CN110510633A - A kind of preparation method of multi-stage porous ZSM-5 molecular sieve - Google Patents
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
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Abstract
A kind of preparation method mixing alkali modification multi-stage porous ZSM-5 molecular sieve: the alkali metal hydroxide and quaternary ammonium salt mixed ammonium/alkali solutions of various concentration and proportion are prepared；Nano-ZSM-5 molecular sieve is mixed with mixed ammonium/alkali solutions by certain solid-to-liquid ratio；It is stirred under 100~200 DEG C of environment.The application has prepared the hollow ZSM-5 molecular sieve that surface has micropore-mesopore composite pore structural, in a relatively short period of time, not only form relatively regular hollow structure, simultaneously in Surface Creation meso-hole structure, the resistance to mass tranfer for improving ZSM-5 molecular sieve is conducive to the transmitting of reactants and products, improves the catalytic performance and service life of catalyst, and method is simple and easy, it is low in cost large batch of to produce.By adjusting the ratio and concentration of alkali metal hydroxide and quaternary ammonium salt, the ZSM-5 molecular sieve of different hollow degree, meso-hole structure can be prepared.
Description
Technical field
The application belongs to molecular sieve art, is related to a kind of preparation method of molecular sieve, and in particular to a kind of multi-stage porous ZSM-5
The preparation method of molecular sieve.
Background technique
ZSM-5 zeolite molecular sieve is the high silicon 3 D straight passage structures zeolite that Mobil company develops the 1970s,
By modification acid range can be catalyzed with modulation.But join it in bigger molecule because of its single microcellular structure (being less than 1nm)
With catalysis react in limited, affect catalytic activity.There is the mesoporous-hollow multiple of mesopore orbit and micropore canals simultaneously
It closes ZSM-5 molecular sieve and has both more excellent Shape-selective, diffusion and coking resistivity.Therefore, attracted in recent years big
Quantity research person studies it, to improve its cellular structure, improve its catalytic activity.
In view of this, special propose the application.
Summary of the invention
One of the application is designed to provide a kind of preparation side for mixing alkali modification and preparing multi-stage porous ZSM-5 molecular sieve
Method, this method not only form relatively regular hollow structure, while in Surface Creation meso-hole structure.Improve ZSM-5 points
The resistance to mass tranfer of son sieve, is conducive to the transmitting of reactants and products, improves the catalytic performance and service life of catalyst.
Further object is to provide a kind of preparation for mixing alkali modification and preparing multi-stage porous ZSM-5 molecular sieve
Method, this method is simple and easy, low in cost large batch of to produce.
To achieve the above object, the application adopts the following technical scheme that
A kind of preparation method of multi-stage porous ZSM-5 molecular sieve, comprising:
ZSM-5 molecular sieve is mixed with mixed ammonium/alkali solutions, is stirred, wherein the solute of mixed ammonium/alkali solutions includes alkali metal hydrogen
The concentration ratio of oxide and quaternary ammonium salt, alkali metal hydroxide and quaternary ammonium salt is 1:4-4:5；
It after stirring, is separated, the solid 1 isolated is dried；
Use NH4NO3Solution mixes progress ammonium with solid 1 and exchanges, and is dried, roasts again to the solid after exchange
Obtain multi-stage porous ZSM-5 molecular sieve.
Alkali metal hydroxide includes sodium hydroxide and/or potassium hydroxide etc..
The ZSM-5 molecular sieve of the application preparation has regular hollow structure, in the Surface Creation meso-hole structure of molecular sieve.
The resistance to mass tranfer for reducing ZSM-5 molecular sieve is conducive to the transmitting of reactants and products, improve catalyst catalytic performance and
Service life.
Detailed description of the invention
Fig. 1 is untreated nano-ZSM-5 molecular sieve (A) and mixing alkali modification multi-stage porous ZSM-5 molecular sieve in embodiment 1
(B) x-ray diffraction pattern.
Fig. 2 is untreated nano-ZSM-5 molecular sieve (A) and mixing alkali modification multi-stage porous ZSM-5 molecular sieve in embodiment 1
(B) transmission electron microscope TEM schemes.
Fig. 3 is untreated nano-ZSM-5 molecular sieve (A) and mixing alkali modification multi-stage porous ZSM-5 molecular sieve in embodiment 1
(B) scanning electron microscope sem figure.
