CN109420520A - A kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst and its preparation method and application - Google Patents
A kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of multilevel structure ZSM-5 zeolite molecular sieve catalysts and its preparation method and application, the preparation method includes: that (1) instills microcellular structure directing agent solution in the mixed solution containing silicon source, silicon source and water, after agitated, precursor solution is obtained；(2) after continuing to stir to get aqueous precursor gel at 30~60 DEG C by gained precursor solution, then through powder dry and processed, dry gel powder is obtained；(3) gained dry gel powder is placed in steam condition at 100~180 DEG C after steam aid in treatment 5~48 hours, then through drying, primary calcining, obtains sodium form ZSM-5 zeolite molecular sieve；(4) by gained sodium form ZSM-5 zeolite molecular sieve after ion exchange, secondary clacining, the multilevel structure ZSM-5 zeolite molecular sieve catalyst is obtained.
Description
Technical field
The invention belongs to inorganic material synthesis and catalytic fields, and in particular to a kind of high-performance methanol catalyst for preparing propene
Preparation method and applications, in particular to a kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst and its preparation method and application.
Background technique
Propylene is a kind of important basic chemical industry raw material, and market demand is huge in recent years.Prepare the low-carbon alkenes such as propylene
Conventional method be lighter hydrocarbons/light oil thermal cracking process, major product is ethylene, and byproduct is propylene.However, petroleum resources
Supply is becoming tight day, along with the energy resource structure of the few oil of the more coals in China, prepares propylene as raw material using petroleum and has been unable to meet market
Demand, therefore, exploitation Non oil-based route production method are of great significance for alleviating current propylene imbalance between supply and demand.Wherein,
It using coal as raw material methanol, then by preparing propylene from methanol is a feasible technique.Therefore, exploitation preparing propylene from methanol technology becomes me
The important development strategy of state's coal chemical technology, wherein prepare the core place that high performance catalyst is the technology.
ZSM-5 zeolite is a kind of novel boiling that Mobile oil company, the U.S. is synthesized in eighties of last century the late sixties
Stone molecular sieve.A large number of studies show that ZSM-5 zeolite has high Propylene Selectivity, adjustable acid and preferable hydrothermal stability,
It is one of the preferred catalyst of current methanol to propylene reaction.But for pure phase micro-pore zeolite, single microcellular structure meeting
The transmission speed of limited reactions object and product in duct may cause intermediate or the more side reactions of product, form carbon deposit,
Reduce the selectivity and catalyst life of target product propylene.
Compared to traditional micro-pore zeolite, hierarchical porous structure zeolite have crystalline microporous zeolite skeleton and auxiliary it is mesoporous/
Macroporous structure, while keeping highly selective traditional zeolite, high stability feature, the meso/macroporous structure of perforation is not only
High specific surface area and more catalytic active sites are provided, and shortens diffusion length of the substance in micropore canals, is mentioned
The express passway for having supplied mass transfer enables reactants and products rapidly to spread arrival or leaves activated centre, it is suppressed that
The generation of side reaction, and then improve reactivity, product yield and catalyst life.Currently, preparing the side of multilevel structure zeolite
Method mainly includes etching method, template etc..However, etching method often destroys the skeleton structure of zeolite, make its hydrothermal stability
Decline, and process is difficult to control, and is readily incorporated unordered mesoporous.And the use of a large amount of templates not only increases original in template
Material cost reduces materials synthesis efficiency, and the template removal in later period needs to consume mass energy, discharges more dioxy
Change carbon, NOxIsothermal chamber gas.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of simple process, low-cost methods to prepare high property
The catalyst for producing propylene with methanol of energy and its application in methanol to propylene reaction.
On the one hand, the present invention provides a kind of preparation methods of multilevel structure ZSM-5 zeolite molecular sieve catalyst, comprising:
(1) microcellular structure directing agent solution is instilled in the mixed solution containing silicon source, silicon source and water, after agitated, before obtaining
Drive liquid solution；
(2) it after continuing to stir to get aqueous precursor gel at 30~60 DEG C by gained precursor solution, then through powder dry and processed, obtains
To dry gel powder；
(3) gained dry gel powder is placed in steam condition at 100~180 DEG C after steam aid in treatment 5~48 hours, then
It is once calcined, obtains sodium form ZSM-5 zeolite molecular sieve；
(4) it by gained sodium form ZSM-5 zeolite molecular sieve after carrying out ion exchange, secondary clacining with ammonium ion, obtains described
Multilevel structure ZSM-5 zeolite molecular sieve catalyst.
