CN107640777A - A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction - Google Patents
A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction Download PDFInfo
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Abstract
The invention discloses a kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction.This method first prepares zeolite molecular sieve crystal seed with organic formwork agent, then by adding a small amount of crystal seed in the Synthesis liquid of zeolite molecular sieve, passes through simple high temperature hydrothermal crystallizing, you can obtains Jie/big-hole zeolite molecular sieve of size uniformity.The product that this method is prepared is formed by 5 500 nm zeolite molecular sieve nanometer rods or nano-particles self assemble, abundant Jie/macropore duct between zeolite molecular sieve nanometer rods or nano particle be present.The method of crystal seed that the present invention uses induction is simple and safe, suitable for ZSM 5, ZSM 11, and the molecular sieve of β types and the types of TS 1.Method proposed by the present invention is simple and safe, and products obtained therefrom purity is high, and crystallinity is high, and Jie/macroporous structure is controllable, is applicable to do separation membrane or the catalyst of catalytic reaction.
Description
Technical field
The present invention relates to zeolite molecular sieve and its preparation field, and in particular to a kind of crystal seed induction prepares big/mesoporous boiling
The method of stone molecular sieve.
Background technology
Molecular sieve is that one kind has crystalline alumino-silicate, and it has the pore passage structure through crystals, and
Pore size is in molecular scale.Molecular sieve has high specific surface area, high heat and hydrothermal stability, the acidity easily adjusted and rule
The advantages that whole skeleton structure, therefore it is widely used in heterogeneous catalysis, ion exchange, many fields such as absorption and separation
（Corma A.,Chem. Rev., 1997, 97, 2373-2420, Cundy CS, Cox PA, Chem. Rev.,
2003, 103, 663-701）.The species of molecular sieve is very more, each not phase of skeleton and pore passage structure of different type molecular sieve
Together.According to the pore size of porous material, IUPAC (IUPAC) is divided into 3 classes：Micropore (<
2 nm), mesoporous (2-50 nm) and macropore (>50 nm).In this 3 class material, though micro-pore zeolite molecular sieve, which has, is easy to modulation
Active sites, preferably heat and hydrothermal stability, these features make it have good adsorbing separation, catalysis, ion exchange etc.
Performance.But the molecule diffusional resistance that the aperture of general micro porous molecular sieve is high all in 1.3 below nm, its micropore seriously limits
Its application in the reaction system for thering is macromolecular to participate in.
Therefore, grinding the person of making internal disorder or usurp proposes many methods to solve the mass transfer problem of conventional microporous zeolite catalyst, such as：(1)
The zeolite molecular sieve of the even more big pore passage structure of 12 yuan of rings is synthesized, including：UTD-1 (Wessels T, Baerlocher C,
McCusker LB, et al.,J. Am. Chem. Soc., 1999,121,6242-6247) and ECR-34
(Strohmaier KG, Vaughan DE, J. Am. Chem. Soc.,2003,125,16035-16039), Yi Jihou
Come be found ITQ-33 (Corma A, D í az-Caba as MJ, Jord á JL, et al.,Nature, 2006,
443, 842-845.)、ITQ-37 (Sun J, Bonneau C, Cantín Á, et al., Nature, 2009, 458,
1154-1157) and ITQ-40 (Corma A, D í az-Caba as M, Jiang J, et al.,PNAS, 2010,
107,13997-14002) etc.；(2) synthesizing ordered mesoporous or large pore material, wherein studying, must to compare more be MCM-41
(Kresge C, Leonowicz M, Roth W, et al., Nature, 1992,359,710-712) and SBA-15
(Zhao D, Feng J, Huo Q, et al., Science, 1998,279,548-552) etc. ordered mesoporous material.It is super
Large micropore molecular sieve and order mesoporous or large pore material are because synthesis template is more expensive, and hydrothermal stability difference and acid intensity are not
The shortcomings of controlling well limits their catalytic applications.Therefore come for the molecular sieve that ZSM-5, ZSM-11, β and TS-1 etc. are specified
Say, scientists attempt with reference to the advantages of both, to synthesize zeolite molecular sieve (such as mesoporous zeolite molecule containing multi-stage artery structure
Sieve) solve this big problem of resistance to mass tranfer.Hierarchical zeolite molecular sieve is not only remained to small molecule reactant or production
The shape selective catalysis performance of thing, while extra mesopore orbit not only contributes to the raising of catalyst mass transfer rate, it is possibility to have effect
Catalysis has the reaction that macromolecular participates in, therefore is considered as very potential catalysis material.And substantial amounts of experimental data is also demonstrate,proved
It is real to be introduced in micro-pore zeolite molecular sieve mesoporous, the mass transfer ability of catalyst can be substantially improved, so as to improve catalyst
Reactivity worth.