Fig. 4 is untreated nano-ZSM-5 molecular sieve (A) and mixing alkali modification multi-stage porous ZSM-5 molecular sieve in embodiment 1
(B)N2Physical absorption-desorption curve figure.
Fig. 5 is the transmission electron microscope TEM figure that the hollow ZSM-5 molecular sieve of alkali modification is mixed in embodiment 2.
Fig. 6 is the transmission electron microscope TEM figure that the hollow ZSM-5 molecular sieve of alkali modification is mixed in embodiment 3.
Fig. 7 is the transmission electron microscope TEM figure that the hollow ZSM-5 molecular sieve of alkali modification is mixed in embodiment 4.
Fig. 8 is the transmission electron microscope TEM figure that the hollow ZSM-5 molecular sieve of alkali modification is mixed in embodiment 5.
Specific embodiment
To keep the purposes, technical schemes and advantages of the embodiment of the present application clearer, below in conjunction with the embodiment of the present application
In attached drawing, the technical solution in embodiment is clearly and completely described, following embodiment for illustrating the application, but
It is not limited to scope of the present application.
In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition or according to institute, manufacturer
It is recommended that condition.Unless otherwise stated, otherwise all percentage, ratio, ratio or number be by weight.
The unit in percent weight in volume in the application is well-known to those skilled in the art, such as is referred to
The weight of solute in 100 milliliters of solution.As used herein, " room temperature " refers to 15-30 DEG C, preferably 20-25 DEG C.
Solid-to-liquid ratio is the ratio of solid masses (g) Yu liquid volume (ml) in the application.
Term " mesoporous ", typically refers to aperture in 2-50nm.
Term " micropore " typically refers to aperture less than 2nm.
Term " hollow " in the application refers to the duct that perforation is formed inside ZSM molecular sieve.
Unless otherwise defined, it anticipates known to all professional and scientific terms as used herein and one skilled in the art
Justice is identical.In addition, any method similar to or equal to what is recorded and material all can be applied in the application method.Wen Zhong
The preferred implement methods and materials are for illustrative purposes only.
In embodiments, the preparation method of the multi-stage porous ZSM-5 molecular sieve of the application, includes the following steps:
ZSM-5 molecular sieve is mixed under conditions of 100~200 DEG C of temperature with mixed ammonium/alkali solutions, is stirred, wherein mixing
The solute of aqueous slkali includes sodium hydroxide and quaternary ammonium salt, the substance withdrawl syndrome of sodium hydroxide and quaternary ammonium salt in mixed ammonium/alkali solutions
Than for 1:4-4:5；
It after stirring, is separated, the solid 1 isolated is dried；
Use NH4NO3Solution mixes progress ammonium with solid 1 and exchanges, and is dried, roasts again to the solid after exchange
Obtain multi-stage porous ZSM-5 molecular sieve.
In this application, at using sodium hydroxide and the alkaline solution of quaternary ammonium salt mixing to above-mentioned ZSM-5 molecular sieve
ZSM-5 molecular sieve is rapidly performed by desiliconization processing according to above-mentioned condition with sodium hydroxide and quaternary ammonium salt, in ZSM-5 molecule by reason
Occur hollow structure in sieve, but can be formed in superficial layer it is mesoporous, and ZSM-5 molecular sieve crystallinity reduce it is very small.In this Shen
The multi-stage porous ZSM-5 molecular sieve that please be prepared includes the mesoporous and micropore that hollow structure, the molecular sieve surface in molecular sieve are formed.
In the application, quaternary ammonium salt is selected from tetramethylammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide and four fourths
One or more kinds of mixing of base ammonium hydroxide；Preferably, quaternary ammonium salt is tetrapropylammonium hydroxide.
In some embodiments, the substance withdrawl syndrome of alkali metal hydroxide and quaternary ammonium salt ratio is 1:3-3:5.Or
The substance withdrawl syndrome of sodium hydroxide and quaternary ammonium salt ratio is 1:3-3:5
In some embodiments, in mixed ammonium/alkali solutions, the substance withdrawl syndrome point of alkali metal hydroxide, quaternary ammonium salt
It Wei not 0.05~0.30mol/L；Or the substance withdrawl syndrome of sodium hydroxide, quaternary ammonium salt is respectively 0.05~0.30mol/L.It is excellent
Choosing, in mixed ammonium/alkali solutions, alkali metal hydroxide, quaternary ammonium salt substance withdrawl syndrome be respectively 0.10~0.20mol/L.Hydrogen
Sodium oxide molybdena, quaternary ammonium salt substance withdrawl syndrome be respectively 0.10~0.20mol/L.