The present invention uniformly mixes silicon source, silicon source and deionized water, obtains mixed solution.Then microcellular structure is added dropwise again to lead
To agent solution into mixed solution, it is carried out while improving mixed solution basicity continue stirring, make silicon source therein and
Silicon source is fully hydrolyzed, and obtains clear precursor solution.Again gained precursor solution is continued to stir to get at 30~60 DEG C
After aqueous precursor gel, then through drying, powder processed obtain dry gel powder.Gained dry gel powder is placed in steam condition 100
It at~180 DEG C after steam aid in treatment 5~48 hours, then is once calcined, obtains sodium form ZSM-5 zeolite molecular sieve.By gained
Sodium form ZSM-5 zeolite molecular sieve, which is passed through, carries out ion exchange with ammonium ion, obtains ammonium type ZSM-5 zeolite molecular sieve.By gained ammonium
Type ZSM-5 zeolite molecular sieve is after secondary clacining, ammonium ion pyrolytic, obtains the multilevel structure ZSM-5 zeolite
Molecular sieve catalyst (i.e., HZSM-5 zeolite molecular sieve).
Preferably, the molar ratio of the silicon source, silicon source and water is (100~400) in step (1): 1:(2000~
7000), preferably (200~300): 1:(4000~5000), the molar ratio of the microcellular structure directed agents and silicon source is (0.07
~0.16): 1, preferably (0.1~0.13): 1.
Preferably, the silicon source is that ethyl orthosilicate, silica nanosphere and mesoporous silicon oxide are received in step (1)
At least one of rice ball, source of aluminium are aluminium isopropoxide and/or sodium metaaluminate, and the microcellular structure directed agents are tetrapropyl hydrogen
Amine-oxides and/or 4-propyl bromide.
Preferably, the mass fraction of microcellular structure directed agents is 20 in the microcellular structure directing agent solution in step (1)
~30wt%, the rate of the instillation are 0.1~1.4g/ minutes, preferably 0.2~0.5g/ minutes.
Preferably, in step (1), the temperature of the stirring is 20~50 DEG C, and the time is 2~5 hours, rate is 300~
500 revs/min.
Preferably, the rate of the stirring is 300~500 revs/min in step (2).
Preferably, the temperature of the drying is 30~60 DEG C in step (2), on the basis of 1mol silicon source proportion, until institute
The quality for obtaining xerogel powder is 100~130 grams.
Preferably, it is described it is primary calcining or/and secondary clacining temperature be 400~600 DEG C, preferably 150~550 DEG C,
Time is 6~10 hours.
Preferably, in step (4), it is described to include: with ammonium ion progress ion exchange
(1) gained sodium form ZSM-5 zeolite molecular sieve is placed in the solution of the ammonium ion containing 0.5~3mol/L, 60~
At 90 DEG C after heating stirring 3~10 hours, using filter and drying, solid product is obtained；
(2) it repeats step (1) 2~5 time, preferably 2~3 times.
Also, preferably, the solution of the ammonium ion is the aqueous solution containing ammonium chloride or/and ammonium nitrate, every gram of control
The volume that the solution of the ammonium ion containing 0.5~3mol/L is added in sodium form ZSM-5 zeolite molecular sieve is 80~120ml.
On the other hand, the present invention also provides a kind of multilevel structure ZSM-5 zeolite molecular sieves prepared according to the above method
Catalyst.The particle ruler for the multilevel structure ZSM-5 zeolite molecular sieve catalyst (ZSM-5 zeolite molecular sieve) that the present invention is prepared
It is very little controllable between 0.05~2 micron,And the density ratio in Lewis acid site is controllable between 2~10, and particle
Inside has the mesoporous channel of random distribution, and aperture is at 3~7 nanometers.