At present, what researcher developed has much for the method for preparing mesoporous zeolite molecular sieve, but the most frequently used main
Have template, alkali process method and heat treating process (Tao Y, Kanoh H, Abrams L, et al.,Chem. Rev.,
2006, 106, 896-910; Serrano D, Pizarro P., Chem. Soc. Rev., 2013, 42, 4004-
4035; Möller K, Bein T., Chem. Soc. Rev.2013, 42, 3689-3707).Template mainly with
The materials such as carbon nano-particles, mesoporous carbon, calcium carbonate, organosilan, high molecular polymer and surfactant are template, are passed through
Interaction or self assembly occurs with silicon source or silicon source in it, so as to form the method for mesopore molecular sieve.The mesoporous boiling of Template synthesis
The synthesis step of stone molecular sieve is typically complex, because the synthesis step of some templates is relatively more, causes synthesising mesoporous zeolite
The totle drilling cost of molecular sieve is higher, and the hole that some common templates are formed is non-intercommunicating pore, and it is wrapped in molecule
The crystals of sieve, thus it is little for the help of molecule diffusion.Alkali process method is referred to by carrying out alkali to zeolite molecular sieve
Processing, the silicon atom on its skeleton is optionally removed, produce molecular sieve structure defective bit, it is mesoporous so as to be formed.Though this method
The degree of desiliconization so can be regulated and controled by adjusting the influence factors such as alkali concn, treatment temperature and time during alkali process,
But typically it is suitable only for high-silica zeolite.Heat treating process refers to directly be heat-treated zeolite molecular sieve, makes on micropore hole wall
Atom migrate, a part of micropore expands or restructuring becomes mesoporous, so as to produce containing transgranular mesoporous zeolite molecular sieve.Though
Right heat treating process is simple, cost is low and reproducible, but if treatment temperature is too high or processing time long can not only reduce
The crystallinity of product, while also result in mesoporous cave in.Therefore, develop the low and simple and easy preparation of a cost it is big/Jie
Hole zeolite molecular sieve turns into catalytic field always grinds one of the focus that makes internal disorder or usurp.
The content of the invention
The problem of it is an object of the invention to overcome existing micro-pore zeolite molecular sieve pores inside diffusional resistance big, there is provided Yi Zhongjing
The method for preparing big/mesoporous zeolite molecular sieve of kind induction, this method can adapt to more in very wide range modulation silica alumina ratio
Kind system with molecular sieve for preparing is standby, and obtained product has substantial amounts of mesoporous and macropore, and purity is high, and crystallinity is high, and Jie/macroporous structure is controllable,
It can be used as high performance catalyst and adsorbent.
To achieve the above objectives, the present invention adopts the following technical scheme that.
A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, comprises the following steps：
（1）TPAOH solution, water and silicon source that mass fraction is 5~60% are pressed into TPAOH, water and silicon
The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C
Hour, obtain type ZSM 5 molecular sieve crystal seed；
（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed is brilliant by type ZSM 5 molecular sieve with alkali source, silicon source, silicon source and water
The SiO in silica, alkali source, silicon source in kind2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~200）：
（0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；
（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form
Greatly/mesoporous type ZSM 5 molecular sieve；
（4）By step（3）Obtained big/mesoporous type ZSM 5 molecular sieve NH of sodium form4NO3After solion exchanges, 450~
It is calcined at 650 DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous type ZSM 5 molecular sieve of Hydrogen.
A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, comprises the following steps：
（1）TBAH solution, water and silicon source that mass fraction is 5~60% are pressed into TBAH, water and silicon
The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C
Hour, obtain ZSM-11 type molecular sieve seeds；
（2）By step（1）Obtained ZSM-11 types molecular sieve seed is with alkali source, silicon source, silicon source and water by ZSM-11 type molecular sieves
The SiO in silica, alkali source, silicon source in crystal seed2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~
200）：（0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；
（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form
Greatly/mesoporous ZSM-11 types molecular sieve；
（4）By step（3）Obtained big/mesoporous ZSM-11 types molecular sieve NH of sodium form4NO3After solion exchanges, 450~
It is calcined at 650 DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous ZSM-11 type molecular sieves of Hydrogen.
A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, comprises the following steps：
（1）By mass fraction be 5~60% tetraethyl ammonium hydroxide solution, water, silicon source and silicon source by tetraethyl ammonium hydroxide,
Water, silicon source and silicon source mol ratio are（10~50）：（300~3000）：（0~20）：（50~200）After well mixed, at 25~70 DEG C
Under continue stirring 0~12 hour, then handled 12~72 hours at 70~150 DEG C, obtain beta molecular sieve crystal seed；
（2）By step（1）Obtained beta molecular sieve crystal seed is with alkali source, silicon source, silicon source and water by two in beta molecular sieve crystal seed
SiO in silica, alkali source, silicon source2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~200）：（0~
12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；
（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form
Greatly/mesoporous beta molecular sieve；
（4）By step（3）Obtained big/mesoporous beta molecular sieve NH of sodium form4NO3After solion exchanges, at 450~650 DEG C
Lower roasting, finally give big/mesoporous zeolite molecular sieve, i.e. big/mesoporous beta molecular sieve of Hydrogen.