When the sodium hydroxide and quaternary ammonium salt in mixed ammonium/alkali solutions substance withdrawl syndrome ratio be 1:3-3:5, and sodium hydroxide,
When the substance withdrawl syndrome of quaternary ammonium salt is respectively 0.05~0.30mol/L, have regular hollow structure in ZSM-5 molecular sieve, and
Surface forms relatively uniform meso-hole structure.
The ZSM-5 molecular sieve with above structure feature that the application prepares due to while with hollow structure again
It can be formed in superficial layer mesoporous, then can change the catalytic performance of ZSM-5 molecular sieve, save efficiency.
In some embodiments, it is 1:5-1:20 (g/ that ZSM-5 molecular sieve and mixed ammonium/alkali solutions, which press solid-liquid mass volume ratio,
ml)；Preferably 1:8-1:12 (g/ml).
In some embodiments, ZSM-5 molecular sieve and mixed ammonium/alkali solutions stir under conditions of 100~200 DEG C of temperature
10~72h.
In some embodiments, ZSM-5 molecular sieve and mixed ammonium/alkali solutions stir under conditions of 150~180 DEG C of temperature
10~48h.
The time that ZSM-5 molecular sieve is mixed with above-mentioned mixed ammonium/alkali solutions in this application is no more than 72h, preferably 10~
48h prepares multi-stage porous ZSM-5 molecular sieve further across subsequent step.
In some embodiments, the NH for ammonium exchange4NO3The concentration of solution is 1.0mol/L.By solid-to-liquid ratio 1:10 into
Row ammonium exchanges 3 times.
In some embodiments, solid 1 and NH4NO3The solid isolated after the exchange of solution ammonium is done at 90-110 DEG C
It is dry.
In some embodiments, the temperature of ZSM-1 molecular sieve roasting is controlled at 500--600 DEG C.
The ZSM-5 molecular sieve of the application can be the ZSM-5 molecular sieve for meeting this technology requirement.Or using this
ZSM-5 molecular sieve made from the preparation method of application, it is preferred to use ZSM-5 molecular sieve made from the preparation method of the application.
ZSM-5 molecular sieve raw material used in this application is nano-ZSM-5 molecular sieve, and Si/Al is 20~80；Preferably, it receives
Rice ZSM-5 molecular sieve Si/Al is 30~50；It is furthermore preferred that nano-ZSM-5 molecular sieve Si/Al is 38.
In this application, raw material nano ZSM-5 molecular sieve partial size is 100~300nm.
ZSM-5 molecular sieve surface richness aluminium used in the present invention, internal Silicon-rich.Preferably, ZSM-5 molecular sieve internal crystallization degree compared with
It is low, so easily preparing hollow structure, meet the ZSM-5 molecular sieve of this technical conditions.
Or the ZSM-5 molecular sieve being prepared by the following method, preparation include the following steps:
(1) silicon source is slowly added in template, obtains solution 1；
(2) aluminium isopropoxide is hydrolyzed, obtains solution 2；
(3) solution 2 is added drop-wise in solution 1 and obtains mixed liquor, ZSM-5 molecular sieve is made in crystallization, post-processing.
Industrial raw material or analysis pure raw material can be selected in the silicon source of the application, silicon source, template.Silicon source, silicon source, template
Agent, alkali source can be silicon source commonly used in the art, silicon source, template, alkali source；Preferably, silicon source is aluminum nitrate, sodium metaaluminate, hydrogen
The one or more of aluminium oxide, aluminium isopropoxide, aluminum sulfate, aluminium oxide, boehmite；Silicon source is silica solution, waterglass, solid
One or more of silica gel, diatomite, silicate and tetraethyl orthosilicate；Template is ethyl alcohol, ammonium hydroxide, n-butylamine, second two
Amine, 4-propyl bromide, tetrapropylammonium hydroxide one or more.