In another aspect, the present invention also provides a kind of if above-mentioned multilevel structure ZSM-5 zeolite molecular sieve catalyst is in first
Application during alcohol propylene.
The advantages of prepared high-performance methanol propylene ZSM-5 zeolite catalyst, is in the present invention:
(1) preparation process is simple, low in cost, reproducible, easily industrially promotes；
(2) regulate and control with can be convenient the silica alumina ratio of zeolite catalyst, particle size,With the density in Lewis acid site
Than to optimize catalytic performance.
Detailed description of the invention
Fig. 1 is that the XRD diagram (a) of multilevel structure ZSM-5 zeolite molecular sieve catalyst obtained by embodiment 1 and nitrogen are inhaled
Attached-desorption isotherm (b)；
Fig. 2 is the SEM photograph (a) and its Cross section polishing of multilevel structure ZSM-5 zeolite molecular sieve catalyst obtained by embodiment 1
SEM photograph (b) and TEM photo (c) afterwards；
Fig. 3 is the pyridine adsorption FTIR spectrogram of multilevel structure ZSM-5 zeolite molecular sieve catalyst obtained by embodiment 1；
Fig. 4 is the SEM photograph (a) and TEM photo (b) of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 2；
Fig. 5 is the TEM photo of mesoporous silica nanospheres used in embodiment 3；
Fig. 6 is the XRD diagram (a) and nitrogen adsorption-desorption of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3
Thermoisopleth (b)；
Fig. 7 is the SEM photograph of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3；
Fig. 8 is the pyridine adsorption FTIR spectrogram of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3；
Fig. 9 is the methanol conversion and Propylene Selectivity of multilevel structure ZSM-5 zeolite molecular sieve catalyst measured by embodiment 4
With the variation in reaction time.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
The progress of microcellular structure directing agent solution is slowly added dropwise in silicon source, silicon source and deionized water by the present invention again after mixing
It is fully hydrolyzed, the gel quality after drying should be controlled in a certain range, and steam auxiliary crystallization handles sodium obtained after a certain period of time
Type ZSM-5 zeolite molecular sieve.Again after ion exchange and calcining, obtains that there is mesoporous channel and particle size and Acidity can
The multilevel structure ZSM-5 zeolite molecular sieve catalyst of control.
Silicon source and silicon source are first uniformly mixed with by the present invention is conducive to improve degree of scatter of the aluminium in system, urges to improve
Change the dispersibility of active site (from aluminium atom), this is conducive to improve catalytic performance.On the other hand, silicon source and silicon source are mixed
After closing uniformly tetrapropylammonium hydroxide is slowly added dropwise again the basicity of system can be made to be gradually increased, is conducive to the equal of silicon source and silicon source
Even slow hydrolysis, to control alumino-silicate hydrolytic condensation process.Illustrate to following exemplary multilevel structure provided by the invention
The preparation method of ZSM-5 zeolite molecular sieve catalyst.
Silicon source, silicon source and deionized water are uniformly mixed, mixed solution is obtained.The silicon source can for ethyl orthosilicate,
At least one of silica nanosphere and mesoporous silica nanospheres.Wherein, silica nanosphere and meso-porous titanium dioxide
The partial size of silicon nanosphere is 20~500 nanometers, preferably 40~60 nanometers.The silicon source can be in aluminium isopropoxide and sodium metaaluminate
It is at least one.The molar ratio of the silicon source, silicon source and water (deionized water) can be (100~400): 1:(2000~7000), it is excellent
It is selected as (200~300): 1:(4000~5000).As an example, by silicon source, silicon source and deionized water at 20~30 DEG C
Stirring 0.5~1 hour, obtains mixed solution.
