CN106115733A - A kind of preparation method of multi-stage porous mordenite molecular sieve - Google Patents
A kind of preparation method of multi-stage porous mordenite molecular sieve Download PDFInfo
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/26—Mordenite type
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention provides the preparation method of a kind of multi-stage porous mordenite molecular sieve, comprise the following steps, after first being mixed in sodium hydroxide solution, silicon source and aluminum source, obtain aluminosilicate gels；Then, after again being mixed by the aluminosilicate gels that Graphene and/or Graphene derivative obtain with above-mentioned steps, mixture is obtained；After finally addition zeolite seed crystal carries out Crystallizing treatment in the mixture that above-mentioned steps obtains, obtain multi-stage porous mordenite molecular sieve.The present invention uses one or more in Graphene and derivant thereof to be mesoporous template, the mordenite molecular sieve with multi-stage porous is directly prepared by the method for Hydrothermal Synthesis, and do not use organic amine structure directing agent and organic solvent, greatly reduce the synthesis cost of molecular sieve, avoid the pollution to environment, there is environment friendly and pollution-free advantage；This synthesising method reacting condition is gentle simultaneously, and technique is simple, is suitable for industrialized great production.
Description
Technical field
The invention belongs to molecular screen material technical field, relate to the preparation method of a kind of mordenite molecular sieve, especially relate to
And the preparation method of a kind of multi-stage porous mordenite molecular sieve.
Background technology
Molecular sieve (also known as synthetic zeolite) refers to have uniform micropore, the class that its aperture is suitable with general molecular size
Material, it is a kind of many microporous crystals of aluminosilicate.It is formed basic framing structure by silica, aluminum-oxygen tetrahedron, at crystalline substance
Lattice also exist metal cation (such as Na+, K+, Ca2+, Li+ etc.), to balance negative charge unnecessary in crystal.The class of molecular sieve
Type is broadly divided into by its crystal structure: A type, X-type, Y type etc..The application of molecular sieve widely, can make highly effective drying agent, choosing
Selecting property adsorbent, catalyst, ion-exchanger etc..Conventional molecular sieve is silicate or the aluminosilicate of crystalline state, is by silica
Tetrahedron or aluminum-oxygen tetrahedron are connected by oxygen bridged bond and form duct and the sky of molecular dimension size (usually 0.3～2nm)
Cavity system, has the ability of the fluid molecule that screening varies in size because binding molecule size and shape is different.International purely with
They, according to molecular sieve bore diameter size, are defined as 3 grades by applied chemistry community: the aperture referred to as micro porous molecular sieve less than 2nm,
The aperture referred to as mesoporous or mesoporous molecular sieve between 2-50nm, the aperture referred to as large pore molecular sieve more than 50nm.
What molecular sieve had been found that has kind more than 1000, and the most important has 35 kinds, common are clinoptilolite, modenite,
Erionite and chabasie etc..Wherein, modenite is one of human knowledge's zeolite the earliest, point natural and synthesis two classes.1948
Year, Barrer etc. is mineralizer with sodium carbonate, makes mixing silicic acid gel and sodium aluminate aqueous solution hydro-thermal at 265-295 DEG C brilliant
Change, synthesize modenite first.Modenite has excellent heat-resisting, an acidproof and water vapor performance, industrial is widely used as
Adsorbent that gas or liquid mixture separate and petrochemical industry and fine chemistry industry catalyst.Use the mercerising of conventional method synthesis
Zeolite powder is low silica-alumina ratio modenite, need to carry out framework dealumination through special process step, to obtain relatively high silica alumina ratio
Modenite.But traditional microporous filament geolyte is generally regarded as one-dimensional tunnel structure zeolite molecular sieve, macromole can not
In duct, parallel or exchange diffusion, can only spread by monolayer, causes diffusion-restricted in catalysis is anticaustic, and molecule is in course of reaction
Blocking duct, causes the catalysis activity of catalyst to reduce, and the service life of catalyst shortens.
