CN106517239B - A kind of pillared layered modenite and preparation method thereof - Google Patents
A kind of pillared layered modenite and preparation method thereof Download PDFInfo
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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Abstract
The invention discloses a kind of pillared layered modenites and preparation method thereof, it using silicon dioxide gel as silicon source, sodium metaaluminate is silicon source that the pillared layered modenite, which is, hexamethylene imine is template, first use the swollen stratiform modenite of dynamic autoclaved technology method synthesis of soluble, then the swellable stratiform modenite of gained with cetyl polyoxyethylene groups cetyl ammonium bromide is swollen, then the stratiform modenite after swelling and ethyl orthosilicate reaction is subjected to pillared obtain.The present invention realizes a kind of preparation of the pillared layered modenite of new structure, it is swollen and pillared process carries out in a mild condition, destructions of the high pH of high temperature to framework of molecular sieve and acidic site is avoided, and sweller used is cheap and easy to get and has been carried out industrialized production.
Description
Technical field
The invention belongs to molecular sieves and porous material technical field, and in particular to a kind of pillared layered modenite and its system
Preparation Method, preparation and its swelling and pillared method including swellable stratiform modenite.
Background technology
Modenite is a kind typical micro porous molecular sieve material, has uniform pore passage structure, suitable acid and good
Good hydrothermal stability, it has also become important petrochemical industry catalysis material, especially in alkylation, hydroisomerization, dewaxing etc.
In reaction.However, modenite is by interconnected twelve-ring duct (0.67nm × 0.70nm) and octatomic ring duct
(0.34nm × 0.48nm) is formed, and since octatomic ring duct is smaller, most of molecules hardly enter, and modenite is typically considered to
With one-dimensional channels system, diffusion limitation is easy to cause.Therefore, in order to which the diffusion of traditional modenite is overcome to limit, Ke Yi
Mesoporous, molecular screen material of the formation with micro--mesoporous hierarchical porous structure, so as to effectively reduce product is introduced in micropore modenite
Diffusion limitation, reduce carbon distribution, improve service life of catalyst.
Document is analyzed and summarized it can be found that the method for preparing multistage porous molecular sieve is mainly the following：(1) it is right
Micro porous molecular sieve carries out alkali or/and acid treatment, and the silicon in skeleton and aluminium are dissolved out, random mesoporous so as to be formed；To micropore
Molecular sieve carries out alkali process, inevitably changes the amount and its intensity distribution in acid site, and be difficult to control mesoporous structure,
Size and its distribution.(2) soft template is oriented to hydro-thermal method and directly synthesizes.Chinese patent ZL201010116302.7 is reported silicon
Crystallization is made after source, silicon source, organic amine structure directing agent (SDA), the mesoporous template of macromolecule and water mix according to a certain percentage
A kind of mesoporous mordenite molecular sieve containing micropore-mesopore composite construction.This method is equally difficult to control mesoporous structure
And distribution.It is template that Chinese patent ZL201210125572.3, which is reported using cetyl trimethyl p-methyl benzenesulfonic acid ammonium salt,
A kind of laminar nano mordenite molecular sieve is prepared in agent, but from XRD results it can be found that the modenite of the method synthesis
Crystallinity is than relatively low.
In addition to above two main means, the important of micro--Jie's multi-stage porous ordered structure molecular sieve is constructed as a kind of
Method, the pillared and stripping of lamellar zeolite cause the extensive concern of domestic and foreign scholars.With MCM-22 molecular sieve precursors
Exemplified by (MCM-22 (P)), it is the stratified material formed by MWW type nano molecular sieve lamella ordered arrangements, passes through swelling and column
Support can prepare the MCM-36 molecular sieves with micro--Jie's multi-stage porous ordered structure.Ryoo etc. (J.Am.Chem.Soc.2010,
132,4169-4177) ZSM-5 nano molecular sieve lamellas have been synthesized using the method for design template agent, then using interlevel oxidation
The pillared method of object equally obtains the pillared ZSM-5 molecular sieve with micro--meso-hole structure.Therefore, exploitation synthesizes other topologys
The layer structure molecular sieve of structure, and the molecular sieve with micro--meso-hole structure can be obtained with pillared method by being swollen,
There is important value for bulky molecular catalysis.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of pillared mercerising boiling with micro--mesoporous hierarchical porous structure
Stone and preparation method thereof.