Microcellular structure directing agent solution is instilled in gained mixed solution, it is carried out while improving mixed solution basicity
(whipping process is hydrolytic process, and the temperature of stirring can be 20~50 DEG C, and the time can be 2~5 hours for lasting stirring.Stirring rate
It can be 300~500 revs/min, be fully hydrolyzed silicon source and silicon source therein, obtain clear precursor solution.Described is micro-
Pore structure directing agent solution can be at least one of tetrapropylammonium hydroxide and the aqueous solution of 4-propyl bromide.The micropore knot
The molar ratio of structure directed agents and silicon source can be 0.07~0.16:1, preferably 0.1~0.13:1.The microcellular structure directing agent solution
The mass fraction of middle microcellular structure directed agents can be 20~30wt%, control the rate of the instillation at 0.1~1.4g/ minutes
Between (preferably 0.2~0.5g/ minutes).As an example, microcellular structure directed agents in the microcellular structure directing agent solution
Mass fraction when can be 2~7g for 20~30wt%, microcellular structure directing agent solution gross mass, the process control of dropwise addition is 5
~20 minutes.
Gained precursor solution is continued to stirring (stirring rate can be 300~500 revs/min) to obtain at 30~60 DEG C
After aqueous precursor gel, then through powder dry and processed, obtain dry gel powder.The temperature of the drying can be 30~60 DEG C, with 1mol
On the basis of silicon source proportion, until the quality of gained xerogel powder or xerogel is 100~130 grams." with 1 mole in the present invention
Subject to the proportion of silicon source, the xerogel quality controlled is 100~130 grams " comprising different effects: firstly, by presoma
Gel drying to certain mass needs the regular hour, mutually can slowly make between the various molecules in presoma in this process
With mutual glue connection forms certain network structure, which is properly termed as " being aged "；Secondly, the inevitable companion during " ageing "
With " drying " process, we control the quality of xerogel at 100~300 grams, at this point, the moisture in xerogel is very
Few, mass transfer during steam auxiliary crystallization in aqueous precursor gel is obstructed, this is conducive to mesoporous in aqueous precursor gel
Structure is retained.It can be illustrated by the IV type thermoisopleth and H1 type hysteresis loop in b in Fig. 1 and the pore structure parameter in table 1
The process advan forms meso-hole structure abundant in zeolite.The mode of powder processed can be grinding, ball milling etc..Wherein aqueous precursor gel
Can carry out, can also carry out under same temperature and environment at different temperatures with drying process, for example, drying temperature be 60 DEG C with
On.As an example, resulting precursor solution is placed in the water bath device of certain temperature (30~60 DEG C), and lasting stirring is straight
To gel drying to certain mass, it is subject to the proportion of 1 mole of silicon source, obtained xerogel quality is 100~130 grams.
Dry gel powder is placed in steam condition at 100~180 DEG C after steam aid in treatment 5~48 hours, then is passed through
Drying obtains solid product.Calcining removes organic matter under high temperature air atmosphere after resulting solid product is sufficiently dried again
Molecule obtains the sodium form ZSM-5 zeolite molecular sieve with mesoporous channel.Wherein, drying can be that drying 12 is small in 80 DEG C of baking ovens
When.The temperature once calcined can be 400~600 DEG C, and preferably 450~550 DEG C, calcination time can be 6~10 hours.As one
Example, the dry gel powder after gained is ground are placed in crucible, and the crucible equipped with dry gel powder is put into polytetrafluoroethylene (PTFE)
Deionized water is added in liner, liner bottom, keeps water not contact with xerogel, polytetrafluoroethyllining lining is then put into stainless steel
It is sealed in water heating kettle, then after a certain period of time, taking-up is put into cold in ice water crystallization under conditions of certain temperature and steam assist
But, crystallization temperature is 100~180 DEG C, and preferably 150~160 DEG C, crystallization time is 5~48 hours, preferably 10~17 hours.
Sodium form ZSM-5 zeolite molecular sieve is mixed, in a water bath heating stirring certain time with ammonium ion solution, is filtered
It is sufficiently dried after obtaining solid product, is repeated several times, obtains ammonium type ZSM-5 zeolite molecular sieve.The ammonium ion solution is
At least one of ammonium chloride and ammonium nitrate.It controls every gram of sodium form ZSM-5 zeolite molecular sieve and the ammonium containing 0.5~3mol/L is added
The volume of the solution of radical ion is 80~120ml.The temperature of the heating stirring can be 60~90 DEG C, preferably 70~80 DEG C, add
The time of thermal agitation can be 3~10 hours, and number of repetition is 2~5 times, preferably 2~3 times.
