of molecular screen material.Compared with traditional hydrothermal synthesis method, dry gum method short, template with crystallization time
The advantages that dosage is few, combined coefficient is high, is the environmentally friendly Zeolite synthesis method of a greenization, therefore receives grind always
Study carefully personnel's concern.Chinese patent CN1583561A, CN1327947A, CN1363519A and CN106629770A,
CN103252252A, CN1935651 are all made of the molecular sieve that the method is successfully prepared different types of structure, this illustrates the synthesis
Method has universality, is suitable for industrialized production.
By above-mentioned finding it is found that preparing multi-stage porous ZSM-5 molecular sieve using dry gum method has unique advantage.This
Invention provide one kind be simple and efficient, it is environmental-friendly and be easy to industrialized multi-stage porous ZSM-5 molecular sieve preparation method will have it is good
Good industrial applications foreground.
Invention content
The present invention in order to overcome the deficiencies of the prior art, provides a kind of simple and effective, environmental-friendly and be easy to industrialized production
Multi-stage porous ZSM-5 molecular sieve preparation method.Multi-stage porous ZSM-5 molecular sieve prepared by this method has purity height, crystallinity
The features such as high and mesoporous-microporous combined multi-stage pore structure, and present in hydrocarbon catalytic cracking reaction for preparing light olefins excellent
Catalytic performance.
The present invention prepares the method for multi-stage porous ZSM-5 molecular sieve specifically, will be mixed with surfactant, silicon source, aluminium first
Zeolite synthesis collosol and gel is made by stirring, ageing in source and Organic structure directing agent and the mixture of deionized water, then
Above-mentioned collosol and gel is dried to obtain Zeolite synthesis dry glue, recycles dry gel conversion method by water vapour auxiliary crystallization, obtains
Multi-stage porous ZSM-5 molecular sieve.
The present invention also provides the preparation method of above-mentioned multi-stage porous ZSM-5 molecular sieve, specific synthesis step is as follows：
(1) surfactant is dissolved in deionized water, stirs 2~12h at room temperature, homogeneous mixture solotion A is made；
(2) sequentially add a certain amount of silicon source and silicon source, 20~80 DEG C of constant temperature water baths stirrings 0~for 24 hours, obtain uniformly mix it is molten
Liquid B；
(3) under stirring, it is added dropwise Organic structure directing agent SDA into above-mentioned mixed solution B, continue 20~
80 DEG C of constant temperature water bath stirrings 0~for 24 hours, starting sol gel mixture is made in abundant aging, and feed molar composition is as follows：50~
100SiO2:0~2Al2O3:5~15SDA:0~5X:4000H2O, wherein X represents surfactant；
(4) above-mentioned starting sol gel mixture is positioned in constant temperature oven, be warming up to 25~120 DEG C drying 0~
48h obtains Zeolite synthesis dry glue；
(5) and then by above-mentioned dry glue it is transferred in crystallizing kettle, using water vapour crystallization auxiliary law, crystallization temperature is 100~
200 DEG C, crystallization time is 6~72h, and after the completion of waiting for crystallization, products obtained therefrom is filtered, is washed, dries and obtains solid product,
That is ZSM-5 molecular sieve original powder；
(6) above-mentioned ZSM-5 molecular sieve original powder is roasted in Muffle furnace at 500~600 DEG C to 4~12h, removes mould therein
Plate agent, to obtain the multi-stage porous ZSM-5 molecular sieve for having mesoporous-micropore compound.Hydrogen multi-stage porous ZSM-5 molecules in order to obtain
Sieve, by above-mentioned sieve sample 1M NH4NO3It is exchanged in solution 3 times, exchanges 4h for 80 DEG C every time；Finally, product filtered, washed
It washs, dry, 550 DEG C of roasting 4h obtain Hydrogen multi-stage porous ZSM-5 molecular sieve catalyst.
Raw material used in the present invention is specific preferably as follows：
In the above preparation method, the silicon source of use can be glass, silicic acid, Ludox, aerosil, white carbon
Or one kind or the double silicon source systems of tetraethyl orthosilicate；Wherein it is preferred to which silicon source is tetraethyl orthosilicate.
In the above preparation method, the silicon source used can be sodium aluminate, aluminium isopropoxide, aluminum sulfate, aluminium chloride, nitric acid
One or more mixtures in aluminium, aluminium hydroxide, boehmite；Wherein it is preferred to which silicon source is aluminium isopropoxide.
