CN104671253A - Preparation method of ZSM-22 molecular sieve nanosheet - Google Patents
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- 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
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Abstract
The invention discloses a preparation method of a ZSM-22 molecular sieve nanosheet, relates to a preparation method of a ZSM-22 molecular sieve, and aims at solving the problems that an organic template agent adopted by an existing method for synthesizing the ZSM-22 molecular sieve is large in amount and high in cost, and molecular sieve grains exist in a form of an aggregate with a relatively large dimension. The preparation method comprises the following steps: 1, preparing prefabricated seed crystal from aluminum sulfate octadecahydrate, ethyl orthosilicate, 1,6-hexamethylendiamine, potassium hydroxide and deionized water; 2, preparing gel from aluminum sulfate octadecahydrate, silica sol, potassium hydroxide and deionized water; and 3, crystallizing and roasting. The ZSM-22 molecular sieve prepared by the method is in a regularly arranged laminated nanometer structure; the sheet thickness is only about 20nm; the amount of the organic template agent is significantly reduced in the synthesis process; the crystallization time is shortened; and the cost is reduced.
Description
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, pore size is 0.45nm × 0.55nm, there is abundant acidic site and stronger strength of acid, be used for the reaction such as alkene and isomerization of paraffins, alkane aromatization, hydrocracking and alkylbenzene selection alkylation as solid acid catalyst.
People (the Journal of Catalysis such as Johan A., 203 (2001) 213-231) with n-decane to n-tetracosane for model compound, evaluate the Hydroisomerization Properties of Pt/H-ZSM-22, and obtain comparatively excellent isomerization reaction performance.The people such as Biscard report and utilize ZSM-22 molecular sieve as acid carrier in US20040186006, are applied to carbon number and are greater than in the isomerization reaction of the normal paraffin of 10, also embody good isomerization performance.Kumar etc. (Applied Catalysis A:General, 139 (1996) 189-199) report the application of ZSM-22 modification H-ZSM-22 in normal butane aromizing.
The method of current synthesis ZSM-22 molecular sieve has employing organic formwork agent and does not adopt organic formwork agent two kinds of methods.The people (Applied Catalysis, 48 (1989) 137-148) such as Johan A. adopt 1,6 hexanediamines to be template, the ZSM-22 molecular sieve with traditional water heat transfer, but the large usage quantity of template.The people such as Meng Xiangju report at (CN103101924) and adopt crystal seed method not use organic formwork agent to synthesize ZSM-22 molecular sieve, and synthesized ZSM-22 molecular sieve is made up of bar-shaped or Acicular aggregates, and size is between 2 ~ 4 μm.
Owing to adopting in the ZSM-22 molecular sieve process of conventional template agent method synthesis, use a large amount of organic formwork agent, cost is higher, the waste gas that organic formwork agent decomposition produces in roasting process also can to environment, although and adopt crystal seed method not use template also can synthesize ZSM-22 molecular sieve, but the grain-size of molecular sieve is comparatively large, when using as catalyzer can in reaction process because generation carbon distribution inactivation, limit its application in the industry.Therefore, the ZSM-22 molecular sieve adopting novel method synthesis to have nanoscale has great importance.