By ammonium type molecular sieve, secondary clacining obtains the Hydrogen ZSM-5 zeolite point with mesoporous channel under high temperature air atmosphere
Sub- sieve catalyst.Wherein, the temperature of secondary clacining can be 400~600 DEG C, and preferably 450~550 DEG C, the time can be small for 6~10
When.
The detailed example of preparation method as a high-performance methanol catalyst for preparing propene, main preparation step are as follows:
Firstly, silicon source, silicon source and deionized water are uniformly mixed, wherein the molar ratio of silicon source and silicon source is 100~400:1；Secondly,
Microcellular structure directing agent solution is slowly added dropwise into above-mentioned mixed solution, wherein mole of microcellular structure directed agents and silicon source
Than for 0.07~0.16:1, the process control of dropwise addition was at 5~20 minutes；Continue stirring 2~5 hours, until silicon source and silicon source water
Solution completely, clarify by precursor mixed solution；Then, precursor solution is dried to obtain xerogel in 30~60 DEG C of water-baths；It connects
Get off, xerogel is levigate, crystallization 5~48 hours under 100~180 DEG C of steam subsidiary conditions；Mixture after crystallization is through filling
6~10 hours are calcined at 400~600 DEG C to remove the organic molecules such as microcellular structure directed agents after dividing drying, obtains that there is Jie
The sodium form ZSM-5 zeolite molecular sieve of hole path；Sodium form molecular sieve is mixed with the ammonium ion solution of 0.5~3 mol/L, and
Heating stirring 3~10 hours at 60~90 DEG C are obtained by filtration after solid product and sufficiently dry, and repeat 2~5 times, obtain ammonium type
ZSM-5 zeolite molecular sieve；Obtain within 6~10 hours that there is mesoporous channel finally, ammonium type molecular sieve is calcined at 400~600 DEG C
Hydrogen ZSM-5 zeolite molecular sieve catalyst.
The present invention also provides a kind of high-performance multilevel structure ZSM-5 zeolite molecular sieve catalysts in preparing propylene from methanol process
In application.Specifically, by the multilevel structure ZSM-5 zeolite molecular sieve catalyst (catalyst) of preparation 5~20MPa pressure
Power lower sheeting is sieved after broken, takes the particle between 40~60 mesh for being catalyzed reaction.Catalysis after taking 0.05~2 gram of granulation
Agent is fitted into the quartz ampoule of fixed bed reactors, and preferably 0.1~0.3 gram.Methanol is in nitrogen dilution, reaction temperature 300~550
DEG C, 0.01~0.5MPa of reaction pressure, 0.3~5g of air speed g-1h-1(looking like for every gram of catalyst of 0.3~5 gram of methanol per hour)
Under conditions of converted, preferable reaction temperature is 450~470 DEG C, preferably reaction pressure is 0.05~0.2MPa, preferably air speed
For 1~2g g-1h-1。
Preparation process of the present invention is simple, and synthesis cost is low, and obtained catalyst can be used in preparing propylene from methanol industry, anti-
Answer 300~550 DEG C of temperature, 0.01~0.5MPa of reaction pressure, 0.5~3g of air speed g-1h-1Under, catalyst of the invention has
The advantages that methanol conversion is high, Propylene Selectivity is high, long catalytic life.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
Embodiment 1
A) that 10.42 grams of ethyl orthosilicates, 0.0511 gram of aluminium isopropoxide and 18 grams of deionized waters are stirred 0.5 under 25 DEG C of water-baths is small
When (rate be 400 revs/min), until being uniformly mixed；
B) 4.0672 grams of tetrapropylammonium hydroxide (25wt% aqueous solution) are slowly dropped into above-mentioned mixed solution, dropwise addition it is excessively program-controlled
System continued 3 hours of stirring (rate is 400 revs/min) until silicon source and the abundant water of silicon source at 10 minutes under 25 DEG C of water-baths
Solution, mixed solution clarification；