Technical solution is that the pillared layered modenite is prepared by following methods used by solving above-mentioned technical problem
It arrives：
1st, swellable stratiform modenite is prepared
According to molar ratio SiO2/Al2O3=20~200, OH/SiO2=0.2~0.5, Na/SiO2=0.2~0.5, HMI/
SiO2=0.4~0.7, H2O/SiO2=10~50, wherein HMI represents hexamethylene imine, weighs raw material sodium metaaluminate, hydrogen-oxygen
Change sodium, silicon dioxide gel, hexamethylene imine, deionized water, sodium hydroxide, sodium metaaluminate are dissolved separately in deionized water
Middle wiring solution-forming sequentially adds silicon dioxide gel, hexamethylene imine into the sodium metaaluminate aqueous solution prepared, then adds dropwise
Enter the sodium hydrate aqueous solution prepared, then gained mixture is transferred to containing polytetrafluoroethyl-ne by stirring at normal temperature 20~30 minutes
In the hydrothermal reaction kettle of alkene liner, and hydrothermal reaction kettle is put into homogeneous reactor, the rotating speed for setting homogeneous reactor is 30
It~100 revs/min, is reacted at 100~200 DEG C 7~10 days, after reaction, takes out hydrothermal reaction kettle and be put into cold water suddenly
It is cold, obtain swellable stratiform modenite suspension.
2nd, the swelling of stratiform modenite
Cetyl polyoxyethylene groups cetyl is added in the swellable stratiform modenite suspension obtained to step 1
Ammonium bromide, quality-volume of cetyl polyoxyethylene groups cetyl ammonium bromide and swellable stratiform modenite suspension
Than for 1g:1~15mL when stirring at normal temperature 16~32 is small, is then centrifuged, and washing when drying at room temperature 24~48 is small, obtains
Stratiform modenite after swelling.
3rd, pillared layered modenite is prepared
Stratiform modenite and ethyl orthosilicate after step 2 is swollen are 1 in mass ratio:3~8 are uniformly mixed, in nitrogen
Under gas atmosphere protection, when 80~100 DEG C of stirrings 3~8 are small, centrifuge, when drying at room temperature 24~48 is small, obtain pillared layered silk
The intermediate is placed in tube furnace by geolyte intermediate, is warming up in a nitrogen atmosphere with 1~5 DEG C/min of heating rate
It 500~600 DEG C, when constant temperature calcining 5~8 is small, is subsequently placed in Muffle furnace and is warming up to 500 with 1~5 DEG C/min of heating rate
~600 DEG C, when constant temperature calcining 5~8 is small, obtain pillared layered modenite.
In above-mentioned steps 1, preferably according to molar ratio SiO2/Al2O3=30~100, OH/SiO2=0.3~0.4, Na/SiO2
=0.3~0.4, HMI/SiO2=0.5~0.6, H2O/SiO2=30~40, weigh raw material sodium metaaluminate, sodium hydroxide, dioxy
SiClx colloidal sol, hexamethylene imine, deionized water.
In above-mentioned steps 1, the rotating speed of homogeneous reactor is further preferably set for 50~60 revs/min, 140~160
It is reacted 7~10 days under the conditions of DEG C.
In above-mentioned steps 2, preferably cetyl polyoxyethylene groups cetyl ammonium bromide and swellable stratiform modenite
Quality-volume ratio of suspension is 1g:1~2mL.
In above-mentioned steps 3, the mass ratio of stratiform modenite and ethyl orthosilicate after being preferably swollen is 1:5.
In above-mentioned steps 3, further preferably pillared layered modenite intermediate is placed in tube furnace, in nitrogen atmosphere
Under with 2~3 DEG C/min of heating rate be warming up to 550 DEG C, when constant temperature calcining 6 is small, be subsequently placed in Muffle furnace with 2~3 DEG C/
The heating rate of minute is warming up to 550 DEG C, when constant temperature calcining 6 is small.
The degree of polymerization of polyoxyethylene groups is 10 in above-mentioned cetyl polyoxyethylene groups cetyl ammonium bromide.