A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, comprises the following steps：
（1）TPAOH solution, water and silicon source that mass fraction is 5~60% are pressed into TPAOH, water and silicon
The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C
Hour, obtain type ZSM 5 molecular sieve crystal seed；
（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed is brilliant by type ZSM 5 molecular sieve with alkali source, silicon source, titanium source and water
The SiO in silica, alkali source, silicon source in kind2, titanium source and water mol ratio be（0.02~20）：（0~25）：（50~200）：
（0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；
（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form
Greatly/mesoporous TS-1 types molecular sieve；
（4）By step（3）Obtained big/mesoporous TS-1 types molecular sieve NH of sodium form4NO3After solion exchanges, 450~
It is calcined at 650 DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous TS-1 type molecular sieves of Hydrogen.
Preferably, described titanium source be positive tetraethyl titanate, titanium tetrachloride, titanyl sulfate, butyl titanate, positive titanium sulfate and
One or more of mixtures in titanium dioxide.
Preferably, described silicon source is sodium metaaluminate, aluminum oxide, aluminum nitrate, aluminic acid aluminium, aluminium isopropoxide, aluminium chloride and bright
One or more of mixtures in alum.
Preferably, described alkali source is the one or more in sodium hydroxide, potassium hydroxide, lithium hydroxide and strontium hydroxide
Mixture；Described silicon source is the one or more in tetraethyl orthosilicate, waterglass, Ludox, silica and sodium metasilicate
Mixture.
Preferably, step（3）The time of the roasting is 4~24 hours.
Preferably, step（4）The NH4NO3The concentration of solution is 0.2~2mol/L.
Preferably, step（4）The time of the roasting is 4~10 hours.
Preferably, the preparation method of big/mesoporous type ZSM 5 molecular sieve, comprises the following steps：
（1）By the TPAOH solution that mass fraction is 5~60%, deionized water is with silicon source with molar ratio（10~
50）：（300~3000）：（50~200）After mixing 0.5~12 hour, then pre- crystallization 1~144 hour at 80~200 DEG C, obtain
To type ZSM 5 molecular sieve crystal seed；
（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed and alkali source, silicon source, silicon source and deionized water are with molar ratio
（0.02~20）：（0~25）：（50~200）：（0~12.5）：（1000~8000）Mixing 0.1~12 hour so that all raw materials mix
Close homogeneous, be then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 1-48 h at 100~220 DEG C；
（3）Treat step（2）In water heating kettle cooling after, product is taken out, and repeatedly wash after, at 70~120 DEG C dry 8~
36 hours, then it is calcined 4~24 hours at 450~700 DEG C, obtains big/mesoporous type ZSM 5 molecular sieve of sodium form；
（4）Big/mesoporous type ZSM 5 molecular sieve 0.2~2mol/L NH of sodium form that step 4 is obtained4NO3After ion exchange,
It is calcined 4~10 hours at 450~650 DEG C, finally gives big/mesoporous type ZSM 5 molecular sieve of Hydrogen.
Preferably, the preparation method of big/mesoporous ZSM-11 type molecular sieves, comprises the following steps：
（1）By the TBAH solution that mass fraction is 5~60%, deionized water is with silicon source with molar ratio（10~
50）：（300~3000）：（50~200）After mixing 0.5~12 hour, then pre- crystallization 1~144 hour at 80~200 DEG C, obtain
To ZSM-11 type molecular sieve seeds；
（2）By step（1）Obtained ZSM-11 types molecular sieve seed and alkali source, silicon source, silicon source and deionized water are with molar ratio
（0.02~20）：（0~25）：（50~200）：（0~12.5）：（1000~8000）Mixing 0.1~12 hour so that all raw materials mix
Close homogeneous, be then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 1-48 h at 100~220 DEG C.
（3）Treat step（2）In water heating kettle cooling after, product is taken out, and repeatedly wash after, at 70~120 DEG C do
Dry 8~36 hours, then it is calcined 4~24 hours at 450~700 DEG C, obtains big/mesoporous ZSM-11 type molecular sieves of sodium form；
（4）Big/mesoporous ZSM-11 types molecular sieve 0.2~2mol/L NH of sodium form that step 4 is obtained4NO3After ion exchange,
It is calcined 4~10 hours at 450~650 DEG C, finally gives big/mesoporous ZSM-11 type molecular sieves of Hydrogen.
Preferably, the preparation method of big/mesoporous beta molecular sieve, comprises the following steps：
（1）By mass fraction be 5~60% tetraethyl ammonium hydroxide solution, water, silicon source and silicon source with molar ratio（10~50）：
（300~3000）：（0~20）：（50~200）After mixing, continue stirring at 25~70 DEG C 0~12 hour, then 70~150
Handled 12~72 hours at DEG C, obtain beta molecular sieve crystal seed；
（2）By step（1）Obtained beta molecular sieve crystal seed and alkali source, silicon source, silicon source and deionized water are with molar ratio（0.02~
20）：（0~25）：（50~200）：（0~12.5）：（1000~8000）Mixing 0.1~12 hour so that all raw material mixing are homogeneous,
It is then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 1-48 h at 100~220 DEG C.