In the above preparation method, the surfactant used can be cetyl trimethylammonium bromide, cetyl
One or more mixtures in trimethyl ammonium chloride or cetyl trimethyl ammonium carbonate, wherein preferred ground surfactant
For cetyl trimethylammonium bromide；
In the above preparation method, the Organic structure directing agent SDA used can be tetraethyl ammonium hydroxide, tetrapropyl hydrogen
One or more mixtures in amine-oxides, tetrabutylammonium hydroxide, wherein preferably Organic structure directing agent SDA is 4 third
Base ammonium hydroxide；
Some processes condition is preferred as follows in the present invention：
In the above preparation method, the drying temperature for preparing Zeolite synthesis dry glue is preferably 80~100 DEG C, drying
Time is preferably 12~for 24 hours；
In the above preparation method, the crystallization temperature of the water vapour auxiliary crystallization process is preferably 120~180 DEG C, brilliant
It is preferably 4~72h to change the time.
Compared with prior art the invention has the advantages that.
(1) present invention is molten by reducing in crystallization process because preparing multi-stage porous ZSM-5 molecular sieve using dry gel conversion method
The dosage of agent water, not only preparation condition is mild, easy to operate, it is easy to accomplish, combined coefficient is also greatly improved, and do not discharge
Waste liquid is synthesized, is conducive to zeolite product and mother liquor detaches, this environmental-friendly multi-stage porous molecular sieve preparation method has notable
Economic benefit and environmental benefit, be suitable for industrialized production, have good industrial applications foreground；
(2) compared with conventional hydrothermal method synthesizes multi-stage porous ZSM-5 molecular sieve, the most prominent advantage of dry gel conversion method is molten
Agent water is not contacted with solid material mixture, is solved influence of the mesoporous template to ZSM-5 molecular sieve microcellular structure crystallization, is kept away
The separation of organic phase and inorganic molecule sieve phase is exempted from, multi-stage porous ZSM-5 molecular sieve sample purity obtained and crystallinity are higher.
(3) the multi-stage porous ZSM-5 molecular sieve obtained by is demonstrated by higher in the reaction of normal octane preparing low-carbon olefin by catalytically cracking
Catalytic activity and yield of light olefins, be a kind of catalyst material haveing excellent performance.
Description of the drawings
In order to facilitate the understanding of those skilled in the art, the present invention will be further described below with reference to the drawings.
The XRD spectra for the multi-stage porous ZSM-5 molecular sieve sample that Fig. 1 embodiment of the present invention 1 synthesizes；
The SEM figures for the multi-stage porous ZSM-5 molecular sieve sample that Fig. 2 embodiment of the present invention 1 synthesizes；
The N for the multi-stage porous ZSM-5 molecular sieve sample that Fig. 3 embodiment of the present invention 1 synthesizes2Adsorption and desorption isotherms；
The XRD spectra of Fig. 4 6ZSM-5 sieve samples of the embodiment of the present invention.
Specific implementation mode
Embodiment 1
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve：By the surfactant cetyl trimethyl bromination of 3.2g
Ammonium is dissolved in the deionized water of 40.0g, is stirred at room temperature to being completely dissolved, is formed mixed solution A；Then the isopropanol of 0.2g is added
The tetraethyl orthosilicate of aluminium and 10.4g, 40 DEG C of waters bath with thermostatic control stir 2h, form mixed solution B；Then add dropwise into B solution
Enter the tetrapropylammonium hydroxide of 3.0g, form mixed solution, above-mentioned mixed solution is warming up to 60 DEG C of water bath with thermostatic control stirrings and carries out for 24 hours
Aging forms mixture Zeolite synthesis starting sol gel；Above-mentioned starting sol gel is placed in 100 DEG C of baking ovens and is dried
Zeolite synthesis dry glue is made for 24 hours, dry glue is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, crystallization temperature are 180 DEG C, and crystallization time 36h, products obtained therefrom obtains molecular screen primary powder through filtering, drying.By molecular screen primary
Powder is placed in 550 DEG C of roasting 6h in Muffle furnace and removes template, obtains sodium form multi-stage porous ZSM-5 molecular sieve.Finally, by above-mentioned molecule
It sieves original powder continuous ammonium in the ammonium nitrate solution that solubility is 1M to exchange 3 times, filter, washing, it is multistage that 550 DEG C of roasting 4h become Hydrogen
Poroid ZSM-5 molecular sieve.Before Hydrogen multi-stage porous ZSM-5 molecular sieve is filled to reaction tube, by original powder carry out tabletting, it is broken,
Sieving, obtains the catalyst granules of 40-60 mesh.