In some embodiments, step (1) silicon source is added in template, and silicon source is added drop-wise to template with 1~2mL/min
In, 20-35 DEG C of stirring is fully hydrolyzed silicon source, and avoiding being added dropwise too fast causes to hydrolyze too fast generation SiO2。
In some embodiments, step (2) aluminium isopropoxide is in 85 DEG C of 0.5~3h of hydrolysis；Preferably, 0.5~2h is hydrolyzed.
Hydrolyze aluminium isopropoxide thoroughly under this condition to improve crystallinity.
In some embodiments, before step (3) crystallization mixed liquor 85 DEG C remove 2~6h of alcohol；Preferably, 2~4h of alcohol is removed.
The application is by removing all alcohol, and the crystallinity by improving ZSM-5 molecular sieve except alcohol except alcohol.
Pass through the inside Silicon-rich for the ZSM-5 molecular sieve that the above method is prepared, surface richness aluminium.
In some embodiments, the condition in crystallization process includes: 150~200 DEG C of crystallization temperature, and crystallization time 48~
100h；Preferably, 160~180 DEG C of crystallization temperature, 60~84h of crystallization time；It is furthermore preferred that 170 DEG C of crystallization temperature, when crystallization
Between 72h.
The application method is by passing through ZSM-5 molecular sieve prepared by above-mentioned crystallization process, internal crystallization degree to mixed liquor
It is lower, so being easier to prepare hollow structure.
In some embodiments, post-processing includes centrifuge separation, is dried, roasting.Drying temperature is 80-110 DEG C, roasting
Temperature is 450-600 DEG C.
Step (3) specifically, mixed liquor is placed in crystallizing kettle crystallization, crystallization product after centrifuge washing, drying and roasting,
Obtain ZSM-5 molecular sieve.
Specifically, crystallization product centrifuge washing 4 times first is subsequently placed in 100 DEG C of oven overnights, is finally placed in neutral
550 DEG C of Muffle furnaces roast 6 hours.
It is best in 550 DEG C of roasting effects, template can be thoroughly burnt up, ZSM-5 molecular sieve is obtained.
Compared with prior art, the application has the following beneficial effects:
The application has not only prepared relatively regular hollow structure, while in Surface Creation meso-hole structure, reducing
The resistance to mass tranfer of ZSM-5 molecular sieve is conducive to the transmitting of reactants and products, improves the catalytic performance of catalyst and uses the longevity
Life.
In addition, with other methods handle ZSM-5 compared with, the application prepare the time used in mesoporous-hollow ZSM-5 molecular sieve compared with
Short, hollow structure is regular, and crystallinity is high, and method is simple and easy, low in cost, large batch of can produce.
ZSM-5 molecular sieve grain partial size provided by the present application is nano particle scope, and intracrystalline diffusion resistance is small, strengthens reaction and produces
Object diffusion reduces coking rate, and then extends catalyst life.
In the synthesis nano-ZSM-5 molecular sieve method that the present invention uses, the concentration of whole system is higher, and water content is very low,
Increase the solid content of whole system, parent ZSM-5 molecular sieve one-pot yield is higher.
Below with reference to specific example to the further details of explanation of present invention content, but do not limit institute of the present invention
Scope of authority to be protected.
Primary analysis method in embodiment:
X-ray diffraction (XRD): Dutch Panaco Panalytical company X ' Pert Pro MPD type X-ray produced
Powder diffractometer；Scanning electron microscope (SEM): the detection of scanning electron microscope under Hitachi S-4000 type scanning electron microscope into
Row；Transmission electron microscope (TEM): TEM sample analysis is the JEM-2100UHR type transmission electron microscopy by Japan Electronics JEOL company
What mirror was completed；N2Physical absorption-desorption: it is measured using the Autosorb IQ instrument of Quantachrome company, the U.S..
Embodiment 1
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38:
The tetrapropylammonium hydroxide solution 32g for taking 25%, 31.1ml tetraethyl orthosilicate solution is slowly added dropwise into 35 DEG C
Magnetic agitation 3.5h under water-bath, this is solution 1；The aluminium isopropoxide of 0.75g is added in 75ml water, magnetic agitation under 85 DEG C of water-baths
1h is hydrolyzed, this is solution 2；Solution 2 is slowly dropped in solution 1,35 DEG C of stirring in water bath 2h, alcohol 2.5h is removed at 85 DEG C, is added
Water is to 150ml；It is added in crystallizing kettle, crystallization 72h at 170 DEG C, centrifuge separation, 100 DEG C of drying, 550 DEG C of roastings obtain nanometer
ZSM-5 zeolite molecular sieve.