（3）Treat step（2）In water heating kettle cooling after, product is taken out, and repeatedly wash after, at 70~120 DEG C do
Dry 8~36 hours, then it is calcined 4~24 hours at 450~700 DEG C, obtains big/mesoporous beta molecular sieve of sodium form；
（4）Big/mesoporous beta molecular sieve 0.2~2mol/L NH of sodium form that step 4 is obtained4NO3After ion exchange, 450
It is calcined 4~10 hours at~650 DEG C, finally gives big/mesoporous beta molecular sieve of Hydrogen.
Preferably, the preparation method of big/mesoporous TS-1 type molecular sieves, comprises the following steps：
（1）By the TPAOH solution that mass fraction is 5~60%, deionized water is with silicon source with molar ratio（10~
50）：（300~3000）：（50~200）After mixing 0.5~12 hour, then pre- crystallization 1~144 hour at 80~200 DEG C, obtain
To type ZSM 5 molecular sieve crystal seed；
（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed and alkali source, silicon source, titanium source and deionized water are with molar ratio
（0.02~20）：（0~25）：（50~200）：（0~12.5）：（1000~8000）Mixing 0.1~12 hour so that all raw materials mix
Close homogeneous, be then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 1-48 h at 100~220 DEG C.
（3）Treat step（2）In water heating kettle cooling after, product is taken out, and repeatedly wash after, at 70~120 DEG C do
Dry 8~36 hours, then it is calcined 4~24 hours at 450~700 DEG C, obtains big/mesoporous TS-1 type molecular sieves of sodium form；
（4）Big/mesoporous TS-1 types molecular sieve 0.2~2mol/L NH of sodium form that step 4 is obtained4NO3After ion exchange,
It is calcined 4~10 hours at 450~650 DEG C, finally gives big/mesoporous TS-1 type molecular sieves of Hydrogen.
Big/mesoporous zeolite molecular sieve that above method is prepared, be by 5-500 nm zeolite molecular sieve nanometer rods or
Nano-particles self assemble forms, and their particle size is 50 nm~20 μm, and specific surface area is 200~700 m2/g。
Prepared big/mesoporous zeolite molecular sieve includes big/mesoporous type ZSM 5 molecular sieve, big/mesoporous ZSM-11 type molecules
Sieve, big/mesoporous beta molecular sieve, big/mesoporous Y type molecular sieve, big/mesoporous TS-1 type molecular sieves.Prepare big/mesoporous ZSM-5 types point
The Si/Al of son sieve molar ratio range is 8:1~infinitely great；Prepare the Si/Al of big/mesoporous ZSM-11 type molecular sieves mol ratio
Scope is 8:1~infinitely great；The mol ratio for preparing the Si/Al of big/mesoporous beta molecular sieve is 10:1~infinitely great；Prepare big/Jie
The Si/Ti of hole TS-1 molecular sieves mol ratio is 8：1~infinitely great.
Compared to the prior art the present invention, has the following advantages that：
1）The method for the crystal seed induction that the present invention uses is simple, wide adaptation range, ZSM-5, ZSM-11, β types can be prepared
And the zeolite molecular sieve of TS-1 types.
2）The raw material sources such as silicon source and silicon source used in the present invention are extensive, and do not have mass loss substantially, while flow
Simply, safe operation, the amount of organic formwork agent used in whole flow process are far below conventional template method, therefore to environment substantially not
It can pollute.
3）Zeolite molecular sieve obtained by the present invention is formed by zeolite molecular sieve nanometer rods or nano-particles self assemble,
Containing substantial amounts of mesoporous and macropore between these nanometer rods or nano particle.
Brief description of the drawings
Fig. 1 is big/mesoporous ZSM-5 prepared by the embodiment of the present invention 1 electron scanning micrograph.
Big/mesoporous ZSM-5's that Fig. 2 is prepared for the embodiment of the present invention 1 distinguishes transmission electron microscope photo.
Fig. 3 is big/mesoporous ZSM-5 prepared by the embodiment of the present invention 1 nitrogen adsorption desorption curve map.
Fig. 4 is big/mesoporous ZSM-5 prepared by the embodiment of the present invention 1 BJH graph of pore diameter distribution.
Fig. 5 is big/mesoporous ZSM-5 prepared by the embodiment of the present invention 4 electron scanning micrograph.
Big/mesoporous ZSM-5's that Fig. 6 is prepared for the embodiment of the present invention 4 distinguishes transmission electron microscope photo.
Fig. 7 is big/mesoporous ZSM-11 prepared by the embodiment of the present invention 4 nitrogen adsorption desorption curve map.
Fig. 8 is big/mesoporous ZSM-11 prepared by the embodiment of the present invention 4 BJH graph of pore diameter distribution.
Embodiment
It is further described below in conjunction with specific implementation of the drawings and examples to the present invention, but the embodiment party of the present invention
Formula not limited to this.
Embodiment 1
TPAOH solution and tetraethyl orthosilicate that 51.6 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：25：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 100 DEG C of pre- h of crystallization 48, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：4：2500 mixing
Stirring 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing, at 180 DEG C
The h of crystallization 48.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, dried 12 hours at 110 DEG C,
Then it is calcined 6 hours at 550 DEG C, obtains big/mesoporous type ZSM 5 molecular sieve of sodium form.By big/mesoporous ZSM-5 type molecules of sodium form
Sieve uses 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, finally gives big/mesoporous ZSM-5 type molecules of Hydrogen
Sieve.