C) bath temperature is increased to 40 DEG C and continues stirring (rate is 400 revs/min) precursor solution and obtain gel, gained
Gel continue dry until its quality reaches 5.7 grams；
D) above-mentioned xerogel is clayed into power with agate mortar and is then transferred to crucible, the crucible equipped with dry gel powder is put into
1 gram of deionized water is added in 80 milliliters of polytetrafluoroethyllining lining, liner bottom, and water is not contacted with xerogel, then by polytetrafluoro
Ethylene liner is put into stainless steel water heating kettle and seals；
E) water heating kettle is put into 150 DEG C of baking ovens after crystallization 10 hours and is taken out, is put into ice water cooling；
F) sample after crystallization is put into 80 DEG C of baking ovens 12 hours dry, then in 550 DEG C of Muffle furnaces, is calcined under air atmosphere
6 hours, heating rate was 2 DEG C/min, obtained the sodium form ZSM-5 zeolite molecular sieve with mesoporous channel；
G) sodium form ZSM-5 zeolite molecular sieve is mixed with the ammonium chloride solution of 1 mol/L, every gram molecule sieve need to be added 100 milliliters
Then ammonium chloride solution filters mixed solution, the solid product that will be obtained by filtration in 80 DEG C of water-baths after heating stirring 6 hours
Drying 12 hours in 80 DEG C of baking ovens are put into, ion exchange process is repeated 3 times, and obtains ammonium type ZSM-5 zeolite molecular sieve；
H) it finally, by ammonium type ZSM-5 zeolite molecular sieve in 550 DEG C of Muffle furnaces, is calcined 6 hours under air atmosphere, heating rate
It is 2 DEG C/min, obtains the Hydrogen ZSM-5 zeolite molecular sieve catalyst with mesoporous channel；
Table 1 is the pore structure parameter of 1 gained sample of embodiment:
Fig. 1 be the present embodiment 1 obtained by multilevel structure ZSM-5 zeolite molecular sieve catalyst XRD diagram (a in Fig. 1) and
Nitrogen adsorption-desorption isotherm (b in Fig. 1).By XRD diagram as it can be seen that catalyst is the zeolite and crystallinity of MFI type topological structure
Height, by the visible typical IV type thermoisopleth of nitrogen adsorption-desorption isotherm and H1 type hysteresis loop, in 0.4 < P/P0< 1.0 exists
Apparent absorption kick, illustrates that there are meso-hole structures in zeolite catalyst；
Fig. 2 is multilevel structure ZSM-5 zeolite molecular sieve catalyst obtained by the present embodiment 1 and its (figure of the SEM after Cross section polishing
A in 2, b) and TEM photo (c in Fig. 2).By a in Fig. 2 as it can be seen that zeolite present 400~500 nanometers of diameter spheric granules and
Surface porosity is porous, from the SEM photograph (b in Fig. 2) of Cross section polishing it can be seen that zeolite granular inside there are random distributions
Mesoporous channel, aperture is at 4~7 nanometers, and TEM photo (c in Fig. 2) is it can be seen that lattice fringe through entire particle, illustrates to make
Standby material is multilevel structure ZSM-5 zeolite molecular sieve；
Fig. 3 is the pyridine adsorption FTIR spectrogram of multilevel structure ZSM-5 zeolite molecular sieve catalyst obtained by the present embodiment 1.By
Fig. 3 as it can be seen that catalyst in 1546cm-1、1455cm-1And 1490cm-1There are three characteristic peaks at place, correspond respectively to pyridine adsorption and existSour site, pyridine adsorption, in the eutectoid content in two kinds of sour sites, illustrate urging for preparation in Lewis acid site and pyridine
Agent has needed for the reaction of catalysis methanol propyleneWith Lewis acid site；
Table 2 is the quantitative result of pyridine adsorption FTIR spectrogram after 200 DEG C of desorptions:
Embodiment 2
The present embodiment difference from example 1 is that: the molar ratio of microcellular structure directed agents and silicon source be 0.13.In remaining
Hold with described in embodiment 1.