For the present invention using silicon dioxide gel as silicon source, sodium metaaluminate is silicon source, and hexamethylene imine (HMI) is template,
First using the swollen stratiform modenite of dynamic autoclaved technology method synthesis of soluble, then by the swellable stratiform modenite of gained with 16
Alkyl polyoxyethylene base cetyl ammonium bromide (CPAB) is swollen, then by the stratiform modenite after swelling and positive silicic acid second
Ester reaction carries out pillared processing and obtains pillared layered modenite.The present invention realizes a kind of system of the pillared zeolite of new structure
Standby, i.e., the preparation of pillared layered modenite, swelling and pillared process carry out in a mild condition, and it is pH pairs high to avoid high temperature
The destruction of framework of molecular sieve and acidic site, and sweller used is cheap and easy to get and has been carried out industrialized production, is suitble to pillared layer
The mass production of shape modenite.
Description of the drawings
Fig. 1 is the XRD diagram of the stratiform modenite and pillared layered modenite after the swelling that embodiment 1 obtains.
The N for the pillared layered modenite that Fig. 2 is modenite and embodiment 1 obtains2- Adsorption and desorption isotherms figure.
Fig. 3 be it is different swelling solvent swells after modenite XRD diagram.
Specific embodiment
The present invention is described in more detail with reference to the accompanying drawings and examples, but protection scope of the present invention is not limited only to
These embodiments.
Embodiment 1
1st, swellable stratiform modenite is prepared
According to molar ratio SiO2/Al2O3=30, OH/SiO2=0.3, Na/SiO2=0.3, HMI/SiO2=0.5, H2O/
SiO2=40, weigh raw material sodium metaaluminate 0.28g, sodium hydroxide 0.42g, silicon dioxide gel 5.05g, HMI1.69g, go from
Sub- water 24.10mL, sodium hydroxide is dissolved in 8.04mL deionized waters and is configured to sodium hydrate aqueous solution, and sodium metaaluminate is molten
Solution is configured to sodium metaaluminate aqueous solution in 16.06mL deionized waters；Two are sequentially added into the sodium metaaluminate aqueous solution prepared
Silica sol, HMI, then the sodium hydrate aqueous solution prepared is added dropwise, stirring at normal temperature 30 minutes, then by gained mixture
It is transferred in the hydrothermal reaction kettle containing polytetrafluoroethylliner liner, and hydrothermal reaction kettle is put into homogeneous reactor, set equal
The rotating speed of phase reaction device is 60 revs/min, is reacted under the conditions of 150 DEG C 7 days, after reaction, takes out hydrothermal reaction kettle and be put into
It is quenched in cold water, obtains the suspension of swellable stratiform modenite.
2nd, the swelling of stratiform modenite
The suspension 4mL for the swellable stratiform modenite that step 1 obtains is taken, and adds in 3.75g cetyls thereto
Polyoxyethylene groups cetyl ammonium bromide, when stirring at normal temperature 16 is small, centrifuges, and washing when drying at room temperature 24 is small, is swollen
Stratiform modenite afterwards.It is characterized using X-ray diffractometer, the result is shown in Figure 1.As seen from the figure, the stratiform after swelling
Modenite shows apparent (001) and (002) characteristic diffraction peak, and corresponding interlamellar spacing is 3.50nm.
3rd, pillared layered modenite is prepared
Stratiform modenite after 1.0g is swollen is uniformly mixed with 5.0g ethyl orthosilicates, under nitrogen atmosphere protection,
When 80 DEG C of stirrings 5 are small, centrifuge, when drying at room temperature 48 is small, obtains pillared layered modenite intermediate, which is put
In tube furnace, 550 DEG C are warming up to 2 DEG C/min of heating rate in a nitrogen atmosphere, when constant temperature calcining 6 is small, is subsequently placed in
550 DEG C, when constant temperature calcining 6 is small are warming up to 2 DEG C/min of heating rate in air atmosphere in Muffle furnace, obtains pillared layer
Shape modenite, interlamellar spacing are 2.50nm (see Fig. 1).The present embodiment synthesizes it can be seen from the BET characterization results of Fig. 2
Pillared layered modenite is compared with traditional micropore modenite, and in low-pressure area, there is similar adsorption isotherm, explanations
Pillared layered modenite remains the microcellular structure of traditional micropore modenite；There is the quick of adsorbance in mesohigh area
Increase, this is mainly due to the pillared processing to stratiform modenite so that generate certain gap between layers and form Jie
Pore structure；And the pillared layered modenite specific surface area of the present embodiment synthesis is 595m2/ g, pore volume 0.33m3/ g, relatively
Traditional modenite is significantly improved, and this is mainly due to the meso-hole structures that pillared layered modenite interlayer is formed.