Fig. 1 is SEM (SEM) photo of big/mesoporous type ZSM 5 molecular sieve manufactured in the present embodiment, is schemed
2 be big/mesoporous type ZSM 5 molecular sieve manufactured in the present embodiment TEM (transmission electron microscope) photo, Fig. 3 the present embodiment
Big/mesoporous ZSM-5 prepared nitrogen adsorption desorption curve, Fig. 4 big/mesoporous ZSM-5 manufactured in the present embodiment BJH pore-size distributions
Figure.It can be seen that the sample is by size is 20-60 nm, specific surface area is 440 m2/ g zeolite molecular sieve nanometer rods are from group
Dress forms, and substantial amounts of mesoporous and macropore between these nanometer rods be present.
Embodiment 2
TPAOH solution and tetraethyl orthosilicate that 32.3 g mass fractions are 40 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：50：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 100 DEG C of pre- h of crystallization 48, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 0.5：3.5：60：4：2500 mixing
Stirring 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing, at 180 DEG C
The lower h of crystallization 48.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, it is small that 12 are dried at 110 DEG C
When, then it is calcined 6 hours at 550 DEG C, obtains big/mesoporous type ZSM 5 molecular sieve of sodium form.By big/mesoporous ZSM-5 types of sodium form
Molecular sieve 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, finally gives big/mesoporous ZSM-5 types of Hydrogen
Molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous type ZSM 5 molecular sieve manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 1, Fig. 2, and it by size is 20-50 nm that the sample, which is, specific surface area is 455 m2/
G zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 3
TPAOH solution and tetraethyl orthosilicate that 51.6 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：50：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 120 DEG C of pre- h of crystallization 24, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：5.5：60：2：2500 mixing
Stirring 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing, at 180 DEG C
The lower h of crystallization 48.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, it is small that 12 are dried at 110 DEG C
When, then it is calcined 6 hours at 550 DEG C, obtains big/mesoporous type ZSM 5 molecular sieve of sodium form.By big/mesoporous ZSM-5 types of sodium form
Molecular sieve 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, finally gives big/mesoporous ZSM-5 types of Hydrogen
Molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous type ZSM 5 molecular sieve manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 1, Fig. 2, and it by size is 50-80 nm that the sample, which is, specific surface area is 390 m2/
G zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 4
TBAH solution and tetraethyl orthosilicate that 36.3 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=100：30：1000：
400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：4：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
Fig. 5 is SEM (SEM) photo of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment,
Fig. 6 be big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment TEM (transmission electron microscope) photo, this implementation of Fig. 7
Big/mesoporous ZSM-11 prepared by example nitrogen adsorption desorption curve map, Fig. 8 big/mesoporous ZSM-11 manufactured in the present embodiment BJH holes
Footpath distribution map, it can be seen that it by 10-40 nm, specific surface area is 429 m that the sample, which is,2/ g zeolite molecular sieve nanometer rods are from group
Dress forms, and substantial amounts of mesoporous and macropore between these nanometer rods be present.
Embodiment 5
TBAH solution and tetraethyl orthosilicate that 36.3 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=50：30：2000：
200（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：4：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 5, Fig. 6, it can be seen that the sample be by size be 10-40 nm, specific surface area
For 430 m2/ g zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 6
TBAH solution and tetraethyl orthosilicate that 22.7 g mass fractions are 40 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=100：60：1000：
400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：4：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 5, Fig. 6, it can be seen that the sample be by size be 40-80 nm, specific surface area
For 400 m2/ g zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 7
TBAH solution and tetraethyl orthosilicate that 36.3 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=100：30：1000：
400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：2.5：60：6：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 5, Fig. 6, it can be seen that the sample be by size be 10-50 nm, specific surface area
For 420 m2/ g zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 8
TBAH solution and tetraethyl orthosilicate that 36.3 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=100：30：1000：
400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 0.5：3.5：60：4：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 5, Fig. 6, it can be seen that the sample be by size be 10-50 nm, specific surface area
For 420 m2/ g zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 9
TBAH solution and tetraethyl orthosilicate that 36.3 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=100：30：1000：
400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- crystallization 48
H, obtain ZSM-11 type molecular sieve seeds.Then by above-mentioned ZSM-11 types molecular sieve seed（Calculated based on silica）With
NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 0.25：3.5：60：4：
2500 mix 1 hour so that and all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing,
The h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, at 110 DEG C
Dry 12 hours, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous ZSM-11 type molecular sieves of sodium form.By sodium form it is big/be situated between
Hole ZSM-11 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous ZSM-11 types molecular sieve.