In the method for existing synthesis of molecular sieve, by introducing mesoporous and macropore in conventional microporous zeolite molecular sieve system
Prepare micropore-mesopore and be combined duct structure molecular screen, not only make it retain the various advantages of former micro porous molecular sieve, concurrently form
Mesopore orbit overcomes molecule diffusion-restricted in zeolite molecular sieve, improves its mass-transfer performance.The most synthesising mesoporous point
All using the material of some special properties as forming mesoporous template during son sieve, zeolite gel grows in template, shape
Become the complex of zeolite and template, then use high-temperature calcination, dissolve or the method such as distillation remove template mesoporous boiling
Stone molecular sieve.Schmidt et al. uses porous carbon nanotube to synthesize mesoporous zeolite monocrystalline (Iver Schmidt, Astrid
Boisen.Chem.Mater,2001,(13):4416-4418)；Fang et al. uses porous carbon to have height as templated synthesis
The mesoporous zeolite molecular sieve of degree of crystallinity (Yunming Fang, Haoquan Hu.J AM CHEM SOC, 2006, (128):
10636-10637.) etc..But these synthetic methods employ a large amount of organic formwork, organic directing agent or organic solvent, system
Standby process is complicated, substantially increases the synthesis cost of molecular sieve, and environmental pollution is bigger.
Therefore, how to obtain the synthetic method of the mordenite molecular sieve of a kind of more safety and environmental protection, and can synthesize
There is the mordenite molecular sieve of multi-stage porous, it has also become one of focus of line research staff's extensive concern in field.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide the synthetic method of a kind of mordenite molecular sieve,
A kind of synthetic method of multi-stage porous mordenite molecular sieve, the synthesis side of the mordenite molecular sieve that the present invention provides
Method, it is possible to synthesis has a mordenite molecular sieve of multi-stage porous, and synthetic method does not use organic directing agent, safety and environmental protection,
Reaction condition is gentle, and technique is simple, is suitable for industrialized great production.
The invention provides the preparation method of a kind of multi-stage porous mordenite molecular sieve, comprise the following steps:
A), after being mixed in sodium hydroxide solution, silicon source and aluminum source, aluminosilicate gels is obtained；
B) after the aluminosilicate gels that Graphene and/or Graphene derivative obtain with above-mentioned steps being mixed again,
To mixture；
C), after addition zeolite seed crystal carries out Crystallizing treatment in the mixture that above-mentioned steps obtains, the boiling of multi-stage porous mercerising is obtained
Stone molecular sieve.
Preferably, described silicon source includes the one in tetraethyl orthosilicate, white carbon, waterglass, Ludox and sodium silicate
Or it is multiple；
Source of aluminium includes one or more in sodium aluminate, boehmite, aluminum sulfate, aluminum chloride and aluminum nitrate.
Preferably, in described aluminosilicate gels, the mol ratio of following component is:
SiO2: A12O3For (8～100): 1；H2O:SiO2For (15～60): 1；Na2O:SiO2For (0.15～0.6): 1.
Preferably, described Graphene derivative includes graphene oxide, Graphene metal composite and Graphene activated carbon
One or more in complex.
Preferably, described Graphene and/or Graphene derivative are in terms of the quality of Graphene, with described aluminosilicate gels
With SiO2Quality meter, both ratio is (0.01～0.2): 1；
The quality of described zeolite seed crystal and described aluminosilicate gels are with SiO2Quality meter, both ratio is (0.008
～0.08): 1.
Preferably, ultrasound treatment step is also included after described mixing again.
Preferably, the temperature of described Crystallizing treatment is 130～200 DEG C, and the time of described Crystallizing treatment is 1～8 day.
Preferably, after described Crystallizing treatment, also include post-processing step；
Described post processing include sucking filtration, wash, be dried and roasting.
Preferably, described dry temperature is 80～130 DEG C, and the described dry time is 6～24h；
The temperature of described roasting is 400～800 DEG C, and described roasting time is 3～10h.