Summary of the invention
The method that the present invention will solve existing synthesis ZSM-22 molecular sieve uses that consumption of template agent is large, cost is high, zeolite crystal with larger-size aggregate form Problems existing, and provides a kind of remarkable minimizing consumption of template agent, reduces costs, the novel method of synthesis of 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, take aluminum sulfate octadecahydrate, tetraethoxy, 1,6 hexanediamines, potassium hydroxide and deionized water are as raw material;
B, the potassium hydroxide taken by step a and deionized water mix, obtained potassium hydroxide aqueous solution after dissolving, the aluminum sulfate octadecahydrate that step a is taken and deionized water mixing, obtained aluminum sulfate aqueous solution after dissolving, taken by step a 1,6 hexanediamines and deionized water mixing, obtain 1 after dissolving, the 6 hexanediamine aqueous solution, the tetraethoxy taken by step a and deionized water are mixed to form suspension liquid;
C, the aluminum sulfate aqueous solution obtained by step b join in potassium hydroxide aqueous solution, and stirring 5 ~ 10min obtains solution A under the rotating speed of 400 ~ 600r/min;
D, 1, the 6 hexanediamine aqueous solution obtained by step b add in the obtained solution A of step c, and stir 5 ~ 10min under the rotating speed of 400 ~ 600r/min, obtain mixture B;
E, the suspension liquid obtained in step b to be added in mixture B, and stir 2 ~ 4h at 300 ~ 600r/min and obtain mixed gel C;
F, the mixed gel C obtained by step e are placed in the stainless steel closed reactor with polytetrafluoroethyllining lining pad, and crystallization 0.5 ~ 7h under the condition of temperature 150 ~ 170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature;
Tetraethoxy wherein described in step a and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.028 ~ 0.045); Described tetraethoxy and 1, the mass ratio of 6 hexanediamines is 1:(0.162 ~ 0.216); Described tetraethoxy and the mass ratio of potassium hydroxide are 1:(0.085 ~ 0.11);
Two, the preparation of mixed gel:
G, take aluminum sulfate octadecahydrate, silicon sol, potassium hydroxide and deionized water as raw material;
H, the potassium hydroxide taken in step g to be mixed with deionized water, potassium hydroxide aqueous solution is obtained after dissolving, the aluminum sulfate octadecahydrate taken in step g is mixed with deionization, obtain aluminum sulfate aqueous solution after dissolving, after being mixed with deionized water by the silicon sol taken in step g, obtain the suspension liquid of silicon-dioxide;
I, the aluminum sulfate aqueous solution obtained in step h to be joined in potassium hydroxide aqueous solution, and under the rotating speed of 400 ~ 600r/min, stir 5 ~ 10min obtain solution D;
J, the suspension liquid of the silicon-dioxide obtained in step h to be joined in solution D, and under the rotating speed of 700 ~ 1000r/min, stir 1 ~ 2h obtain mixed gel E;
Silicon sol wherein described in step g and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.022 ~ 0.042); Described silicon sol and the mass ratio of potassium hydroxide are 1:(0.083 ~ 0.128);
Three, crystallization and roasting: prefabricated crystal seed step one obtained directly joins in the mixed gel E that step 2 obtains, 10 ~ 30min is stirred under the rotating speed of 700 ~ 1200r/min, then the stainless steel closed reactor with polytetrafluoroethyllining lining pad is placed in, take out after crystallization 10h ~ 72h under the condition of temperature 140 ~ 180 DEG C, be cooled to room temperature, carry out again centrifugal, washing 3 ~ 4 times, retort furnace is put into after drying treatment, at the roasting temperature 3 ~ 20h of 500 ~ 700 DEG C, obtain ZSM-22 molecular sieve.
The method of the present invention's prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet comprises following beneficial effect:
1, the present invention adopts prefabricated crystal seed method to prepare ZSM-22 molecular sieve nanometer sheet, the bar-shaped ZSM-22 Molecular sieve aggregate that its pattern and conventional hydrothermal method are synthesized has marked difference, the thickness of nanometer sheet only has about 20nm, reactant and the diffusion of product in molecular sieve pore passage can be improved significantly as catalyzer, improve the accessibility of catalyst activity position, thus increase substantially its catalytic activity, and effectively suppress the generation of carbon distribution, the work-ing life of extending catalyst.
2, the organic formwork dosage used when the present invention synthesizes ZSM-22 molecular sieve nanometer sheet significantly reduces, template and SiO
2mol ratio be reduced to (0.03 ~ 0.06): 1, be only 1/5 ~ 1/10 of traditional method consumption, reduce cost significantly.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrum of ZSM-22 molecular sieve nanometer sheet prepared by embodiment one;
Fig. 2 is the electron scanning micrograph of ZSM-22 molecular sieve nanometer sheet prepared by embodiment one;
Fig. 3 is the X-ray diffraction spectrum of ZSM-22 molecular sieve nanometer sheet prepared by embodiment two;
Fig. 4 is the electron scanning micrograph of ZSM-22 molecular sieve nanometer sheet prepared by embodiment two.