SEM (SEM) photos and TEM of big/mesoporous ZSM-11 type molecular sieves manufactured in the present embodiment
(transmission electron microscope) photo is similar to Fig. 5, Fig. 6, it can be seen that the sample be by size be 20-40 nm, specific surface area
For 430 m2/ g zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 10
By 30 g mass fractions be 25 % tetraethyl ammonium hydroxide solution, aluminum nitrate and tetraethyl orthosilicate be added to containing go from
2 h are stirred in the round-bottomed flask of sub- water so that the molar ratio of mixed liquor is SiO2： Al(NO3)3.9H2O： TBPOH： H2O：
EtOH=100：4：30：1000：400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, then the mixed liquor is added
Heat obtains beta molecular sieve crystal seed to 120 DEG C of pre- h of crystallization 48.Then by above-mentioned beta molecular sieve crystal seed（Based on silica come
Calculate）With NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：
3.5：60：4：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydro-thermal of sealing
In crystallizing kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing,
Dried 12 hours at 110 DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous beta molecular sieve of sodium form.By sodium form it is big/
Mesoporous beta molecular sieve 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, it is big/mesoporous finally gives Hydrogen
Beta molecular sieve.
Big/mesoporous beta molecular sieve manufactured in the present embodiment be by size be 10-70 nm, specific surface area be 550 m2/g
The self assembly of zeolite molecular sieve nanometer rods into-.
Embodiment 11
Tetraethyl ammonium hydroxide solution and tetraethyl orthosilicate that 30 g mass fractions are 25 % are added to containing deionized water
2 h are stirred in round-bottomed flask so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=100：30：1000：400
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 120 DEG C of pre- h of crystallization 48, obtained
To beta molecular sieve crystal seed.Then by above-mentioned beta molecular sieve crystal seed（Calculated based on silica）With NaOH, 29 g 40wt%
Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：4：2500 mixings 1 are small
When so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 48 at 180 DEG C
h.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, dried 12 hours at 110 DEG C, Ran Hou
It is calcined 6 hours at 550 DEG C, obtains big/mesoporous beta molecular sieve of sodium form.By big/mesoporous beta molecular sieve 1mol/L of sodium form
NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, finally gives big/mesoporous beta molecular sieve of Hydrogen.
It by size is 20-50 nm that big/mesoporous beta molecular sieve manufactured in the present embodiment, which is, specific surface area is 610 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 12
Tetraethyl ammonium hydroxide solution and tetraethyl orthosilicate that 30 g mass fractions are 25 % are added to containing deionized water
2 h are stirred in round-bottomed flask so that the molar ratio of mixed liquor is SiO2： TBPOH： H2O： EtOH=50：30：1000：200
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 110 DEG C of pre- h of crystallization 48, obtained
To beta molecular sieve crystal seed.Then by above-mentioned beta molecular sieve crystal seed（Calculated based on silica）With NaOH, 29 g 40wt%
Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 2.5：3.5：60：6：2500 mixings 1 are small
When so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing kettle of sealing, the crystallization 48 at 180 DEG C
h.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, dried 12 hours at 110 DEG C, Ran Hou
It is calcined 6 hours at 550 DEG C, obtains big/mesoporous beta molecular sieve of sodium form.By big/mesoporous beta molecular sieve 1mol/L of sodium form
NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, finally gives big/mesoporous beta molecular sieve of Hydrogen.
It by size is 40-80 nm that big/mesoporous beta molecular sieve manufactured in the present embodiment, which is, specific surface area is 540 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 13
By 30 g mass fractions be 25 % tetraethyl ammonium hydroxide solution, aluminum nitrate and tetraethyl orthosilicate be added to containing go from
2 h are stirred in the round-bottomed flask of sub- water so that the molar ratio of mixed liquor is SiO2： Al(NO3)3.9H2O： TBPOH： H2O：
EtOH=100：4：30：1000：400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, then the mixed liquor is added
Heat obtains beta molecular sieve crystal seed to 120 DEG C of pre- h of crystallization 48.Then by above-mentioned beta molecular sieve crystal seed（Based on silica come
Calculate）With NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 0.5：
3.5：60：4：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydro-thermal of sealing
In crystallizing kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing,
Dried 12 hours at 110 DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous beta molecular sieve of sodium form.By sodium form it is big/
Mesoporous beta molecular sieve 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, it is big/mesoporous finally gives Hydrogen
Beta molecular sieve.
It by size is 10-30 nm that big/mesoporous beta molecular sieve manufactured in the present embodiment, which is, specific surface area is 570 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 14
By 30 g mass fractions be 25 % tetraethyl ammonium hydroxide solution, aluminum nitrate and tetraethyl orthosilicate be added to containing go from
2 h are stirred in the round-bottomed flask of sub- water so that the molar ratio of mixed liquor is SiO2： Al(NO3)3.9H2O： TBPOH： H2O：
EtOH=100：4：30：1000：400（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, then the mixed liquor is added
Heat obtains beta molecular sieve crystal seed to 120 DEG C of pre- h of crystallization 48.Then by above-mentioned beta molecular sieve crystal seed（Based on silica come
Calculate）With NaOH, 29 g 40wt% Ludox（Based on SiO2To calculate）, NaAlO2With deionized water with mol ratio 0.25：
3.5：60：4：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydro-thermal of sealing
In crystallizing kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing,
Dried 12 hours at 110 DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous beta molecular sieve of sodium form.By sodium form it is big/
Mesoporous beta molecular sieve 1mol/L NH4NO3After ion exchange, it is calcined 6 hours at 550 DEG C, it is big/mesoporous finally gives Hydrogen
Beta molecular sieve.
