CN104671253B - A kind of preparation method of ZSM-22 molecular sieve nanometer sheet - Google Patents

A kind of preparation method of ZSM-22 molecular sieve nanometer sheet Download PDF

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CN104671253B
CN104671253B CN201510084713.5A CN201510084713A CN104671253B CN 104671253 B CN104671253 B CN 104671253B CN 201510084713 A CN201510084713 A CN 201510084713A CN 104671253 B CN104671253 B CN 104671253B
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molecular sieve
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potassium hydroxide
deionized water
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CN104671253A (en
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吴伟
张建伟
戚鑫
魏小盟
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Heilongjiang University
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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
    • C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
    • C—CHEMISTRY; METALLURGY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
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Abstract

A kind of preparation method of ZSM 22 molecular sieve nanometer sheet, the present invention relates to the preparation method of ZSM 22 molecular sieve, it uses, for the method solving existing synthesis ZSM 22 molecular sieve, the problem that consumption of template agent is big, cost is high, zeolite crystal exists with larger-size aggregate form.Preparation method: one, use aluminum sulfate octadecahydrate, tetraethyl orthosilicate, 1,6 hexamethylene diamines, potassium hydroxide and deionized water to prepare prefabricated crystal seed；Two, aluminum sulfate octadecahydrate, Ludox, potassium hydroxide and deionized water is used to prepare gel；Three, crystallization and roasting.ZSM 22 molecular sieve prepared by the present invention is regularly arranged lamination nanometer sheet structure, and lamellar spacing only has about 20nm, and significantly reduces the consumption of organic formwork agent in building-up process, shortens crystallization time, reduces cost.

Description

A kind of preparation method of ZSM-22 molecular sieve nanometer sheet
Technical field
The present invention relates to the preparation method of ZSM-22 molecular sieve.
Background technology
ZSM-22 zeolite molecular sieve has one-dimensional linear non-crossing straight hole road, and pore size is 0.45nm × 0.55nm, has Abundant acidic site and stronger acid strength, as solid acid catalyst for alkene and isomerization of paraffins, alkane aromatization, It is hydrocracked and selects the reactions such as alkylation with alkylbenzene.
Johan A. et al. (Journal of Catalysis, 203 (2001) 213-231) is with n-decane to n-tetracosane as model Compound, evaluates the Hydroisomerization Properties of Pt/H-ZSM-22, and has obtained more excellent isomerization reaction performance. Biscard et al. reports in US20040186006 and utilizes ZSM-22 molecular sieve as acid carrier, is applied to carbon number More than in the isomerization reaction of the n-alkane of 10, also embody good isomerization performance.(the Applied such as Kumar Catalysis A:General, 139 (1996) 189-199) report ZSM-22 modification H-ZSM-22 at normal butane virtue Application in structure.
The method of synthesis ZSM-22 molecular sieve has employing organic formwork agent and does not use two kinds of methods of organic formwork agent at present. Johan A. et al. (Applied Catalysis, 48 (1989) 137-148) uses 1, and 6 hexamethylene diamines are template, with traditional Water heat transfer ZSM-22 molecular sieve, but the large usage quantity of template.Meng Xiangju et al. is at (CN103101924) Reporting employing crystal seed method does not use organic formwork agent to synthesize ZSM-22 molecular sieve, and synthesized ZSM-22 molecular sieve is Being made up of bar-shaped or Acicular aggregates, size is between 2～4 μm.
During using the ZSM-22 molecular sieve that conventional template agent method synthesizes, use a large amount of organic formwork agent, cost Higher, the waste gas that organic formwork agent decomposition produces in roasting process also to environment, and can use crystal seed method not make Although ZSM-22 molecular sieve can also be synthesized by template, but the crystallite dimension of molecular sieve is relatively big, uses as catalyst Time can in course of reaction because occur carbon distribution and inactivate, limit its application in the industry.Therefore, new method synthesis is used The ZSM-22 molecular sieve with nanoscale has great importance.
Summary of the invention
The invention solves the problems that existing synthesis ZSM-22 molecular sieve method use consumption of template agent is big, cost is high, point The son sieve problem that exists with larger-size aggregate form of crystal grain, and provide one substantially reduce consumption of template agent, Reduce cost, the new method of synthesis nano-sheet ZSM-22 molecular sieve.