Preferably, described step A) particularly as follows:
A1), after being mixed with silicon source by sodium hydroxide solution, the first mixed liquor is obtained；
After sodium hydroxide solution and aluminum source being mixed, obtain the second mixed liquor；
A2), after the first mixed liquor above-mentioned steps obtained and the mixing of the second mixed liquor, aluminosilicate gels is obtained.
The invention provides the preparation method of a kind of multi-stage porous mordenite molecular sieve, comprise the following steps, first by hydrogen
After sodium hydroxide solution, silicon source and the mixing of aluminum source, obtain aluminosilicate gels；Then by Graphene and/or Graphene derivative with
After the aluminosilicate gels that above-mentioned steps obtains mixes again, obtain mixture；Last in the mixture that above-mentioned steps obtains
After addition zeolite seed crystal carries out Crystallizing treatment, obtain multi-stage porous mordenite molecular sieve.Compared with prior art, the present invention uses
One or more in Graphene and derivant thereof are mesoporous template, directly prepared by the method for Hydrothermal Synthesis have multistage
The mordenite molecular sieve in hole, effectively solves the modenite of synthesis in prior art and contains only micropore, do not contain mesoporous
Or mesoporous less and wider distribution, it is impossible to it is used as the limitation that macromole participates in the catalyst of reaction, and does not use organic amine
Structure directing agent and organic solvent, greatly reduce the synthesis cost of molecular sieve, it is to avoid the pollution to environment, have environmental protection without
The advantage polluted；This synthesising method reacting condition is gentle simultaneously, and technique is simple, is suitable for industrialized great production.Experimental result table
Bright, multi-stage porous mordenite molecular sieve prepared by the present invention not only has microcellular structure, and simultaneously possibly together with meso-hole structure, it compares table
Area 365～412m2/ g, mesoporous pore volume 0.12～0.25mL/g.
Accompanying drawing explanation
Fig. 1 is the X-ray powder diffraction pattern of the multi-stage porous modenite of the 2-in-1 one-tenth of the embodiment of the present invention；
Fig. 2 is the isothermal nitrogen adsorption-desorption figure of the multi-stage porous modenite of the 2-in-1 one-tenth of the embodiment of the present invention.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but
Should be appreciated that these descriptions are intended merely to further illustrate the features and advantages of the present invention rather than to invention claim
Limit.
The all raw materials of the present invention, are not particularly limited its source, that commercially buy or according to people in the art
Prepared by the conventional method known to Yuan.
The all raw materials of the present invention, are not particularly limited its purity, present invention preferably employs analytical pure or capacitor area
The conventional purity used.
The invention provides the preparation method of a kind of multi-stage porous mordenite molecular sieve, comprise the following steps:
A), after being mixed in sodium hydroxide solution, silicon source and aluminum source, aluminosilicate gels is obtained；
B) after the aluminosilicate gels that Graphene and/or Graphene derivative obtain with above-mentioned steps being mixed again,
To mixture；
C), after addition zeolite seed crystal carries out Crystallizing treatment in the mixture that above-mentioned steps obtains, the boiling of multi-stage porous mercerising is obtained
Stone molecular sieve.
After first sodium hydroxide solution, silicon source and aluminum source are mixed by the present invention, obtain aluminosilicate gels.