Prepared molecular sieve by XRD analysis be ZSM-5 molecular sieve, have typical MFI topological structures, sample it is pure
Degree and quality are higher；Shown in Fig. 1-3, SEM schemes it is found that the ZSM-5 molecular sieve crystal morphology is regular, and grain size is about 0.5 μ
m；By N2Adsorption and desorption isotherms hysteresis loop occur it is found that sample is Jie's micropore combined multi-stage hole ZSM-5 molecular sieve.
Embodiment 2
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve：By the surfactant cetyl trimethyl bromination of 2.8g
Ammonium is dissolved in the deionized water of 36.0g, is stirred at room temperature to being completely dissolved, is formed mixed solution A；Then the isopropanol of 0.4g is added
The tetraethyl orthosilicate of aluminium and 20.8g, 40 DEG C of waters bath with thermostatic control stir 2h, form mixed solution B；Then add dropwise into B solution
Enter the tetrapropylammonium hydroxide of 6.0g, form mixed solution, above-mentioned mixed solution is warming up to 60 DEG C of water bath with thermostatic control stirrings and carries out for 24 hours
Aging forms mixture Zeolite synthesis starting sol gel；Above-mentioned starting sol gel is placed in 100 DEG C of baking ovens and is dried
Zeolite synthesis dry glue is made for 24 hours, dry glue is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, crystallization temperature are 180 DEG C, and crystallization time 36h, products obtained therefrom obtains molecular screen primary powder through filtering, drying.By molecular screen primary
Powder is placed in 550 DEG C of roasting 6h in Muffle furnace and removes template, obtains sodium form multi-stage porous ZSM-5 molecular sieve.Finally, by above-mentioned molecule
It sieves original powder continuous ammonium in the ammonium nitrate solution that solubility is 1M to exchange 3 times, filter, washing, it is multistage that 550 DEG C of roasting 4h become Hydrogen
Poroid ZSM-5 molecular sieve.Before Hydrogen multi-stage porous ZSM-5 molecular sieve is filled to reaction tube, by original powder carry out tabletting, it is broken,
Sieving, obtains the catalyst granules of 40-60 mesh.
Embodiment 3
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve：By the surfactant cetyl trimethyl bromination of 1.6g
Ammonium is dissolved in the deionized water of 40.0g, is stirred at room temperature to being completely dissolved, is formed mixed solution A；Then the isopropanol of 0.2g is added
The tetraethyl orthosilicate of aluminium and 10.4g, 40 DEG C of waters bath with thermostatic control stir 2h, form mixed solution B；Then add dropwise into B solution
Enter the tetrapropylammonium hydroxide of 6.0g, form mixed solution, above-mentioned mixed solution is warming up to 60 DEG C of water bath with thermostatic control stirrings and carries out for 24 hours
Aging forms mixture Zeolite synthesis starting sol gel；Above-mentioned starting sol gel is placed in 100 DEG C of baking ovens and is dried
Zeolite synthesis dry glue is made for 24 hours, dry glue is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, crystallization temperature are 180 DEG C, and crystallization time 36h, products obtained therefrom obtains molecular screen primary powder through filtering, drying.By molecular screen primary
Powder is placed in 550 DEG C of roasting 6h in Muffle furnace and removes template, obtains sodium form multi-stage porous ZSM-5 molecular sieve.Finally, by above-mentioned molecule
It sieves original powder continuous ammonium in the ammonium nitrate solution that solubility is 1M to exchange 3 times, filter, washing, it is multistage that 550 DEG C of roasting 4h become Hydrogen
Poroid ZSM-5 molecular sieve.Before Hydrogen multi-stage porous ZSM-5 molecular sieve is filled to reaction tube, by original powder carry out tabletting, it is broken,
Sieving, obtains the catalyst granules of 40-60 mesh.