The preparation method of ZSM-22 molecular sieve nanometer sheet of the present invention realizes according to following steps:
One, the preparation of prefabricated crystal seed:
A, weigh aluminum sulfate octadecahydrate, tetraethyl orthosilicate, 1,6 hexamethylene diamines, potassium hydroxide and deionized water as raw material；
B, potassium hydroxide step a weighed and deionized water mixing, prepare potassium hydroxide aqueous solution, by step after dissolving Aluminum sulfate octadecahydrate and deionized water that a weighs mix, and prepare aluminum sulfate aqueous solution, 1,6 step a weighed after dissolving Hexamethylene diamine and deionized water mixing, prepare 1,6 hexamethylene diamine aqueous solutions, tetraethyl orthosilicate step a weighed and going after dissolving Ionized water is mixed to form suspension；
C, aluminum sulfate aqueous solution step b obtained join in potassium hydroxide aqueous solution, and 400～600r/min Stir 5～10min under rotating speed and obtain solution A；
D, 1,6 hexamethylene diamine aqueous solutions step b obtained add in the solution A that step c prepares, and 400～600r/min Rotating speed under stir 5～10min, obtain mixture B；
In e, the suspension addition mixture B that will obtain in step b, and obtain in 300～600r/min stirrings 2～4h Mixed gel C；
F, mixed gel C step e obtained are placed in the rustless steel closed reactor with polytetrafluoroethyllining lining pad, Crystallization 0.5～7h under conditions of temperature 150～170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature；
Wherein the tetraethyl orthosilicate described in step a is 1:(0.028～0.045 with the mass ratio of aluminum sulfate octadecahydrate)；Described The mass ratio of tetraethyl orthosilicate and 1,6 hexamethylene diamines is 1:(0.162～0.216)；Described tetraethyl orthosilicate and potassium hydroxide Mass ratio is 1:(0.085～0.11)；
Two, the preparation of mixed gel:
G, weigh aluminum sulfate octadecahydrate, Ludox, potassium hydroxide and deionized water as raw material；
H, the potassium hydroxide weighed in step g is mixed with deionized water, after dissolving, obtain potassium hydroxide aqueous solution, will step The aluminum sulfate octadecahydrate weighed in rapid g mixes with deionization, obtains aluminum sulfate aqueous solution, by weigh in step g after dissolving Ludox obtains the suspension of silicon dioxide with deionized water after mixing；
I, the aluminum sulfate aqueous solution obtained in step h is joined in potassium hydroxide aqueous solution, and 400～600r/min Stir 5～10min under rotating speed and obtain solution D；
J, the suspension of the silicon dioxide obtained in step h is joined in solution D, and 700～1000r/min turn The lower stirring 1～2h of speed obtains mixed gel E；
Wherein the Ludox described in step g is 1:(0.022～0.042 with the mass ratio of aluminum sulfate octadecahydrate)；Described silicon is molten Glue is 1:(0.083～0.128 with the mass ratio of potassium hydroxide)；
Three, crystallization and roasting: prefabricated crystal seed step one obtained is added directly in the mixed gel E that step 2 obtains, Under the rotating speed of 700～1200r/min, stir 10～30min, be subsequently placed in the rustless steel with polytetrafluoroethyllining lining pad close Close in reactor, take out after crystallization 10h～72h under conditions of temperature 140～180 DEG C, be cooled to room temperature, then be centrifuged, Washing 3～4 times, put in Muffle furnace after dried, at a temperature of 500～700 DEG C, roasting 3～20h, obtain ZSM-22 Molecular sieve.
The method of the present invention prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet comprises following beneficial effect:
1, the present invention uses prefabricated crystal seed method to prepare ZSM-22 molecular sieve nanometer sheet, its pattern and the synthesis of conventional hydrothermal method Bar-shaped ZSM-22 Molecular sieve aggregate has marked difference, and the thickness of nanometer sheet only has about 20nm, as catalyst energy Enough significantly improve reactant and the product diffusion in molecular sieve pore passage, improve the accessibility of catalyst activity position, from And increase substantially its catalysis activity, and effectively suppress the generation of carbon distribution, extend the service life of catalyst.