The concentration of described sodium hydroxide solution is not particularly limited by the present invention, with well known to those skilled in the art for
Preparing the concentration of the conventional sodium hydroxide solution of mordenite molecular sieve, those skilled in the art can be according to actual production
Situation, product requirement and prescription select and adjust, the concentration of sodium hydroxide solution of the present invention be preferably 1%～
20%, more preferably 3%～17%, more preferably 6%～14%, most preferably 9%～11%.Described silicon source is not had by the present invention
There is restriction especially, with well known to those skilled in the art for preparing the silicon source that mordenite molecular sieve is conventional, this area
Technical staff can select according to practical condition, product requirement and prescription and adjust, silicon source of the present invention
Preferably include one or more in tetraethyl orthosilicate, white carbon, waterglass, Ludox and sodium silicate, the most positive silicon
Acid tetra-ethyl ester, white carbon, waterglass, Ludox or sodium silicate.Source of aluminium is not particularly limited by the present invention, with this area skill
The aluminum source for preparing mordenite molecular sieve routine known to art personnel, those skilled in the art can be raw according to reality
Product situation, product requirement and prescription select and adjust, and aluminum source of the present invention preferably includes sodium aluminate, intends thin water aluminum
One or more in stone, aluminum sulfate, aluminum chloride and aluminum nitrate, more preferably sodium aluminate, boehmite, aluminum sulfate, chlorination
Aluminum or aluminum nitrate.
Described mixing is not particularly limited by the present invention, and those skilled in the art can be according to practical condition, product
Requiring and prescription selects and adjusts, mixing of the present invention preferably stirs mixing.The present invention is for improving all
The effect of even mixing, described step A) it is particularly preferred as:
A1), after being mixed with silicon source by sodium hydroxide solution, the first mixed liquor is obtained；
After sodium hydroxide solution and aluminum source being mixed, obtain the second mixed liquor；
A2), after the first mixed liquor above-mentioned steps obtained and the mixing of the second mixed liquor, aluminosilicate gels is obtained.
The present invention is to described step A1) in hybrid mode be not particularly limited, those skilled in the art can be according to reality
The border condition of production, product requirement and prescription select and adjust, and mixing of the present invention is preferably magnetic force uniform stirring
Clarify to solution.The present invention is to described step A2) in hybrid mode be not particularly limited, those skilled in the art can basis
Practical condition, product requirement and prescription select and adjust, and mixing of the present invention preferably stirs shape
Become aluminosilicate gels.
The present invention is in described aluminosilicate gels, and the concrete ratio of the compositions such as sial is not particularly limited, with this area
Corresponding component ratio in aluminosilicate gels known to technical staff, those skilled in the art can be according to actual production
Situation, product requirement and prescription select and adjust, in aluminosilicate gels of the present invention, with molar ratio computing, institute
State SiO2: A12O3It is preferably (8～100): 1, more preferably (20～90): 1, more preferably (30～80): 1, most preferably (50
～60): 1；Described H2O:SiO2It is preferably (15～60): 1, more preferably (20～55): 1, more preferably (25～50): 1,
It is preferably (30～40): 1；Described Na2O:SiO2It is preferably (0.15～0.6): 1, more preferably (0.2～0.55): 1, more preferably
For (0.25～0.5): 1, most preferably (0.3～0.4): 1.
Then the aluminosilicate gels that Graphene and/or Graphene derivative and above-mentioned steps obtain is mixed by the present invention again
After conjunction, obtain mixture.
Described Graphene derivative is not particularly limited by the present invention, derives with Graphene well known to those skilled in the art
Thing, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, this
Invent described Graphene derivative to preferably include in graphene oxide, Graphene metal composite and Graphene activated carbon complex
One or more, more preferably graphene oxide, Graphene metal composite or Graphene activated carbon complex, more preferably
Graphene oxide or Graphene activated carbon complex.The addition of described Graphene and/or Graphene derivative is not had by the present invention
Having restriction especially, those skilled in the art can select according to practical condition, product requirement and prescription and adjust
Whole, Graphene of the present invention and/or Graphene derivative are in terms of the quality of Graphene, with described aluminosilicate gels with SiO2
Quality meter, described Graphene and described SiO2Mass ratio be preferably (0.01～0.2): 1, more preferably (0.04～
0.17): 1, more preferably (0.07～0.14): 1, most preferably (0.09～0.12): 1.