It by size is 40-60 nm that big/mesoporous beta molecular sieve manufactured in the present embodiment, which is, specific surface area is 620 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 15
TPAOH solution and tetraethyl orthosilicate that 51.6 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：25：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 100 DEG C of pre- h of crystallization 48, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, C8H20O4Ti（Positive tetraethyl titanate）With deionized water with mol ratio 2.5：3.5：
60：4：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing of sealing
In kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, 110
Dried 12 hours at DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous TS-1 type molecular sieves of sodium form.By sodium form it is big/
Mesoporous TS-1 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous TS-1 types molecular sieve.
SEM (SEM) photos of big/mesoporous TS-1 type molecular sieves manufactured in the present embodiment are (saturating with TEM
Penetrate electron microscope) photo is similar to Fig. 1, Fig. 2, and it by size is 10-50 nm that the sample, which is, specific surface area is 440 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 16
TPAOH solution and tetraethyl orthosilicate that 51.6 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：25：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 100 DEG C of pre- h of crystallization 48, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, C8H20O4Ti（Positive tetraethyl titanate）With deionized water with mol ratio 0.5：3.5：
60：6：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing of sealing
In kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, 110
Dried 12 hours at DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous TS-1 type molecular sieves of sodium form.By sodium form it is big/
Mesoporous TS-1 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous TS-1 types molecular sieve.
SEM (SEM) photos of big/mesoporous TS-1 type molecular sieves manufactured in the present embodiment are (saturating with TEM
Penetrate electron microscope) photo is similar to Fig. 1, Fig. 2, and it by size is 20-60 nm that the sample, which is, specific surface area is 390 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Embodiment 17
TPAOH solution and tetraethyl orthosilicate that 51.6 g mass fractions are 25 % are added to containing deionized water
Round-bottomed flask in stir 2 h so that the molar ratio of mixed liquor is SiO2： TPAOH： H2O： EtOH=92：50：900：368
（Hydrolysis of the wherein EtOH from tetraethyl orthosilicate and water）, the mixed liquor is then heated to 100 DEG C of pre- h of crystallization 48, obtained
To type ZSM 5 molecular sieve crystal seed.Then by above-mentioned type ZSM 5 molecular sieve crystal seed（Calculated based on silica）With NaOH, 29
G 40wt% Ludox（Based on SiO2To calculate）, C8H20O4Ti（Positive tetraethyl titanate）With deionized water with mol ratio 1：3.5：
60：4：2500 mix 1 hour so that all raw material mixing are homogeneous, are then added into the high pressure hydrothermal crystallizing of sealing
In kettle, the h of crystallization 48 at 180 DEG C.After water heating kettle is cooled to normal temperature, product is taken out and filtered, and repeatedly after washing, 110
Dried 12 hours at DEG C, be then calcined 6 hours at 550 DEG C, obtain big/mesoporous TS-1 type molecular sieves of sodium form.By sodium form it is big/
Mesoporous TS-1 types molecular sieve 1mol/L NH4NO3After ion exchange, be calcined 6 hours at 550 DEG C, finally give Hydrogen it is big/
Mesoporous TS-1 types molecular sieve.
SEM (SEM) photos of big/mesoporous TS-1 type molecular sieves manufactured in the present embodiment are (saturating with TEM
Penetrate electron microscope) photo is similar to Fig. 1, Fig. 2, and it by size is 20-40 nm that the sample, which is, specific surface area is 450 m2/ g's
Zeolite molecular sieve nanometer rods self assembly forms.
Above-described embodiment is used for illustrating the present invention, rather than limits the invention, the present invention spirit and
In scope of the claims, to any modifications and changes of the invention made, protection scope of the present invention is both fallen within.
Claims (10)
- A kind of 1. method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, it is characterised in that comprise the following steps：（1）TPAOH solution, water and silicon source that mass fraction is 5~60% are pressed into TPAOH, water and silicon The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C Hour, obtain type ZSM 5 molecular sieve crystal seed；（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed is brilliant by type ZSM 5 molecular sieve with alkali source, silicon source, silicon source and water The SiO in silica, alkali source, silicon source in kind2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~200）： （0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form Greatly/mesoporous type ZSM 5 molecular sieve；（4）By step（3）Obtained big/mesoporous type ZSM 5 molecular sieve NH of sodium form4NO3After solion exchanges, 450~ It is calcined at 650 DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous type ZSM 5 molecular sieve of Hydrogen.
- A kind of 2. method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, it is characterised in that comprise the following steps：（1）TBAH solution, water and silicon source that mass fraction is 5~60% are pressed into TBAH, water and silicon The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C Hour, obtain ZSM-11 type molecular sieve seeds；（2）By step（1）Obtained ZSM-11 types molecular sieve seed is with alkali source, silicon source, silicon source and water by ZSM-11 type molecular sieves The SiO in silica, alkali source, silicon source in crystal seed2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~ 200）：（0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form Greatly/mesoporous ZSM-11 types molecular sieve；（4）By step（3）Obtained big/mesoporous ZSM-11 types molecular sieve NH of sodium form4NO3After solion exchanges, 450~ It is calcined at 650 DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous ZSM-11 type molecular sieves of Hydrogen.