2, the organic formwork dosage that the present invention uses when synthesizing ZSM-22 molecular sieve nanometer sheet substantially reduces, template and SiO2 Mol ratio be reduced to (0.03～0.06): 1, be only the 1/5～1/10 of traditional method consumption, cost be greatly reduced.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum of the ZSM-22 molecular sieve nanometer sheet of embodiment one preparation；
Fig. 2 is the electron scanning micrograph of the ZSM-22 molecular sieve nanometer sheet of embodiment one preparation；
Fig. 3 is the X-ray diffraction spectrum of the ZSM-22 molecular sieve nanometer sheet of embodiment two preparation；
Fig. 4 is the electron scanning micrograph of the ZSM-22 molecular sieve nanometer sheet of embodiment two preparation.
Detailed description of the invention
Detailed description of the invention one: present embodiment prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet method according to Lower step is implemented:
One, the preparation of prefabricated crystal seed:
A, weigh aluminum sulfate octadecahydrate, tetraethyl orthosilicate, 1,6 hexamethylene diamines, potassium hydroxide and deionized water as raw material；
B, potassium hydroxide step a weighed and deionized water mixing, prepare potassium hydroxide aqueous solution, by step after dissolving Aluminum sulfate octadecahydrate and deionized water that a weighs mix, and prepare aluminum sulfate aqueous solution, 1,6 step a weighed after dissolving Hexamethylene diamine and deionized water mixing, prepare 1,6 hexamethylene diamine aqueous solutions, tetraethyl orthosilicate step a weighed and going after dissolving Ionized water is mixed to form suspension；
C, aluminum sulfate aqueous solution step b obtained join in potassium hydroxide aqueous solution, and 400～600r/min Stir 5～10min under rotating speed and obtain solution A；
D, 1,6 hexamethylene diamine aqueous solutions step b obtained add in the solution A that step c prepares, and 400～600r/min Rotating speed under stir 5～10min, obtain mixture B；
In e, the suspension addition mixture B that will obtain in step b, and obtain in 300～600r/min stirrings 2～4h Mixed gel C；
F, mixed gel C step e obtained are placed in the rustless steel closed reactor with polytetrafluoroethyllining lining pad, Crystallization 0.5～7h under conditions of temperature 150～170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature；
Wherein the tetraethyl orthosilicate described in step a is 1:(0.028～0.045 with the mass ratio of aluminum sulfate octadecahydrate)；Described The mass ratio of tetraethyl orthosilicate and 1,6 hexamethylene diamines is 1:(0.162～0.216)；Described tetraethyl orthosilicate and potassium hydroxide Mass ratio is 1:(0.085～0.11)；
Two, the preparation of mixed gel:
G, weigh aluminum sulfate octadecahydrate, Ludox, potassium hydroxide and deionized water as raw material；
H, the potassium hydroxide weighed in step g is mixed with deionized water, after dissolving, obtain potassium hydroxide aqueous solution, will step The aluminum sulfate octadecahydrate weighed in rapid g mixes with deionization, obtains aluminum sulfate aqueous solution, by weigh in step g after dissolving Ludox obtains the suspension of silicon dioxide with deionized water after mixing；
I, the aluminum sulfate aqueous solution obtained in step h is joined in potassium hydroxide aqueous solution, and 400～600r/min Stir 5～10min under rotating speed and obtain solution D；
J, the suspension of the silicon dioxide obtained in step h is joined in solution D, and 700～1000r/min turn The lower stirring 1～2h of speed obtains mixed gel E；
Wherein the Ludox described in step g is 1:(0.022～0.042 with the mass ratio of aluminum sulfate octadecahydrate)；Described silicon is molten Glue is 1:(0.083～0.128 with the mass ratio of potassium hydroxide)；
Three, crystallization and roasting: prefabricated crystal seed step one obtained is added directly in the mixed gel E that step 2 obtains, Under the rotating speed of 700～1200r/min, stir 10～30min, be subsequently placed in the rustless steel with polytetrafluoroethyllining lining pad close Close in reactor, take out after crystallization 10h～72h under conditions of temperature 140～180 DEG C, be cooled to room temperature, then be centrifuged, Washing 3～4 times, put in Muffle furnace after dried, at a temperature of 500～700 DEG C, roasting 3～20h, obtain ZSM-22 Molecular sieve.