The present invention to described again mixing be not particularly limited, those skilled in the art can according to practical condition,
Product requirement and prescription select and adjust, and mixing again of the present invention is preferably magnetic agitation and uniformly mixes.This
Invention, for improving the uniformity of mixing, improves the Dominance of the mesoporous pore size of final products, after described mixing again preferably also
Including ultrasound treatment step；The actual conditions of described supersound process is not particularly limited by the present invention, with those skilled in the art
Known to supersound process condition, those skilled in the art can be according to practical condition, product requirement and prescription
Selecting and adjust, the time of supersound process of the present invention is preferably 0.5～3h, more preferably 1～2.5h, most preferably
1.5～2h.
The present invention finally adds after zeolite seed crystal carries out Crystallizing treatment in the mixture that above-mentioned steps obtains, and obtains multistage
Hole mordenite molecular sieve.
Described zeolite seed crystal is not particularly limited by the present invention, with modenite crystal seed well known to those skilled in the art i.e.
Can, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, the present invention
The modenite of described zeolite seed crystal preferably non-dealuminzation or silica alumina ratio are preferably the dealuminium mordenite of 40～80, described sial
Ratio can also be 50～70.The addition of described zeolite seed crystal is not particularly limited by the present invention, and those skilled in the art are permissible
Select according to practical condition, product requirement and prescription and adjust, the quality of zeolite seed crystal of the present invention with
Described aluminosilicate gels is with SiO2Quality meter, the quality of described zeolite seed crystal and described SiO2Quality ratio be preferably
(0.008～0.08): 1, more preferably (0.01～0.07): 1, more preferably (0.02～0.06): 1, most preferably (0.03～
0.05): 1.
The actual conditions of described Crystallizing treatment is not particularly limited by the present invention, with crystallization well known to those skilled in the art
The condition processed, those skilled in the art can select according to practical condition, product requirement and prescription
And adjustment, the temperature of Crystallizing treatment of the present invention is preferably 130～200 DEG C, more preferably 140～190 DEG C, more preferably
150～180 DEG C, most preferably 160～170 DEG C；The time of described Crystallizing treatment is preferably 1～8 day, more preferably 2～7 days,
More preferably 3～6 days, most preferably 4～5 days.The equipment of described Crystallizing treatment is not particularly limited by the present invention, this area skill
Art personnel can select according to practical condition, product requirement and prescription and adjust, at crystallization of the present invention
The equipment of reason is preferably hydrothermal crystallizing still.
The present invention is to improve the quality of final products, after described Crystallizing treatment, the most also includes post-processing step；The present invention
The detailed process of described post processing is not particularly limited, with the post-processing step of hydro-thermal reaction well known to those skilled in the art
, those skilled in the art can select according to practical condition, product requirement and prescription and adjust, this
Bright described post processing preferably includes sucking filtration, washs, is dried and roasting, more preferably includes sucking filtration successively, washs, is dried and roasting
Step；The actual conditions of above-mentioned steps is not particularly limited by the present invention, with above-mentioned steps well known to those skilled in the art
Normal condition, those skilled in the art can carry out selecting according to practical condition, product requirement and prescription and
Adjusting, dry temperature of the present invention is preferably 80～130 DEG C, more preferably 90～120 DEG C, most preferably 100～110
℃；The described dry time is preferably 6～24h；More preferably 8～22h, more preferably 10～20h, most preferably 12～18h；
The temperature of described roasting is preferably 400～800 DEG C, more preferably 450～750 DEG C, more preferably 500～700 DEG C, most preferably
550～650 DEG C；Described roasting time is preferably 3～10h, more preferably 4～9h, more preferably 5～8h, most preferably 6～
7h。
The present invention has prepared multi-stage porous mordenite molecular sieve through above-mentioned steps, the present invention use Graphene and