Embodiment 2
1st, swellable stratiform modenite is prepared
According to SiO2/Al2O3Molar ratio is 50, OH/SiO2Molar ratio is 0.3, Na/SiO2Molar ratio is 0.3, HMI/SiO2
Molar ratio is 0.6, H2O/SiO2Molar ratio is 40, weighs raw material sodium metaaluminate 0.16g, sodium hydroxide 0.41g, titanium dioxide respectively
Ludox 4.98g, HMI 1.99g, deionized water 23.89mL, sodium hydroxide is dissolved in 7.99mL deionized waters and is configured to
Sodium metaaluminate is dissolved in 15.9mL deionized waters and is configured to sodium metaaluminate aqueous solution by sodium hydrate aqueous solution；To what is prepared
Silicon dioxide gel, HMI are sequentially added in sodium metaaluminate aqueous solution, then the sodium hydrate aqueous solution prepared, room temperature is added dropwise
Gained mixture, is then transferred in the hydrothermal reaction kettle containing polytetrafluoroethylliner liner by stirring 30 minutes, and hydro-thermal is anti-
Kettle is answered to be put into homogeneous reactor, the rotating speed of homogeneous reactor is set for 60 revs/min, reacts 10 days under the conditions of 140 DEG C, instead
After answering, taking-up hydrothermal reaction kettle, which is put into cold water, to be quenched, and obtains the suspension of swellable stratiform modenite.
2nd, the swelling of stratiform modenite
The suspension 8mL for the swellable stratiform modenite that step 1 obtains is taken, and adds in 7.5g cetyls thereto and gathers
Oxyethylene group cetyl ammonium bromide when stirring at normal temperature 24 is small, centrifuges, washing, when drying at room temperature 48 is small, after obtaining swelling
Stratiform modenite, interlamellar spacing 3.70nm.
3rd, pillared layered modenite is prepared
Stratiform modenite after 1.0g is swollen is uniformly mixed with 5.0g ethyl orthosilicates, under nitrogen atmosphere protection,
When 80 DEG C of stirrings 5 are small, centrifuge, when drying at room temperature 48 is small, obtain pillared layered modenite intermediate, it then will be among this
Body is placed in tube furnace, is warming up to 550 DEG C in a nitrogen atmosphere with 2 DEG C/min of heating rate, when constant temperature calcining 6 is small, finally
550 DEG C, when constant temperature calcining 6 is small are warming up to 2 DEG C/min of heating rate in Muffle furnace, obtains pillared layered modenite,
Its interlamellar spacing is 2.50nm.
Embodiment 3
1st, swellable stratiform modenite is prepared
According to SiO2/Al2O3Molar ratio is 100, OH/SiO2Molar ratio is 0.4, Na/SiO2Molar ratio is 0.4, HMI/
SiO2Molar ratio is 0.5, H2O/SiO2Molar ratio is 30, weighs raw material sodium metaaluminate 0.1g, sodium hydroxide 0.7g, dioxy respectively
SiClx colloidal sol 6.32g, HMI 2.11g, deionized water 22.72mL, sodium hydroxide is dissolved in 7.57mL deionized waters and is prepared
Into sodium hydrate aqueous solution, sodium metaaluminate is dissolved in 15.15mL deionized waters and is configured to sodium metaaluminate aqueous solution；To preparing
Sodium metaaluminate aqueous solution in sequentially add silicon dioxide gel, HMI, then the sodium hydrate aqueous solution prepared is added dropwise, often
Gained mixture, is then transferred in the hydrothermal reaction kettle containing polytetrafluoroethylliner liner by temperature stirring 30 minutes, and by hydro-thermal
Reaction kettle is put into homogeneous reactor, and the rotating speed of homogeneous reactor is set to be reacted 8 days under the conditions of 160 DEG C for 50 revs/min,
After reaction, taking-up hydrothermal reaction kettle, which is put into cold water, is quenched, and obtains the suspension of swellable stratiform modenite.