Fig. 4 is the SEM (a in Fig. 4) and TEM photo of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 2
(b in Fig. 4).From fig. 4, it can be seen that 200~250 nanometers of diameter of spheric granules is presented for zeolite and surface porosity is porous, zeolite
Intragranular portion has mesoporous channel (4~7nm of channel diameter)；
Table 3 is the quantitative result of pyridine adsorption FTIR spectrogram after 200 DEG C of desorptions:
Embodiment 3
The present embodiment difference from example 1 is that: use mesoporous silica nanospheres as silicon source, dosage is 3 grams,
Microcellular structure directed agents are added simultaneously with silicon source, silicon source and deionized water and mix, and crystallization temperature is 110 DEG C, crystallization time 48
Hour.Remaining content is the same as described in embodiment 1.
Fig. 5 is the TEM photo of mesoporous silica nanospheres used in embodiment 3.As seen from the figure, mesoporous silicon oxide is received
The diameter of rice ball has meso-hole structure, 3~5nm of channel diameter in 40 rans；
Fig. 6 is the XRD diagram (a in Fig. 6) and nitrogen adsorption-of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3
Desorption isotherm (a in Fig. 6).By XRD diagram as it can be seen that catalyst is similarly the zeolite of MFI type topological structure and crystallinity is high, by nitrogen
The equally visible typical IV type thermoisopleth of gas adsorption-desorption isothermal and H1 type hysteresis loop, in 0.4 < P/P0There are bright by < 1.0
Aobvious absorption kick illustrates that there are meso-hole structures in zeolite catalyst；
Fig. 7 is the SEM photograph of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3.As seen from Figure 7, zeolite is in
The spheric granules and surface porosity of existing 1.2~1.4 microns of diameter are porous, illustrate the material of preparation for multilevel structure ZSM-5 boiling
Stone molecular sieve；
Fig. 8 is the pyridine adsorption FTIR spectrogram of multilevel structure ZSM-5 zeolite molecular sieve catalyst made from embodiment 3.It can by Fig. 8
See, catalyst is equally in 1546cm-1、1455cm-1And 1490cm-1There are three characteristic peaks at place, correspond respectively to pyridine adsorption and existSour site, pyridine adsorption, in the eutectoid content in two kinds of sour sites, illustrate urging for preparation in Lewis acid site and pyridine
Agent has needed for the reaction of catalysis methanol propyleneWith Lewis acid site；
Table 4 is the quantitative result of pyridine adsorption FTIR spectrogram after 200 DEG C of desorptions:
Embodiment 4
The experimental provision of the present embodiment is fixed bed micro anti-evaluation device, and reactor is quartz tube reactor, and reactor is by thermoelectricity
Even three sections of temperature controls, center thermometric.Firstly, pressure lower sheeting of the catalyst fines that embodiment 1 is prepared in 10MPa, is protected
Pressure is crushed sieving after 30 seconds, take the particle between 40~60 mesh for being catalyzed reaction.Catalyst after taking 0.2 gram of granulation is packed into stone
In English pipe reactor, catalyst is filled between two silica wools.Then, the nitrogen of 50 ml/mins is continually fed into pipeline,
The temperature of catalyst layer is risen to 550 DEG C simultaneously, pretreatment is down to needed for reaction 460 DEG C of temperature after 2 hours.Next, with
Material benzenemethanol (>=99.5wt%) is squeezed into vaporizing chamber, methanol air speed 1gg by peristaltic pump-1·h-1, reaction pressure is
0.1MPa.Methanol after vaporization is passed into quartz tube reactor under the dilution of nitrogen, and the product after reaction is by gas-chromatography
Instrument is analyzed, and methanol conversion and Propylene Selectivity are finally calculated.
Fig. 9 is methanol conversion and the propylene choosing of multilevel structure ZSM-5 zeolite molecular sieve catalyst measured by embodiment 4
Selecting property with the reaction time variation.As seen from Figure 9, catalyst prepared by the present invention has methanol conversion height, Propylene Selectivity
The advantages that height, long catalytic life.
To sum up, the multilevel structure ZSM-5 zeolite molecular sieve catalyst for preparing not only silica alumina ratio, particle ruler in the present invention
It is very little, Acidity is controllable, and have in preparing propylene from methanol catalysis reaction that methanol conversion is high, Propylene Selectivity is high, the catalysis longevity
The advantages that long is ordered, is expected to realize industrial applications.