One or more in derivant are mesoporous template, and by creative improvement modenite synthetic technological condition, hydro-thermal is closed
Become to have the mordenite molecular sieve of multi-stage porous, and by adding crystal seed and the method for supersound process, prepare mesoporous hole
The multi-stage porous modenite of footpath narrow distribution, and further control process conditions, finally give and there is less crystal grain chi
Very little, abundant micro--mesoporous, bigger specific surface area, narrower mesoporous distribution, the multi-stage porous mercerising of higher purity and degree of crystallinity
Zeolite.The synthetic method that the present invention provides does not uses organic amine structure directing agent and organic solvent, greatly reduces molecular sieve
Synthesis cost, it is to avoid pollution to environment, has environment friendly and pollution-free advantage；And this synthesising method reacting condition is gentle,
Technique is simple, is suitable for industrialized great production.Test result indicate that, multi-stage porous mordenite molecular sieve prepared by the present invention is not only
There is microcellular structure, simultaneously possibly together with meso-hole structure, its specific surface area 365～412m2/ g, mesoporous pore volume 0.12～0.25mL/
g。
In order to further illustrate the present invention, a kind of multi-stage porous modenite provided the present invention below in conjunction with embodiment divides
The preparation method of son sieve is described in detail, but it is to be understood that these embodiments are premised on technical solution of the present invention
Under implement, give detailed embodiment and concrete operating process, simply for further illustrating inventive feature
With advantage rather than limiting to the claimed invention, protection scope of the present invention is also not necessarily limited to following embodiment.
Embodiment 1
4.55gNaOH is joined in 158.8g distilled water, stir to clarify solution, be divided into A, B two parts standby.Will
The sodium aluminate of 2.68g joins and stirs in solution A to all dissolving formation C mixed liquor, the white carbon of 20.5g is joined B molten
Liquid stirs to all dissolving, form D mixed liquor.C mixed liquor is under agitation slowly added dropwise in D mixed liquor formation aluminosilicate
Salt gel E.The mol ratio of Primogel is: SiO2/Al2O3=30, H2O:SiO2=26, Na2O:SiO2=0.2.
Weigh a certain amount of Graphene, the quality of the Graphene wherein added and SiO in aluminosilicate gels2Mass ratio
It is 0.01, above-mentioned Graphene is dissolved in the deionized water of 33.8g and stirs to being uniformly dispersed, obtain graphene solution F, in stirring
Under the conditions of graphene solution F be slowly added dropwise in E gel be uniformly mixed, then carry out ultrasonic Treatment 1h and obtain G solution.
Weigh a certain amount of crystal seed, the quality of the crystal seed wherein added and SiO in aluminosilicate gels2Mass ratio be
0.01, add G solution and obtain mixture H.
Finally mixture H is proceeded in the rustless steel crystallizing kettle of teflon lined, crystallization 2 days, product at 170 DEG C
Through sucking filtration, washing, be dried 12h at 100 DEG C, after 500 DEG C of roasting 10h multi-stage porous modenite product.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 1 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 379m2/ g, mesoporous pore volume 0.15mL/g.
Embodiment 2
3.79gNaOH is joined in 98.1g distilled water, stir to clarify solution, be divided into A, B two parts standby.Will
The sodium aluminate of 1.43g joins and stirs in solution A to all dissolving formation C mixed liquor, and the Ludox of 49g is joined B solution
Middle stirring, to all dissolving, forms D mixed liquor.C mixed liquor is under agitation slowly added dropwise in D mixed liquor formation aluminosilicate
Gel E.The mol ratio of Primogel is: SiO2/Al2O3=28, H2O:SiO2=30, Na2O:SiO2=0.23.
Weigh a certain amount of Graphene, the quality of the Graphene wherein added and SiO in aluminosilicate gels2Mass ratio
It is 0.02, above-mentioned Graphene is dissolved in the deionized water of 20g and stirs to being uniformly dispersed, obtain graphene solution F, at stirring bar
Under part, graphene solution F is slowly added dropwise in E gel and is uniformly mixed, then carry out ultrasonic Treatment 1h and obtain G solution.
Weigh a certain amount of crystal seed, the quality of the crystal seed wherein added and SiO in aluminosilicate gels2Mass ratio be
0.02, add G solution and obtain mixture H.