2nd, the swelling of stratiform modenite
The suspension 8mL for the swellable stratiform modenite that step 1 obtains is taken, and adds in 7.5g cetyls thereto and gathers
Oxyethylene group cetyl ammonium bromide when stirring at normal temperature 24 is small, centrifuges, washing, when drying at room temperature 48 is small, after obtaining swelling
Stratiform modenite, interlamellar spacing 3.80nm.
3rd, pillared layered modenite is prepared
Stratiform modenite after 1.0g is swollen is uniformly mixed with 3.0g ethyl orthosilicates, under nitrogen atmosphere protection,
When 80 DEG C of stirrings 5 are small, centrifuge, when drying at room temperature 48 is small, obtain pillared layered modenite intermediate, it then will be among this
Body is placed in tube furnace, is warming up to 500 DEG C in a nitrogen atmosphere with 2 DEG C/min of heating rate, when constant temperature calcining 8 is small, finally
500 DEG C, when constant temperature calcining 8 is small are warming up to 2 DEG C/min of heating rate in Muffle furnace, obtains pillared layered modenite,
Its interlamellar spacing is 2.60nm.
Embodiment 4
1st, swellable stratiform modenite is prepared
According to SiO2/Al2O3Molar ratio is 200, OH/SiO2Molar ratio is 0.5, Na/SiO2Molar ratio is 0.5, HMI/
SiO2Molar ratio is 0.7, H2O/SiO2Molar ratio is 50, weighs raw material sodium metaaluminate 0.03g, sodium hydroxide 0.57g, two respectively
Silica sol 4.11g, HMI 1.92g, deionized water 24.64mL, sodium hydroxide is dissolved in 4.11mL deionized waters and is matched somebody with somebody
Sodium hydrate aqueous solution is made, sodium metaaluminate is dissolved in 20.53mL deionized waters and is configured to sodium metaaluminate aqueous solution；To with
Silicon dioxide gel, HMI are sequentially added in good sodium metaaluminate aqueous solution, then the sodium hydrate aqueous solution prepared is added dropwise,
Gained mixture, is then transferred in the hydrothermal reaction kettle containing polytetrafluoroethylliner liner by stirring at normal temperature 30 minutes, and by water
Thermal response kettle is put into homogeneous reactor, and the rotating speed of homogeneous reactor is set to react 7 under the conditions of 150 DEG C for 50 revs/min
My god, after reaction, taking-up hydrothermal reaction kettle, which is put into cold water, to be quenched, and obtains the suspension of swellable stratiform modenite.
2nd, the swelling of stratiform modenite
The suspension 8mL for the swellable stratiform modenite that step 1 obtains is taken, and adds in 7.5g cetyls thereto and gathers
Oxyethylene group cetyl ammonium bromide when stirring at normal temperature 24 is small, centrifuges, washing, when drying at room temperature 48 is small, after obtaining swelling
Stratiform modenite, interlamellar spacing 3.8nm.
3rd, pillared layered modenite is prepared
Stratiform modenite after 1.0g is swollen is uniformly mixed with 8.0g ethyl orthosilicates, under nitrogen atmosphere protection,
When 80 DEG C of stirrings 5 are small, centrifuge, when drying at room temperature 48 is small, obtain pillared layered modenite intermediate, it then will be among this
Body is placed in tube furnace, is warming up to 600 DEG C in a nitrogen atmosphere with 3 DEG C/min of heating rate, when constant temperature calcining 5 is small, finally
600 DEG C, when constant temperature calcining 5 is small are warming up to 3 DEG C/min of heating rate in Muffle furnace, obtains pillared layered modenite,
Its interlamellar spacing is 2.6nm.