Present embodiment uses prefabricated crystal seed method synthesis ZSM-22 molecular sieve, and preparation process reduces the use of organic formwork agent Amount, and then reduction synthesis cost, and in minimizing roasting process, organic formwork agent decomposes the waste gas the produced pollution to environment；Close The ZSM-22 sieve sample become is regularly arranged nanometer sheet, and this structure shortens reactant and product effectively at molecular sieve Diffusion path in duct away from, improve the diffusion of product, while improving catalytic reaction activity, the generation of suppression carbon distribution, Extend the service life of catalyst.As nano molecular sieve in fine chemistry industry, the catalysis of field of petrochemical industry, adsorb and divide All there is from aspect important using value, be a kind of eco-friendly method synthesizing nano molecular sieve, simple to operate, easily In accomplishing scale production.
Detailed description of the invention two: in present embodiment step one unlike detailed description of the invention one described in step a Tetraethyl orthosilicate with SiO2The mass fraction of meter is 28%.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: institute in step a in present embodiment step one unlike detailed description of the invention two The tetraethyl orthosilicate stated is 1:(3.1～5.0 with the mass ratio of deionized water).Other step and parameter and detailed description of the invention two Identical.
Detailed description of the invention four: walk in present embodiment step one unlike one of detailed description of the invention one to three Rapid f crystallization 2～5h under conditions of temperature 155～165 DEG C.Other step and parameter and detailed description of the invention one to three it One is identical.
Detailed description of the invention five: present embodiment is step 2 step unlike one of detailed description of the invention one to four Ludox described in g is with SiO2The mass fraction of meter is 25.9%.Other step and parameter and detailed description of the invention one to four One of identical.
Detailed description of the invention six: described in present embodiment step 2 step g unlike detailed description of the invention five Ludox is 1:(2～3.15 with the mass ratio of deionized water).Other step and parameter are identical with detailed description of the invention five.
Detailed description of the invention seven: described in present embodiment step 3 unlike one of detailed description of the invention one to six Dried be in 100～120 DEG C of baking ovens be dried 12～15h.Other step and parameter and detailed description of the invention one to six One of identical.
Detailed description of the invention eight: present embodiment step 3 unlike one of detailed description of the invention one to seven is dried Put into after process in Muffle furnace, in 2～4h, be warming up to 500～700 DEG C.Other step and parameter and detailed description of the invention one Identical to one of seven.
Detailed description of the invention nine: present embodiment step 3 unlike one of detailed description of the invention one to eight is dried Putting into after process in Muffle furnace, 3h is warming up to 550 DEG C of roasting 18h.Other step and parameter and detailed description of the invention one to eight One of identical.
Detailed description of the invention ten: present embodiment unlike one of detailed description of the invention one to nine step 3 in temperature Crystallization 30h～40h under conditions of spending 150～170 DEG C.Other step and parameter are identical with one of detailed description of the invention one to nine.
Detailed description of the invention 11: present embodiment step 3 unlike one of detailed description of the invention one to ten is pre- The addition of combinations kind is the 5～20wt.% of mixed gel E mass.Other step and parameter and detailed description of the invention one to One of ten identical.
Embodiment one: the method for the present embodiment prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet is real according to following steps Execute:
One, the preparation of prefabricated crystal seed:
A, weigh 0.276g aluminum sulfate octadecahydrate, 6.166g mass fraction is 28% (with SiO2Meter) tetraethyl orthosilicate, The deionized water of 1,6 hexamethylene diamines of 1g, the potassium hydroxide of 0.54g and 19.167g is as raw material；