Mix the preparation of mesoporous-hollow compound ZSM-5 molecular sieve of alkali modification:
It takes the above-mentioned nano-ZSM-5 molecular sieve of 10g to be placed in a beaker, 100ml mixed ammonium/alkali solutions is added, in mixed ammonium/alkali solutions
In, the concentration of sodium hydroxide is 0.10mol/L, and the concentration 0.20mol/L of tetrapropylammonium hydroxide is stirring evenly and then adding into crystallization
It in kettle, is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3
Secondary ammonium exchange, 100 DEG C of drying, 550 DEG C of roastings are to get multi-stage porous ZSM-5 molecular sieve.
To without alkaline solution treatment nano-sized ZSM-5 zeolite molecular sieve (A sample) and mixed alkali liquor that treated is multistage
Hole ZSM-5 molecular sieve (B sample) carries out XRD, TEM, SEM, N2The performance detections such as physical absorption-desorption:
A is untreated solid nano-ZSM-5 molecular sieve (the i.e. raw material nano ZMS-5 zeolite of the preparation of embodiment 1 in Fig. 1
Molecular sieve), the tetrapropylammonium hydroxide mixed ammonium/alkali solutions processing that B is the sodium hydroxide+0.20mol/L that concentration is 0.10mol/L
The hollow compound ZSM-5 molecular sieve of the micropore-mesopore-obtained afterwards.By mixed base, treated it can be seen from Fig. 1 XRD spectra
ZSM-5 molecular sieve crystal form does not change, and crystallinity reduction is very small, illustrates that TPAOH is recrystallized while desiliconization.
Schemed to obtain the hollow ZSM-5 with meso-hole structure points of surface after it is obvious that mixing alkali process by Fig. 2 TEM
Son sieve.
By Fig. 3 SEM figure, it can be seen that, significant change, table occur for ZSM-5 molecular sieve surface topography after mixing alkali process
Face forms irregular protrusion, and the hollow ZSM-5 molecular sieve of only a few is broken.
By Fig. 4 N2In physical absorption-desorption figure, from the hysteresis loop formed from adsorption curve and desorption curve may determine that
The hole of sample is transgranular hole after reason.
Embodiment 2
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38 is same as Example 1.
Mix the preparation of the hollow ZSM-5 molecular sieve of alkali modification:
It takes the above-mentioned nano-ZSM-5 molecular sieve of 10g to be placed in a beaker, 100ml mixed ammonium/alkali solutions is added, in mixed ammonium/alkali solutions
In, the concentration of sodium hydroxide is 0.05mol/L, and the concentration 0.25mol/L of tetrapropylammonium hydroxide is stirring evenly and then adding into crystallization
It in kettle, is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3
Secondary ammonium exchange, 100 DEG C of drying, 550 DEG C of roastings are to get hollow ZSM-5 molecular sieve.
Embodiment 3
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38 is same as Example 1.
Mix the preparation of the hollow ZSM-5 molecular sieve of alkali modification:
It takes 10g nano-ZSM-5 molecular sieve to be placed in a beaker, 100ml mixed ammonium/alkali solutions, in mixed ammonium/alkali solutions, hydrogen is added
The concentration of sodium oxide molybdena is 0.10mol/L, and the concentration of tetrapropylammonium hydroxide is 0.30mol/L, is stirring evenly and then adding into crystallizing kettle
In, it is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3 times
Ammonium exchange, 100 DEG C of drying, 550 DEG C of roastings are to get micro- multi-stage porous ZSM-5 molecular sieve.
Embodiment 4
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38 is same as Example 1.
Mix the preparation of the hollow ZSM-5 molecular sieve of alkali modification:
It takes 10g nano-ZSM-5 molecular sieve to be placed in a beaker, 100ml mixed ammonium/alkali solutions, in mixed ammonium/alkali solutions, hydrogen is added
The concentration of sodium oxide molybdena is 0.15mol/L, and the concentration of tetrapropylammonium hydroxide is 0.25mol/L, is stirring evenly and then adding into crystallizing kettle
In, it is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3 times
Ammonium exchange, 100 DEG C of drying, 550 DEG C of roastings are to get multi-stage porous ZSM-5 molecular sieve.