In order to determine optimised process step of the present invention, inventor has carried out substantial amounts of laboratory research experiment, specific to test
Situation is as follows：
1st, influence of the charging sequence to synthesis product structure
Weigh 24.10g deionized waters, 0.21g sodium hydroxides, 0.28g sodium metaaluminates, 1.69g HMI and 5.05g titanium dioxides
Then mentioned reagent is uniformly mixed by Ludox according to different charging sequence (table 1) successively, 30 points are stirred under normal temperature condition
Clock, then add it in the hydrothermal reaction kettle that 50mL contains polytetrafluoroethylliner liner, by dynamic autoclaved technology method, 60
Rev/min, react 7 days under the conditions of 150 DEG C.Hydrothermal reaction kettle is taken out after hydro-thermal reaction to be quenched with cold water, and reaction solution is fallen
Enter in centrifuge tube and centrifuge, neutrality is washed to, when 60 DEG C of dryings 24 are small.Using D8Advance types x-ray diffractometer (Germany
Brooker company) products therefrom is characterized, it the results are shown in Table 1.
The structure of the obtained product of the different charging sequences of table 1
As shown in Table 1, dropwise addition order also has larger impact to modenite building-up process；Identical proportioning, according to A：NaOH、
NaAlO2、SiO2, HMI sequencings be added dropwise successively, easily generate MCM-22；According to E：NaOH、SiO2、HMI、NaAlO2Successively
Order is added dropwise successively, easily generates modenite.
2nd, influence of the reaction time to synthetic product
Weigh 24.19g deionized waters, 0.42g sodium hydroxides, 0.28g sodium metaaluminates, 1.68g HMI and 5.05g titanium dioxides
Sodium hydroxide is dissolved in 8.06mL deionized waters and is configured to sodium hydrate aqueous solution, sodium metaaluminate is dissolved in by Ludox
Sodium metaaluminate aqueous solution is configured in 16.13mL deionized waters；Titanium dioxide is sequentially added into the sodium metaaluminate aqueous solution prepared
Ludox, HMI, then the sodium hydrate aqueous solution prepared is added dropwise, then stirring at normal temperature 30 minutes shifts gained mixture
It is put into the hydrothermal reaction kettle containing polytetrafluoroethylliner liner, and by hydrothermal reaction kettle in homogeneous reactor, setting is contrary
The rotating speed of device is answered as 60 revs/min, is reacted respectively under the conditions of 150 DEG C 1 day, 3 days, 5 days, 7 days, after reaction, takes out water
Thermal response kettle, which is put into cold water, to be quenched, and reaction solution is poured into centrifuge tube and is centrifuged, and is washed to neutrality, and 60 DEG C of dryings 24 are small
When.Products therefrom is characterized by XRD, SEM, and experimental result is shown in Table 2.
Influence of the 2 differential responses time of table to product structure
As shown in Table 2, when reacted between when being 1 day, reaction generates irregular unformed substance, illustrates the reaction time too
It is short；When being 3 days between when reacted, the MCM-22 (P) of reaction generation sheet；When being 5 days and 7 days between when reacted, reaction life
Into the modenite of sheet；The building-up process for illustrating modenite under the conditions of this is with the extension of time, crystal is by MCM-
22 (P) turn brilliant process to modenite.Preferred reaction time of the present invention is 7 days.
3rd, influence of the sweller species to modenite swelling result
Cetyl trimethylammonium bromide (CTAB) and cetyl polyoxyethylene groups cetyl ammonium bromide is respectively adopted
(CPAB) as sweller, its influence to being swollen result is investigated.The suspension for taking two parts of swellable stratiform modenites is each
4mL, on the basis of CPAB according to CTAB and CPAB molar ratio be 1:1 is separately added into 2.15g CTAB, 3.75g CPAB, room temperature
Stir 16 it is small when, centrifuge, wash 4 times, when drying at room temperature 24 is small.The results are shown in Figure 3 for the XRD characterization of products therefrom.
When it can be seen from the XRD results of Fig. 3 using CPAB as sweller, low angle area occurs one strong in XRD spectrum
Diffraction maximum, corresponding interlamellar spacing are 3.50nm；On the contrary, during using CTAB as sweller, representative is not occurred in XRD spectrum
The diffraction maximum of layer structure, illustrate CPAB it is unique be structurally characterized in that form the key of stratiform modenite.