Finally mixture H is proceeded in the rustless steel crystallizing kettle of teflon lined, crystallization 1.5 days at 170 DEG C, produce
Thing through sucking filtration, washing, be dried 12h at 110 DEG C, after 550 DEG C of roasting 10h multi-stage porous modenite product.
The multi-stage porous modenite multi-stage porous mordenite molecular sieve of the embodiment of the present invention 2 preparation is detected, sees
Fig. 1, Fig. 1 are the X-ray powder diffraction pattern of the multi-stage porous modenite of the 2-in-1 one-tenth of the embodiment of the present invention.As shown in Figure 1, solid
Product is modenite through X-ray analysis.
See the isothermal nitrogen adsorption-desorption figure of the multi-stage porous modenite that Fig. 2, Fig. 2 are the 2-in-1 one-tenth of the embodiment of the present invention.
As shown in Figure 2, in isothermal nitrogen adsorption-desorption figure, there is obvious hysteresis loop in isothermal line, returns the closing point of stagnant ring at P/P0=
Between 0.40～0.45, illustrate to introduce in mordenite molecular sieve mesoporous, record specific surface area 412m2/ g, mesoporous pore volume
0.25mL/g。
Embodiment 3
In addition to replacing the white carbon in embodiment 1 as silicon source with sodium silicate, other preparation conditions all with embodiment 1 phase
With, the solid product obtained--multi-stage porous mordenite molecular sieve.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 3 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 387m2/ g, mesoporous pore volume 0.18mL/g.
Embodiment 4
In addition to replacing the white carbon in embodiment 1 as silicon source with tetraethyl orthosilicate, other preparation conditions all with enforcement
Example 1 is identical, the solid product obtained--multi-stage porous mordenite molecular sieve.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 4 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 365m2/ g, mesoporous pore volume 0.12mL/g.
Embodiment 5
In addition to replacing the sodium aluminate in embodiment 2 as aluminum source with aluminum sulfate, other preparation conditions all with embodiment 2 phase
With, the solid product obtained--multi-stage porous mordenite molecular sieve.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 5 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 403m2/ g, mesoporous pore volume 0.21mL/g.
Embodiment 6
In addition to replacing the sodium aluminate in embodiment 2 as aluminum source with aluminum nitrate, other preparation conditions all with embodiment 2 phase
With, the solid product obtained--multi-stage porous mordenite molecular sieve.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 6 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 382m2/ g, mesoporous pore volume 0.16mL/g.
Embodiment 7
In addition to replacing the sodium aluminate in embodiment 2 as aluminum source with aluminum chloride, other preparation conditions all with embodiment 2 phase
With, the solid product obtained--multi-stage porous mordenite molecular sieve.
Detecting the multi-stage porous mordenite molecular sieve of the embodiment of the present invention 7 preparation, solid product is through X-ray analysis
For modenite, isothermal nitrogen adsorption-desorption records specific surface area 380m2/ g, mesoporous pore volume 0.15mL/g.
Above the preparation method of a kind of multi-stage porous mordenite molecular sieve that the present invention provides is described in detail,
Principle and the embodiment of the present invention are set forth by specific case used herein, and the explanation of above example is simply used
In helping to understand method and the core concept thereof of the present invention, including best mode, and also make any technology people of this area
Member can put into practice the present invention, including manufacturing and using any device or system, and the method implementing any combination.Should refer to
Go out, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention
Carrying out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.Patent of the present invention
Protection scope be defined by the claims, and those skilled in the art can be included it is conceivable that other embodiments.If
These other embodiments have the structural element being not different from claim character express, if or they include and right
The character express required is without the equivalent structural elements of essence difference, then these other embodiments also should be included in claim
In the range of.