Embodiment 5
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38 is identical as example 1.
Mix the preparation of the hollow ZSM-5 molecular sieve of alkali modification:
It takes 10g nano-ZSM-5 molecular sieve to be placed in a beaker, 100ml mixed ammonium/alkali solutions, in mixed ammonium/alkali solutions, hydrogen is added
The concentration of sodium oxide molybdena is 0.15mol/L, and tetrapropylammonium hydroxide concentration 0.15mol/L is stirring evenly and then adding into crystallizing kettle, In
It is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3 ammoniums and hands over
It changes, 100 DEG C of drying, 550 DEG C of roastings are to get hollow ZSM-5 molecular sieve.
Carry out TEM electron microscope analysis to embodiment 2-5 treated product: Fig. 5,6,7,8 are respectively embodiment 2,3,4,5 four
Hollow ZSM-5 molecular sieve obtained by kind processing method.The tetrapropyl hydroxide of the sodium hydroxide+0.25mol/L of 0.05mol/L
After the processing of ammonium mixed ammonium/alkali solutions, formd as shown in Figure 5 than more complete hollow structure, than tetrapropylammonium hydroxide is used alone
It handles out hollow shorten and handles the time, but not formed meso-hole structure.Concentration is the sodium hydroxide+0.30mol/L of 0.10mol/L
The hollow structure surface that handles out of tetrapropylammonium hydroxide mixed ammonium/alkali solutions form numerous apparent meso-hole structures (as schemed
6)；The hollow structure table that the tetrapropylammonium hydroxide mixed ammonium/alkali solutions of the sodium hydroxide+0.25mol/L of 0.15mol/L are handled out
Face has been similarly formed numerous apparent meso-hole structures, and relatively uniform (such as Fig. 7)；The sodium hydroxide of 0.15mol/L+
The hollow structure that the tetrapropylammonium hydroxide mixed ammonium/alkali solutions of 0.15mol/L are handled out, surface is substantially without meso-hole structure (as schemed
8)。
Embodiment 6
10g nano-ZSM-5 molecular sieve is taken to be placed in a beaker, the Si/Al in molecular sieve is 32, and molecular sieve partial size is sieve partial size
For 100~300nm.100ml mixed ammonium/alkali solutions are added, in mixed ammonium/alkali solutions, the concentration of sodium hydroxide is 0.15mol/L, four
The concentration 0.25mol/L of butyl ammonium hydroxide, is stirring evenly and then adding into crystallizing kettle, stirs under the conditions of 100 DEG C for 24 hours, centrifugation
It separates, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3 ammonium exchanges, and 100 DEG C of drying, 550 DEG C roast,
Up to multi-stage porous ZSM-5 molecular sieve.
Embodiment 7
10g nano-ZSM-5 molecular sieve is taken to be placed in a beaker, the Si/Al in molecular sieve is 45, and molecular sieve partial size is sieve partial size
For 100~300nm.100ml mixed ammonium/alkali solutions are added, in mixed ammonium/alkali solutions, the concentration of sodium hydroxide is 0.10mol/L, four
The concentration of propyl ammonium hydroxide is 0.20mol/L, is stirring evenly and then adding into crystallizing kettle, stirs 48h under the conditions of 100 DEG C, from
The heart separates, and dries under the conditions of 100 DEG C, uses the NH of 1mol/L4NO3Solution carries out 3 ammonium exchanges, 100 DEG C of drying, 550 DEG C of roastings
It burns to get multi-stage porous ZSM-5 molecular sieve.
Embodiment 8
The synthesis for the nano-sized ZSM-5 zeolite molecular sieve that Si/Al is 38 is identical as example 1.
Mix the preparation of mesoporous-hollow compound ZSM-5 molecular sieve of alkali modification:
It takes the above-mentioned nano-ZSM-5 molecular sieve of 10g to be placed in a beaker, 100ml mixed ammonium/alkali solutions is added, in mixed ammonium/alkali solutions
In, the concentration of sodium hydroxide is 0.10mol/L, and the concentration 0.20mol/L of tetrapropylammonium hydroxide is stirring evenly and then adding into crystallization
It in kettle, is stirred under the conditions of 170 DEG C for 24 hours, centrifuge separation, is dried under the conditions of 100 DEG C, use the NH of 1mol/L4NO3Solution carries out 3
Secondary ammonium exchange, 100 DEG C of drying, 550 DEG C of roastings are to get multi-stage porous ZSM-5 molecular sieve.