B, potassium hydroxide step a weighed and the mixing of 4.787g deionized water, prepare potassium hydroxide aqueous solution after dissolving, Aluminum sulfate octadecahydrate step a weighed and the deionized water mixing of 6.389g, prepare aluminum sulfate aqueous solution after dissolving, will 1,6 hexamethylene diamines and the deionized water of 4.787g that step a weighs mix, and prepare 1,6 hexamethylene diamine aqueous solutions after dissolving, will step Tetraethyl orthosilicate and the deionized water of 3.204g that rapid a weighs are mixed to form suspension；
C, aluminum sulfate aqueous solution step b obtained join in potassium hydroxide aqueous solution, and under the rotating speed of 480r/min Stirring 10min obtains solution A；
D, 1,6 hexamethylene diamine aqueous solutions step b obtained add in the solution A that step c prepares, and 480r/min's Stir 10min under rotating speed, obtain mixture B；
In e, the suspension addition mixture B that will obtain in step b, and stirring 3h obtains under the rotating speed of 400r/min Mixed gel C；
F, mixed gel C step e obtained are placed in the rustless steel closed reactor with polytetrafluoroethyllining lining pad, Crystallization 1.0h under conditions of temperature 160 DEG C, obtains prefabricated crystal seed after being cooled to room temperature；
Two, the preparation of mixed gel:
G, weigh the aluminum sulfate octadecahydrate of 1.047g, 25g SiO2The Ludox that mass fraction is 25.9%, 2.103g hydrogen Potassium oxide and 51.54g deionized water are as raw material；
H, the potassium hydroxide weighed in step g is mixed with 17.18g deionized water, after dissolving, obtains potassium hydroxide aqueous solution, The aluminum sulfate octadecahydrate weighed in step g is mixed with 17.18g deionization, after dissolving, obtains aluminum sulfate aqueous solution, will step The Ludox weighed in rapid g obtains the suspension of silicon dioxide with the deionized water of 17.18g after mixing；
I, the aluminum sulfate aqueous solution obtained in step h is added gradually in potassium hydroxide aqueous solution, and 500r/min's Stir 10min under rotating speed and obtain solution D；
J, the suspension of the silicon dioxide obtained in step h is joined in solution D, and stir under the rotating speed of 755r/min Mix 1.5h and obtain mixed gel E；
Three, crystallization and roasting: the prefabricated crystal seed of 19.126g step one obtained directly (without any process) joins step In the mixed gel E that rapid two obtain, under the rotating speed of 966r/min, stir 10min, be subsequently placed in politef In the rustless steel closed reactor of inner liner, take out after crystallization 38h under conditions of temperature 160 DEG C, be cooled to room temperature, then Being centrifuged, wash 3 times, put in Muffle furnace after being dried 12h in 110 DEG C of baking ovens, 3h is warming up to 550 DEG C of roasting 18h, Obtain ZSM-22 molecular sieve.
It is 20wt.% that pre-crystallization crystal seed described in the present embodiment step 3 accounts for the content of mixed gel F, the ZSM-22 of preparation The SiO of molecular sieve nanometer sheet2/Al2O3It is 71 (mol ratios in mixed gel).
ZSM-22 molecular sieve nanometer sheet X-ray diffraction spectrum prepared by the present embodiment as it is shown in figure 1, as seen from the figure, at 2 θ It is 8.15 °, 10.16 °, 20.3 °, 24.1 °, 24.2 °, the feature diffraction of TON topological structure all occurs at 24.6 ° and 25.7 ° Peak, and without other stray crystal.
ZSM-22 molecular sieve nanometer sheet electron scanning micrograph prepared by the present embodiment as in figure 2 it is shown, as seen from the figure, ZSM-22 molecular sieve prepared by the present embodiment be thickness be the nanometer sheet of 20～30nm.
Embodiment two: in the present embodiment step 2 unlike embodiment one, step g weighs the 18 water sulphuric acid of 0.598g Aluminum, 25g SiO2The Ludox that mass fraction is 25.9%, 2.103g potassium hydroxide and 51.54g deionized water as raw material； Step 3 is crystallization 54h under conditions of temperature 160 DEG C.
The SiO of ZSM-22 molecular sieve nanometer sheet prepared by the present embodiment2/Al2O3It is 120 (mol ratios in mixed gel).
ZSM-22 molecular sieve X-ray diffraction spectrum prepared by the present embodiment as it is shown on figure 3, as seen from the figure, is 8.15 ° at 2 θ, 10.16 °, 20.3 °, 24.1 °, 24.2 °, the characteristic diffraction peak of TON topological structure, and nothing all occur at 24.6 ° and 25.7 ° Other stray crystal.
ZSM-22 molecular sieve electron scanning micrograph prepared by the present embodiment as shown in Figure 4, as seen from the figure, this enforcement ZSM-22 molecular sieve prepared by example be thickness be the nanometer sheet of 20～30nm.