Embodiment
Embodiment one: the method for present embodiment prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet is implemented according to following steps:
One, the preparation of prefabricated crystal seed:
A, take aluminum sulfate octadecahydrate, tetraethoxy, 1,6 hexanediamines, potassium hydroxide and deionized water are as raw material;
B, the potassium hydroxide taken by step a and deionized water mix, obtained potassium hydroxide aqueous solution after dissolving, the aluminum sulfate octadecahydrate that step a is taken and deionized water mixing, obtained aluminum sulfate aqueous solution after dissolving, taken by step a 1,6 hexanediamines and deionized water mixing, obtain 1 after dissolving, the 6 hexanediamine aqueous solution, the tetraethoxy taken by step a and deionized water are mixed to form suspension liquid;
C, the aluminum sulfate aqueous solution obtained by step b join in potassium hydroxide aqueous solution, and stirring 5 ~ 10min obtains solution A under the rotating speed of 400 ~ 600r/min;
D, 1, the 6 hexanediamine aqueous solution obtained by step b add in the obtained solution A of step c, and stir 5 ~ 10min under the rotating speed of 400 ~ 600r/min, obtain mixture B;
E, the suspension liquid obtained in step b to be added in mixture B, and stir 2 ~ 4h at 300 ~ 600r/min and obtain mixed gel C;
F, the mixed gel C obtained by step e are placed in the stainless steel closed reactor with polytetrafluoroethyllining lining pad, and crystallization 0.5 ~ 7h under the condition of temperature 150 ~ 170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature;
Tetraethoxy wherein described in step a and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.028 ~ 0.045); Described tetraethoxy and 1, the mass ratio of 6 hexanediamines is 1:(0.162 ~ 0.216); Described tetraethoxy and the mass ratio of potassium hydroxide are 1:(0.085 ~ 0.11);
Two, the preparation of mixed gel:
G, take aluminum sulfate octadecahydrate, silicon sol, potassium hydroxide and deionized water as raw material;
H, the potassium hydroxide taken in step g to be mixed with deionized water, potassium hydroxide aqueous solution is obtained after dissolving, the aluminum sulfate octadecahydrate taken in step g is mixed with deionization, obtain aluminum sulfate aqueous solution after dissolving, after being mixed with deionized water by the silicon sol taken in step g, obtain the suspension liquid of silicon-dioxide;
I, the aluminum sulfate aqueous solution obtained in step h to be joined in potassium hydroxide aqueous solution, and under the rotating speed of 400 ~ 600r/min, stir 5 ~ 10min obtain solution D;
J, the suspension liquid of the silicon-dioxide obtained in step h to be joined in solution D, and under the rotating speed of 700 ~ 1000r/min, stir 1 ~ 2h obtain mixed gel E;
Silicon sol wherein described in step g and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.022 ~ 0.042); Described silicon sol and the mass ratio of potassium hydroxide are 1:(0.083 ~ 0.128);
Three, crystallization and roasting: prefabricated crystal seed step one obtained directly joins in the mixed gel E that step 2 obtains, 10 ~ 30min is stirred under the rotating speed of 700 ~ 1200r/min, then the stainless steel closed reactor with polytetrafluoroethyllining lining pad is placed in, take out after crystallization 10h ~ 72h under the condition of temperature 140 ~ 180 DEG C, be cooled to room temperature, carry out again centrifugal, washing 3 ~ 4 times, retort furnace is put into after drying treatment, at the roasting temperature 3 ~ 20h of 500 ~ 700 DEG C, obtain ZSM-22 molecular sieve.
Present embodiment adopts prefabricated crystal seed method to synthesize ZSM-22 molecular sieve, and preparation process reduces the consumption of organic formwork agent, and then reduces synthesis cost, and the waste gas that in minimizing roasting process, organic formwork agent decomposition produces is to the pollution of environment; The ZSM-22 sieve sample of synthesis is regularly arranged nanometer sheet, this structure shortens reactant and the diffusion path distance of product in molecular sieve pore passage effectively, improves the diffusion of product, while improving catalytic reaction activity, suppress the generation of carbon distribution, the work-ing life of extending catalyst.All having important using value as nano molecular sieve in the catalysis of fine chemistry industry, field of petrochemical industry, absorption with in being separated, is a kind of eco-friendly method of synthesis of nano molecular sieve, simple to operate, is easy to accomplish scale production.