The application is described in detail, and its object is to allow those skilled in the art that can understand the application's
Content is simultaneously implemented, and can not limit the protection scope of the application with this, it is all according to spirit herein substantially done etc.
Changes or modifications are imitated, should all be covered within the scope of protection of this application.
Claims (10)
1. a kind of preparation method of multi-stage porous ZSM-5 molecular sieve, comprising: mix ZSM-5 molecular sieve with mixed ammonium/alkali solutions, stir
Mix, wherein the solute of mixed ammonium/alkali solutions includes alkali metal hydroxide and quaternary ammonium salt, alkali metal hydroxide and quaternary ammonium salt it is dense
Degree is than being 1:4-4:5；
It after stirring, is separated, the solid 1 isolated is dried；
Use NH4NO3Solution mixes progress ammonium with solid 1 and exchanges, and is dried, roasts again to the solid after exchange, can be obtained
Multi-stage porous ZSM-5 molecular sieve.
2. preparation method according to claim 1, which is characterized in that in mixed ammonium/alkali solutions, alkali metal hydroxide with
The substance withdrawl syndrome ratio of quaternary ammonium salt is 1:3-3:5.
3. preparation method according to claim 1 or 2, which is characterized in that by ZSM-5 molecular sieve and mixed ammonium/alkali solutions in temperature
It mixes and stirs under conditions of 100~200 DEG C of degree, wherein alkali metal hydroxide includes sodium hydroxide and/or potassium hydroxide.
4. preparation method according to claim 1-3, which is characterized in that in mixed ammonium/alkali solutions, alkali metal hydrogen
Oxide, quaternary ammonium salt substance withdrawl syndrome be respectively 0.05~0.30mol/L；It is preferred that in mixed ammonium/alkali solutions, alkali metal hydrogen
Oxide, quaternary ammonium salt substance withdrawl syndrome be respectively 0.10~0.20mol/L.
5. preparation method according to claim 1-4, which is characterized in that ZSM-5 molecular sieve and mixed ammonium/alkali solutions
It is 1:5g/ml -1:20g/ml by solid-liquid mass volume ratio；Preferably 1:8g/ml -1:12g/ml.
6. preparation method according to claim 1-4, which is characterized in that ZSM-5 molecular sieve and mixed ammonium/alkali solutions
10~72h is stirred under conditions of 100~200 DEG C of temperature；
It is preferred that ZSM-5 molecular sieve and mixed ammonium/alkali solutions stir 10~48h under conditions of 150~180 DEG C of temperature.
7. preparation method according to claim 1-6, which is characterized in that ZSM-5 molecular sieve raw material is nanometer
ZSM-5 molecular sieve, Si/Al are 20~80；Preferably, nano-ZSM-5 molecular sieve Si/Al is 30~50；It is furthermore preferred that nanometer
ZSM-5 molecular sieve Si/Al is 38.
8. preparation method according to claim 7, which is characterized in that nano-ZSM-5 molecular sieve partial size is 100~300nm.
9. preparation method according to claim 1 or claim 7, which is characterized in that the preparation of ZSM-5 molecular sieve raw material includes as follows
Step:
(1) silicon source is slowly added in template, obtains solution 1；
(2) aluminium isopropoxide is hydrolyzed, obtains solution 2；
(3) solution 2 is added drop-wise in solution 1 and obtains mixed liquor, ZSM-5 molecular sieve is made in crystallization, post-processing；
Preferably, step (1) silicon source is added in template, and silicon source is added drop-wise in template with 1~2mL/min, and 20-35 DEG C is stirred
It mixes；
Preferably, step (2) aluminium isopropoxide is in 85 DEG C of 0.5~3h of hydrolysis.
10. according to the method described in claim 9, it is characterized in that, mixed liquor is at 85 DEG C except 2~6h of alcohol before step (3) crystallization；
Preferably, 2~4h of alcohol is removed.
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