Claims (10)
1. the preparation method of a multi-stage porous mordenite molecular sieve, it is characterised in that comprise the following steps:
A), after being mixed in sodium hydroxide solution, silicon source and aluminum source, aluminosilicate gels is obtained；
B), after the aluminosilicate gels that Graphene and/or Graphene derivative obtain with above-mentioned steps being mixed again, mixed
Compound；
C), after addition zeolite seed crystal carries out Crystallizing treatment in the mixture that above-mentioned steps obtains, obtain multi-stage porous modenite and divide
Son sieve.
Preparation method the most according to claim 1, it is characterised in that described silicon source include tetraethyl orthosilicate, white carbon,
One or more in waterglass, Ludox and sodium silicate；
Source of aluminium includes one or more in sodium aluminate, boehmite, aluminum sulfate, aluminum chloride and aluminum nitrate.
Preparation method the most according to claim 1, it is characterised in that in described aluminosilicate gels, rubbing of following component
That is than being:
SiO2: A12O3For (8～100): 1；H2O:SiO2For (15～60): 1；Na2O:SiO2For (0.15～0.6): 1.
Preparation method the most according to claim 1, it is characterised in that described Graphene derivative include graphene oxide,
One or more in Graphene metal composite and Graphene activated carbon complex.
Preparation method the most according to claim 1, it is characterised in that described Graphene and/or Graphene derivative are with stone
The quality meter of ink alkene, with described aluminosilicate gels with SiO2Quality meter, both ratio is (0.01～0.2): 1；
The quality of described zeolite seed crystal and described aluminosilicate gels are with SiO2Quality meter, both ratio be (0.008～
0.08): 1.
Preparation method the most according to claim 1, it is characterised in that also include that supersound process walks after described mixing again
Suddenly.
Preparation method the most according to claim 1, it is characterised in that the temperature of described Crystallizing treatment is 130～200 DEG C,
The time of described Crystallizing treatment is 1～8 day.
Preparation method the most according to claim 1, it is characterised in that after described Crystallizing treatment, also includes post-processing step；
Described post processing include sucking filtration, wash, be dried and roasting.
Preparation method the most according to claim 8, it is characterised in that described dry temperature is 80～130 DEG C, described dry
The dry time is 6～24h；
The temperature of described roasting is 400～800 DEG C, and described roasting time is 3～10h.
Preparation method the most according to claim 1, it is characterised in that described step A) particularly as follows:
A1), after being mixed with silicon source by sodium hydroxide solution, the first mixed liquor is obtained；
After sodium hydroxide solution and aluminum source being mixed, obtain the second mixed liquor；
A2), after the first mixed liquor above-mentioned steps obtained and the mixing of the second mixed liquor, aluminosilicate gels is obtained.
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| CN108786767A (en) * | 2018-04-28 | 2018-11-13 | 中国石油大学(华东) | A kind of preparation method of nanoscale molecular sieve@graphene oxide coupling materials |
| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN114590818A (en) * | 2022-02-25 | 2022-06-07 | 厦门大学 | Lamellar MOR molecular sieve, preparation method thereof, catalyst for preparing ethanol by using synthesis gas and method |
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| CN103880036A (en) * | 2014-03-25 | 2014-06-25 | 南京工业大学 | Synthetic method of mesoporous mordenite |
| CN104909384A (en) * | 2015-05-27 | 2015-09-16 | 中国科学院广州地球化学研究所 | Mordenite having diatomite morphology and multi-level pore channel structure, and preparation method thereof |
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| CN112250083A (en) * | 2019-07-22 | 2021-01-22 | 青岛科技大学 | Micro-mesoporous composite aluminum phosphate molecular sieve and preparation method thereof |
| CN114590818A (en) * | 2022-02-25 | 2022-06-07 | 厦门大学 | Lamellar MOR molecular sieve, preparation method thereof, catalyst for preparing ethanol by using synthesis gas and method |
| CN114590818B (en) * | 2022-02-25 | 2023-08-08 | 厦门大学 | Lamellar MOR molecular sieve and preparation method thereof, catalyst for preparing ethanol by using synthesis gas and preparation method thereof |
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