Embodiment 4
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve：By the surfactant cetyl trimethyl bromination of 3.2g
Ammonium is dissolved in the deionized water of 40.0g, is stirred at room temperature to being completely dissolved, is formed mixed solution A；Then the isopropanol of 0.2g is added
The tetraethyl orthosilicate of aluminium and 20.8g, 40 DEG C of waters bath with thermostatic control stir 2h, form mixed solution B；Then add dropwise into B solution
Enter the tetrapropylammonium hydroxide of 6.0g, form mixed solution, above-mentioned mixed solution is warming up to 60 DEG C of water bath with thermostatic control stirrings and carries out for 24 hours
Aging forms mixture Zeolite synthesis starting sol gel；Above-mentioned starting sol gel is placed in 100 DEG C of baking ovens and is dried
Zeolite synthesis dry glue is made for 24 hours, dry glue is transferred in crystallizing kettle, realizes that molecular sieve turns brilliant mistake using water vapour auxiliary crystallization method
Journey, crystallization temperature are 180 DEG C, and crystallization time 36h, products obtained therefrom obtains molecular screen primary powder through filtering, drying.By molecular screen primary
Powder is placed in 550 DEG C of roasting 6h in Muffle furnace and removes template, obtains sodium form multi-stage porous ZSM-5 molecular sieve.Finally, by above-mentioned molecule
It sieves original powder continuous ammonium in the ammonium nitrate solution that solubility is 1M to exchange 3 times, filter, washing, it is multistage that 550 DEG C of roasting 4h become Hydrogen
Poroid ZSM-5 molecular sieve.Before Hydrogen multi-stage porous ZSM-5 molecular sieve is filled to reaction tube, by original powder carry out tabletting, it is broken,
Sieving, obtains the catalyst granules of 40-60 mesh.
Embodiment 5
The multi-stage porous ZSM-5 molecular sieve particle in 0.75g embodiments 1 is weighed, on the fixed-bed micro-reactor of laboratory
Its catalytic cracking reaction performance is evaluated, concrete operations are that the volume flow of carrier gas nitrogen is 400mL/min, are continuously passed through 0.5h
Heating is opened afterwards, and reaction temperature section is 400-650 DEG C, waits after being warming up to reaction temperature, is passed through raw material normal octane 2ml/h, is produced
Object tests and analyzes product composition and content by gas chromatograph.The primary product of normal octane preparing low-carbon olefin by catalytically cracking reaction
Distribution is shown in Table 1, wherein " BTX " represents benzene,toluene,xylene, " C2 =+C3 =" represent the total recovery of ethylene and propylene.
The normal octane preparing low-carbon olefin by catalytically cracking reactivity worth result of 1 embodiment of table, 1 sample
Embodiment 6
Embodiment 6 is comparative example, and the ZSM-5 molecular sieve sample of use, synthetic method is not in addition to adding surfactant
Except cetyl trimethylammonium bromide, other preparation process are completely consistent with embodiment 1, and the normal octane catalysis of the catalyst is split
Method and the embodiment 1 for solving producing light olefins are also essentially identical.The primary product of normal octane preparing low-carbon olefin by catalytically cracking reaction
Distribution is shown in Table 2.Wherein, " BTX " represents benzene,toluene,xylene, " C2 =+C3 =" represent the total recovery of ethylene and propylene.
The normal octane preparing low-carbon olefin by catalytically cracking reactivity worth result of 2 comparative example of table
The feature of multi-stage porous ZSM-5 molecular sieve prepared by the present invention characterizes with the following method：
The phase structure and crystallinity of molecular sieve are characterized using powder x-ray diffraction (XRD)；
The crystal morphology and size of molecular sieve can be intuitively observed very much using scanning electron microscope (SEM).
Using the surface area and adsorption isothermal curve of nitrogen adsorption measuring molecular sieve, pore-size distribution judges that its hole is tied
Structure.
For the catalytic performance of multi-stage porous ZSM-5 molecular sieve prepared by investigation, the present invention also provides a kind of catalysis of normal octane to split
The method for solving producing light olefins, this method include using above-mentioned multi-stage porous ZSM-5 molecular sieve as catalyst.
In above-mentioned normal octane preparing low-carbon olefin by catalytically cracking method, preferably reaction condition is, reaction temperature 400~700
DEG C, synthesis under normal pressure, carrier gas type is nitrogen, carrier gas flow 400ml/min, normal octane inlet amount 2ml/h, catalyst amount
0.75g。
Present invention disclosed above preferred embodiment is only intended to help to illustrate the present invention.There is no detailed for preferred embodiment
All details are described, are not limited the invention to the specific embodiments described.Obviously, according to the content of this specification,
It can make many modifications and variations.These embodiments are chosen and specifically described to this specification, is in order to preferably explain the present invention
Principle and practical application, to enable skilled artisan to be best understood by and utilize the present invention.The present invention is only
It is limited by claims and its full scope and equivalent.