Finally it is necessary to explanations: above embodiments are served only for saying technical solution of the present invention in further detail
It is bright, it should not be understood as limiting the scope of the invention, those skilled in the art's above content according to the present invention is made
Some nonessential modifications and adaptations all belong to the scope of protection of the present invention.
Claims (12)
1. a kind of preparation method of multilevel structure ZSM-5 zeolite molecular sieve catalyst characterized by comprising
(1) microcellular structure directing agent solution is instilled in the mixed solution containing silicon source, silicon source and water, after agitated, before obtaining
Drive liquid solution；
(2) it after continuing to stir to get aqueous precursor gel at 30~60 DEG C by gained precursor solution, then through powder dry and processed, obtains
To dry gel powder；
(3) gained dry gel powder is placed in steam condition at 100~180 DEG C after steam aid in treatment 5~48 hours, then
Through drying, primary calcining, sodium form ZSM-5 zeolite molecular sieve is obtained；
(4) by gained sodium form ZSM-5 zeolite molecular sieve after ion exchange, secondary clacining, the multilevel structure ZSM-5 boiling is obtained
Stone molecular sieve catalyst.
2. preparation method according to claim 1, which is characterized in that in step (1), the silicon source, silicon source and water rub
You are than being (100~400): 1:(2000~7000), preferably (200~300): 1:(4000~5000), the microcellular structure
The molar ratio of directed agents and silicon source is (0.07~0.16): 1, preferably (0.1~0.13): 1.
3. preparation method according to claim 1 or 2, which is characterized in that in step (1), the silicon source is positive silicic acid second
At least one of ester, silica nanosphere and mesoporous silica nanospheres, source of aluminium are aluminium isopropoxide and/or inclined aluminium
Sour sodium, the microcellular structure directed agents are tetrapropylammonium hydroxide and/or 4-propyl bromide.
4. preparation method according to any one of claim 1-3, which is characterized in that in step (1), the microcellular structure
The mass fraction of microcellular structure directed agents is 20~30 wt% in directing agent solution, and the rate of the instillation is 0.1~1.4g/ points
Clock, preferably 0.2~0.5 g/ minutes.
5. preparation method described in any one of -4 according to claim 1, which is characterized in that in step (1), the temperature of the stirring
Degree is 20~50 DEG C, and the time is 2~5 hours, and rate is 300~500 revs/min.
6. preparation method according to any one of claims 1-5, which is characterized in that in step (2), the speed of the stirring
Rate is 300~500 revs/min.
7. preparation method according to claim 1 to 6, which is characterized in that in step (2), the temperature of the drying
Degree is 30~60 DEG C, on the basis of 1mol silicon source proportion, until the quality of gained xerogel powder is 100~130 grams.
8. preparation method described in any one of -7 according to claim 1, which is characterized in that it is described it is primary calcining or/and it is secondary
The temperature of calcining is 400~600 DEG C, and preferably 150~550 DEG C, the time is 6~10 hours.
9. preparation method according to claim 1 to 8, which is characterized in that in step (4), the ion exchange
Include:
(1) gained sodium form ZSM-5 zeolite molecular sieve is placed in the solution of the ammonium ion containing 0.5~3mol/L, 60~
At 90 DEG C after heating stirring 3~10 hours, using filter and drying, solid product is obtained；
(2) it repeats step (1) 2~5 time, preferably 2~3 times.
10. preparation method according to claim 9, which is characterized in that the solution of the ammonium ion is to contain ammonium chloride
Or/and the aqueous solution of ammonium nitrate, control every gram of sodium form ZSM-5 zeolite molecular sieve be added the ammonium root containing 0.5~3mol/L from
The volume of the solution of son is 80~120ml.
11. a kind of multilevel structure ZSM-5 zeolite molecular sieve of method preparation according to claim 1 to 10 is urged
Agent.
12. a kind of multilevel structure ZSM-5 zeolite molecular sieve catalyst as claimed in claim 11 is during preparing propylene from methanol
Application.
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