- A kind of 3. method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, it is characterised in that comprise the following steps：（1）By mass fraction be 5~60% tetraethyl ammonium hydroxide solution, water, silicon source and silicon source by tetraethyl ammonium hydroxide, The mol ratio of water, silicon source and silicon source is（10~50）：（300~3000）：（0~20）：（50~200）After well mixed, 25~70 Continue stirring at DEG C 0~12 hour, then handled 12~72 hours at 70~150 DEG C, obtain beta molecular sieve crystal seed；（2）By step（1）Obtained beta molecular sieve crystal seed is with alkali source, silicon source, silicon source and water by two in beta molecular sieve crystal seed SiO in silica, alkali source, silicon source2, silicon source and water mol ratio be（0.02~20）：（0~25）：（50~200）：（0~ 12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form Greatly/mesoporous beta molecular sieve；（4）By step（3）Obtained big/mesoporous beta molecular sieve NH of sodium form4NO3After solion exchanges, at 450~650 DEG C Lower roasting, finally give big/mesoporous zeolite molecular sieve, i.e. big/mesoporous beta molecular sieve of Hydrogen.
- A kind of 4. method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction, it is characterised in that comprise the following steps：（1）TPAOH solution, water and silicon source that mass fraction is 5~60% are pressed into TPAOH, water and silicon The mol ratio in source is（10~50）：（300~3000）：（50~200）After well mixed, then the pre- crystallization 1~144 at 80~200 DEG C Hour, obtain type ZSM 5 molecular sieve crystal seed；（2）By step（1）Obtained type ZSM 5 molecular sieve crystal seed is brilliant by type ZSM 5 molecular sieve with alkali source, silicon source, titanium source and water The SiO in silica, alkali source, silicon source in kind2, titanium source and water mol ratio be（0.02~20）：（0~25）：（50~200）： （0~12.5）：（1000~8000）It is well mixed, then the crystallization 1-48 h at 100~220 DEG C；（3）Treat step（2）In crystallization product cooling after, wash, dry, be then calcined at 450~700 DEG C, obtain sodium form Greatly/mesoporous TS-1 types molecular sieve；（4）By step（3）Obtained big/mesoporous TS-1 types molecular sieve NH of sodium form4NO3After solion exchanges, 450~650 It is calcined at DEG C, finally gives big/mesoporous zeolite molecular sieve, i.e. big/mesoporous TS-1 type molecular sieves of Hydrogen.
- 5. according to the method for claim 4, it is characterised in that described titanium source is positive tetraethyl titanate, titanium tetrachloride, sulfuric acid One or more of mixtures in oxygen titanium, butyl titanate, positive titanium sulfate and titanium dioxide.
- 6. according to the method described in claim any one of 1-3, it is characterised in that described silicon source be sodium metaaluminate, aluminum oxide, One or more of mixtures in aluminum nitrate, aluminic acid aluminium, aluminium isopropoxide, aluminium chloride and alum.
- 7. according to the method described in claim any one of 1-4, it is characterised in that described alkali source is sodium hydroxide, hydroxide One or more of mixtures in potassium, lithium hydroxide and strontium hydroxide；Described silicon source is tetraethyl orthosilicate, waterglass, silicon One or more of mixtures in colloidal sol, silica and sodium metasilicate.
- 8. according to the method described in claim any one of 1-4, it is characterised in that step（3）The time of the roasting is 4~24 Hour.
- 9. according to the method described in claim any one of 1-4, it is characterised in that step（4）The NH4NO3The concentration of solution is 0.2~2mol/L.
- 10. according to the method described in claim any one of 1-4, it is characterised in that step（4）The time of the roasting be 4~ 10 hours.
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| CN109304141A (en) * | 2018-12-13 | 2019-02-05 | 吉林大学 | It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant |
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| CN112723377A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Preparation method and application of titanium-silicon molecular sieve containing mesopores |
| CN111013531A (en) * | 2019-11-15 | 2020-04-17 | 石家庄汉创环保科技有限公司 | Preparation method of titanium dioxide zeolite molecular sieve for adsorbing volatile organic pollutants |
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| CN115196650A (en) * | 2021-04-09 | 2022-10-18 | 中国石油化工股份有限公司 | Metal modified mesoporous ZSM-5 molecular sieve and preparation method thereof |
| CN116099570A (en) * | 2021-11-10 | 2023-05-12 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN116099570B (en) * | 2021-11-10 | 2024-10-01 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
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| CN116174023B (en) * | 2021-11-29 | 2024-08-09 | 中国石油天然气股份有限公司 | Preparation method of high-yield high-octane gasoline additive |
| CN116119681A (en) * | 2023-01-11 | 2023-05-16 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
| CN116119681B (en) * | 2023-01-11 | 2024-08-02 | 中国石油大学(华东) | Preparation method for rapidly synthesizing ZSM-5 molecular sieve by inducer |
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