Claims (6)
1. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve, which is characterized in that include the following steps：By in silicon source, aluminium
In the synthetic system in source, Organic structure directing agent and deionized water, cationic surface active agent cetyl trimethyl is added
Ammonium bromide is thoroughly mixed as soft template and is formed uniformly Zeolite synthesis collosol and gel, then dries above-mentioned gel
Zeolite synthesis dry glue is obtained, dry gel conversion method is recycled to promote molecular sieve to turn crystalline substance by water vapour auxiliary crystallization, is prepared multistage
Hole ZSM-5 molecular sieve；
Specifically include following synthesis step：
(1) surfactant, silicon source, silicon source and Organic structure directing agent SDA are dissolved in deionized water, stirring is equal to mixing
Even, mixture stirs under preference temperature and forms Zeolite synthesis precursor sol gel, by above-mentioned collosol and gel suitable for temperature
The lower drying of degree obtains dry glue；
(2) it after being fully ground above-mentioned dry glue, is transferred in the crystallizing kettle of polytetrafluoroethyllining lining, using water vapour auxiliary crystallization
Method carries out crystallization, wherein crystallization temperature is 100-200 DEG C, and crystallization time is 0~96h, and after the completion of waiting for crystallization, it is solid to filter separation
Body product, dry, Muffle furnace high-temperature roasting removes organic matter, obtains multi-stage porous ZSM-5 molecular sieve original powder；By above-mentioned molecular screen primary
Powder is in NH4NO3It is exchanged repeatedly in solution 3 times, product is filtered, washing, is dried, roasting obtains Hydrogen multi-stage porous ZSM-5 molecular sieve.
2. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve according to claim 1, which is characterized in that specific synthesis
Steps are as follows：
(1) surfactant is dissolved in deionized water, stirs 2~12h at room temperature, homogeneous mixture solotion A is made；
(2) silicon source and silicon source are sequentially added, 20~80 DEG C of constant temperature water baths stirrings 0~for 24 hours, obtain homogeneous mixture solotion B；
(3) under stirring, Organic structure directing agent SDA is added dropwise into above-mentioned mixed solution B, continues at 20~80 DEG C
Constant temperature water bath stirring 0~for 24 hours, starting sol gel mixture is made in abundant aging, and feed molar composition is as follows：50~
100SiO2:0~2Al2O3:5~15SDA:0~5X:4000H2O, wherein X represents surfactant；
(4) above-mentioned starting sol gel mixture is positioned in constant temperature oven, is warming up to 25~120 DEG C of 0~48h of drying, obtains
To Zeolite synthesis dry glue；
(5) and then by above-mentioned dry glue it is transferred in crystallizing kettle, using water vapour crystallization auxiliary law, crystallization temperature is 100~200
DEG C, crystallization time is 6~72h, and after the completion of waiting for crystallization, products obtained therefrom is filtered, is washed, dries and obtains solid product, i.e.,
ZSM-5 molecular sieve original powder；
(6) above-mentioned ZSM-5 molecular sieve original powder is roasted in Muffle furnace at 500~600 DEG C to 4~12h, removes template therein
Agent, to obtain the multi-stage porous ZSM-5 molecular sieve for having mesoporous-micropore compound, Hydrogen multi-stage porous ZSM-5 molecules in order to obtain
Sieve, by above-mentioned sieve sample 1M NH4NO3It is exchanged in solution 3 times, exchanges 4h for 80 DEG C every time；Finally, product filtered, washed
It washs, dry, 550 DEG C of roasting 4h obtain Hydrogen multi-stage porous ZSM-5 molecular sieve catalyst.
3. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (1)
In, the surfactant X used is cetyl trimethylammonium bromide, hexadecyltrimethylammonium chloride or cetyl front three
One or more mixtures in base ammonium carbonate.
4. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve according to claim 1, it is characterised in that：What is used has
Machine structure directing agent SDA is one or more mixed in tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide
Close object.
5. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve according to claim 1, it is characterised in that：In step (1)
In, the silicon source is one or more mixtures in tetraethyl orthosilicate, aerosil, white carbon or Ludox；
The silicon source is aluminum sulfate, aluminum nitrate, sodium metaaluminate, one or more in boehmite, boehmite or aluminium isopropoxide
Mixture.
6. according to the application of multi-stage porous ZSM-5 molecular sieve prepared by claim 1-5 the methods, it is characterised in that：It is obtained
Multi-stage porous ZSM-5 molecular sieve is used as the catalyst in hydrocarbon catalytic cracking reaction for preparing light olefins.
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