Embodiment two: present embodiment and embodiment one unlike the tetraethoxy in step one described in step a with SiO
2the massfraction of meter is 28%.Other step and parameter identical with embodiment one.
Embodiment three: present embodiment and embodiment two are 1:(3.1 ~ 5.0 unlike the mass ratio of the tetraethoxy in step one described in step a and deionized water).Other step and parameter identical with embodiment two.
Embodiment four: one of present embodiment and embodiment one to three are unlike the crystallization 2 ~ 5h under the condition of temperature 155 ~ 165 DEG C of step f in step one.Other step and parameter identical with one of embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike the silicon sol described in step 2 step g with SiO
2the massfraction of meter is 25.9%.Other step and parameter identical with one of embodiment one to four.
Embodiment six: present embodiment and embodiment five are 1:(2 ~ 3.15 unlike the mass ratio of the silicon sol described in step 2 step g and deionized water).Other step and parameter identical with embodiment five.
Embodiment seven: one of present embodiment and embodiment one to six are dry 12 ~ 15h in 100 ~ 120 DEG C of baking ovens unlike the drying treatment described in step 3.Other step and parameter identical with one of embodiment one to six.
Embodiment eight: one of present embodiment and embodiment one to seven put into retort furnace unlike after step 3 drying treatment, is warming up to 500 ~ 700 DEG C in 2 ~ 4h.Other step and parameter identical with one of embodiment one to seven.
Embodiment nine: one of present embodiment and embodiment one to eight put into retort furnace unlike after step 3 drying treatment, 3h is warming up to 550 DEG C of roasting 18h.Other step and parameter identical with one of embodiment one to eight.
Embodiment ten: one of present embodiment and embodiment one to nine are unlike step 3 crystallization 30h ~ 40h under the condition of temperature 150 ~ 170 DEG C.Other step and parameter identical with one of embodiment one to nine.
Embodiment 11: one of present embodiment and embodiment one to ten are 5 ~ 20wt.% of mixed gel E quality unlike the add-on of the prefabricated crystal seed of step 3.Other step and parameter identical with one of embodiment one to ten.
Embodiment one: the method for the present embodiment prefabricated crystal seed method synthesis ZSM-22 molecular sieve nanometer sheet is implemented according to following steps:
One, the preparation of prefabricated crystal seed:
A, take 0.276g aluminum sulfate octadecahydrate, 6.166g massfraction is 28% (with SiO
2meter) the deionized water of tetraethoxy, 1,6 hexanediamines of 1g, the potassium hydroxide of 0.54g and 19.167g as raw material;
B, the potassium hydroxide taken by step a and 4.787g deionized water mix, obtained potassium hydroxide aqueous solution after dissolving, the deionized water mixing of the aluminum sulfate octadecahydrate that step a is taken and 6.389g, obtained aluminum sulfate aqueous solution after dissolving, taken by step a 1, the deionized water mixing of 6 hexanediamines and 4.787g, obtains 1 after dissolving, the 6 hexanediamine aqueous solution, the tetraethoxy taken by step a and the deionized water of 3.204g are mixed to form suspension liquid;
C, the aluminum sulfate aqueous solution obtained by step b join in potassium hydroxide aqueous solution, and under the rotating speed of 480r/min, stir 10min obtain solution A;
D, 1, the 6 hexanediamine aqueous solution obtained by step b add in the obtained solution A of step c, and stir 10min under the rotating speed of 480r/min, obtain mixture B;
E, the suspension liquid obtained in step b to be added in mixture B, and under the rotating speed of 400r/min, stir 3h obtain mixed gel C;
F, the mixed gel C obtained by step e are placed in the stainless steel closed reactor with polytetrafluoroethyllining lining pad, and crystallization 1.0h under the condition of temperature 160 DEG C, obtains prefabricated crystal seed after being cooled to room temperature;