Claims (8)

1. the preparation method of a ZSM-22 molecular sieve nanometer sheet, it is characterised in that be to follow these steps to realize:
One, the preparation of prefabricated crystal seed:
A, weigh aluminum sulfate octadecahydrate, tetraethyl orthosilicate, 1,6 hexamethylene diamines, potassium hydroxide and deionized water as raw material；
B, potassium hydroxide step a weighed and deionized water mixing, prepare potassium hydroxide aqueous solution, by step a after dissolving The aluminum sulfate octadecahydrate weighed and deionized water mixing, after dissolving prepare aluminum sulfate aqueous solution, 1 that step a is weighed, 6 oneself two Amine and deionized water mixing, prepare 1,6 hexamethylene diamine aqueous solutions, tetraethyl orthosilicate step a weighed and deionized water after dissolving It is mixed to form suspension；
C, aluminum sulfate aqueous solution step b obtained join in potassium hydroxide aqueous solution, and 400～600r/min turn The lower stirring 5～10min of speed obtains solution A；
D, 1,6 hexamethylene diamine aqueous solutions step b obtained add in the solution A that step c prepares, and 400～600r/min Rotating speed under stir 5～10min, obtain mixture B；
In e, the suspension addition mixture B that will obtain in step b, and mixed in 300～600r/min stirrings 2～4h Close gel C；
F, mixed gel C step e obtained are placed in the rustless steel closed reactor with polytetrafluoroethyllining lining pad, Crystallization 0.5～7h under conditions of temperature 150～170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature；
Wherein the tetraethyl orthosilicate described in step a is 1:(0.028～0.045 with the mass ratio of aluminum sulfate octadecahydrate)；Described The mass ratio of tetraethyl orthosilicate and 1,6 hexamethylene diamines is 1:(0.162～0.216)；Described tetraethyl orthosilicate and the matter of potassium hydroxide Amount ratio is 1:(0.085～0.11)；Tetraethyl orthosilicate described in step a is with SiO2The mass fraction of meter is 28%, positive silicic acid Ethyl ester is 1:(3.1～5.0 with the mass ratio of deionized water)；
Two, the preparation of mixed gel:
G, weigh aluminum sulfate octadecahydrate, Ludox, potassium hydroxide and deionized water as raw material；
H, the potassium hydroxide weighed in step g is mixed with deionized water, obtain potassium hydroxide aqueous solution after dissolving, by step The aluminum sulfate octadecahydrate weighed in g mixes with deionization, obtains aluminum sulfate aqueous solution after dissolving, the silicon that will weigh in step g Colloidal sol obtains the suspension of silicon dioxide with deionized water after mixing；
I, the aluminum sulfate aqueous solution obtained in step h is joined in potassium hydroxide aqueous solution, and 400～600r/min turn The lower stirring 5～10min of speed obtains solution D；
J, the suspension of the silicon dioxide obtained in step h is joined in solution D, and at the rotating speed of 700～1000r/min Lower stirring 1～2h obtains mixed gel E；
Wherein the Ludox described in step g is 1:(0.022～0.042 with the mass ratio of aluminum sulfate octadecahydrate)；Described silicon is molten Glue is 1:(0.083～0.128 with the mass ratio of potassium hydroxide)；
Three, crystallization and roasting: prefabricated crystal seed step one obtained is added directly in the mixed gel E that step 2 obtains, Under the rotating speed of 700～1200r/min, stir 10～30min, be subsequently placed in the rustless steel with polytetrafluoroethyllining lining pad airtight In reactor, take out after crystallization 10h～72h under conditions of temperature 140～180 DEG C, be cooled to room temperature, then be centrifuged, Washing 3～4 times, put in Muffle furnace after dried, at a temperature of 500～700 DEG C, roasting 3～20h, obtain ZSM-22 Molecular sieve.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step one Middle step f is crystallization 2～5h under conditions of temperature 155～165 DEG C.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step 2 Ludox described in step g is with SiO2The mass fraction of meter is 25.9%.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 3, it is characterised in that step 2 Ludox described in step g is 1:(2～3.15 with the mass ratio of deionized water).
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step 3 Put into after dried in Muffle furnace, in 2～4h, be warming up to 500～700 DEG C.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step 3 Putting into after dried in Muffle furnace, 3h is warming up to 550 DEG C of roasting 18h.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step 3 Crystallization 30h～40h under conditions of temperature 150～170 DEG C.
The preparation method of a kind of ZSM-22 molecular sieve nanometer sheet the most according to claim 1, it is characterised in that step 3 The addition of prefabricated crystal seed is the 5～20wt.% of mixed gel E mass.
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CN109502607A (en) * 2018-11-30 2019-03-22 中国科学院山西煤炭化学研究所 A kind of synthetic method of nanometer of ZSM-22 molecular sieve
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