Claims (8)
1. a kind of preparation method of pillared layered modenite, it is characterised in that it is made of following step：
（1）Prepare swellable stratiform modenite
According to molar ratio SiO2/Al2O3=20~200, OH/SiO2=0.2~0.5, Na/SiO2=0.2~0.5, HMI/SiO2=0.4
~0.7, H2O/SiO2=10~50, wherein HMI represents hexamethylene imine, weighs raw material sodium metaaluminate, sodium hydroxide, titanium dioxide
Sodium hydroxide, sodium metaaluminate are dissolved separately in wiring solution-forming in deionized water by Ludox, hexamethylene imine, deionized water,
Silicon dioxide gel, hexamethylene imine are sequentially added into the sodium metaaluminate aqueous solution prepared, then the hydrogen prepared is added dropwise
Aqueous solution of sodium oxide, stirring at normal temperature 20~30 minutes, is then transferred to the water containing polytetrafluoroethylliner liner by gained mixture
In thermal response kettle, and hydrothermal reaction kettle is put into homogeneous reactor, the rotating speed for setting homogeneous reactor is 30~100 revs/min
Clock reacts 7~10 days at 100~200 DEG C, and after reaction, taking-up hydrothermal reaction kettle, which is put into cold water, to be quenched, and is obtained solvable
Swollen stratiform modenite suspension；
（2）The swelling of stratiform modenite
To step（1）Cetyl polyoxyethylene groups hexadecane bromide is added in obtained swellable stratiform modenite suspension
Change ammonium, quality-volume ratio of cetyl polyoxyethylene groups cetyl ammonium bromide and swellable stratiform modenite suspension
For 1g:1~15mL when stirring at normal temperature 16~32 is small, is then centrifuged, and washing when drying at room temperature 24~48 is small, obtains molten
Stratiform modenite after swollen；
（3）Prepare pillared layered modenite
By step（2）Stratiform modenite and ethyl orthosilicate after swelling are 1 in mass ratio:3~8 are uniformly mixed, in nitrogen
Under atmosphere protection, when 80~100 DEG C of stirrings 3~8 are small, centrifuge, when drying at room temperature 24~48 is small, obtain pillared layered mercerising
The intermediate is placed in tube furnace by zeolite intermediate, is warming up in a nitrogen atmosphere with 1~5 DEG C/min of heating rate
It 500~600 DEG C, when constant temperature calcining 5~8 is small, is subsequently placed in Muffle furnace and is warming up to 500 with 1~5 DEG C/min of heating rate
~600 DEG C, when constant temperature calcining 5~8 is small, obtain pillared layered modenite.
2. the preparation method of pillared layered modenite according to claim 1, it is characterised in that：In step（1）In, it presses
According to molar ratio SiO2/Al2O3=30~100, OH/SiO2=0.3~0.4, Na/SiO2=0.3~0.4, HMI/SiO2=0.5~0.6,
H2O/SiO2=30~40, weigh raw material sodium metaaluminate, sodium hydroxide, silicon dioxide gel, hexamethylene imine, deionized water.
3. the preparation method of pillared layered modenite according to claim 1 or 2, it is characterised in that：In step（1）
In, the rotating speed of homogeneous reactor is set to be reacted 7~10 days under the conditions of 140~160 DEG C for 50~60 revs/min.
4. the preparation method of pillared layered modenite according to claim 1, it is characterised in that：In step（2）In, institute
The cetyl polyoxyethylene groups cetyl ammonium bromide and quality-volume ratio of swellable stratiform modenite suspension stated be
1g:1~2mL.
5. the preparation method of pillared layered modenite according to claim 1, it is characterised in that：In step（3）In, institute
The mass ratio for stating the stratiform modenite after swelling and ethyl orthosilicate is 1:5.
6. the preparation method of pillared layered modenite according to claim 1 or 5, it is characterised in that：In step（3）
In, pillared layered modenite intermediate is placed in tube furnace, in a nitrogen atmosphere with 2~3 DEG C/min of heating rate liter
Temperature is to 550 DEG C, when constant temperature calcining 6 is small, is subsequently placed in Muffle furnace and is warming up to 550 DEG C with 2~3 DEG C/min of heating rate, perseverance
When temperature roasting 6 is small.
7. the preparation method of pillared layered modenite according to claim 1, it is characterised in that：The cetyl
The degree of polymerization of polyoxyethylene groups is 10 in polyoxyethylene groups cetyl ammonium bromide.
8. the pillared layered modenite that claim 1 the method is prepared.
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