Two, the preparation of mixed gel:
G, the aluminum sulfate octadecahydrate taking 1.047g, 25g SiO
2massfraction be 25.9% silicon sol, 2.103g potassium hydroxide and 51.54g deionized water be as raw material;
H, the potassium hydroxide taken in step g to be mixed with 17.18g deionized water, potassium hydroxide aqueous solution is obtained after dissolving, the aluminum sulfate octadecahydrate taken in step g is mixed with 17.18g deionization, obtain aluminum sulfate aqueous solution after dissolving, after being mixed with the deionized water of 17.18g by the silicon sol taken in step g, obtain the suspension liquid of silicon-dioxide;
I, the aluminum sulfate aqueous solution obtained in step h to be joined in potassium hydroxide aqueous solution gradually, and under the rotating speed of 500r/min, stir 10min obtain solution D;
J, the suspension liquid of the silicon-dioxide obtained in step h to be joined in solution D, and under the rotating speed of 755r/min, stir 1.5h obtain mixed gel E;
Three, crystallization and roasting: the prefabricated crystal seed of 19.126g step one obtained directly (without any process) joins in the mixed gel E that step 2 obtains, 10min is stirred under the rotating speed of 966r/min, then the stainless steel closed reactor with polytetrafluoroethyllining lining pad is placed in, take out after crystallization 38h under the condition of temperature 160 DEG C, be cooled to room temperature, carry out again centrifugal, washing 3 times, retort furnace is put into after dry 12h in 110 DEG C of baking ovens, 3h is warming up to 550 DEG C of roasting 18h, obtains ZSM-22 molecular sieve.
The content that pre-crystallization crystal seed described in the present embodiment step 3 accounts for mixed gel F is 20wt.%, the SiO of the ZSM-22 molecular sieve nanometer sheet of preparation
2/ Al
2o
3be 71 (mol ratios in mixed gel).
ZSM-22 molecular sieve nanometer sheet X-ray diffraction spectrum prepared by the present embodiment as shown in Figure 1, as seen from the figure, is 8.15 ° at 2 θ, 10.16 °, 20.3 °, 24.1 °, 24.2 °, locate the characteristic diffraction peak all occurring TON topological framework for 24.6 ° and 25.7 °, and without other stray crystal.
ZSM-22 molecular sieve nanometer sheet electron scanning micrograph prepared by the present embodiment as shown in Figure 2, as seen from the figure, the nanometer sheet of ZSM-22 molecular sieve prepared by the present embodiment to be thickness be 20 ~ 30nm.
Embodiment two: the present embodiment and embodiment one take aluminum sulfate octadecahydrate, the 25g SiO of 0.598g unlike step g in step 2
2massfraction be 25.9% silicon sol, 2.103g potassium hydroxide and 51.54g deionized water be as raw material; Step 3 crystallization 54h under the condition of temperature 160 DEG C.
The SiO of ZSM-22 molecular sieve nanometer sheet prepared by the present embodiment
2/ Al
2o
3be 120 (mol ratios in mixed gel).
ZSM-22 molecular sieve X-ray diffraction spectrum prepared by the present embodiment as shown in Figure 3, as seen from the figure, is 8.15 ° at 2 θ, 10.16 °, 20.3 °, 24.1 °, 24.2 °, locate the characteristic diffraction peak all occurring TON topological framework for 24.6 ° and 25.7 °, and without 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, the nanometer sheet of ZSM-22 molecular sieve prepared by the present embodiment to be thickness be 20 ~ 30nm.
Claims (10)
1. a preparation method for ZSM-22 molecular sieve nanometer sheet, it is characterized in that following these steps to realize:
One, the preparation of prefabricated crystal seed:
A, take aluminum sulfate octadecahydrate, tetraethoxy, 1,6 hexanediamines, potassium hydroxide and deionized water are as raw material;
B, the potassium hydroxide taken by step a and deionized water mix, obtained potassium hydroxide aqueous solution after dissolving, the aluminum sulfate octadecahydrate that step a is taken and deionized water mixing, obtained aluminum sulfate aqueous solution after dissolving, taken by step a 1,6 hexanediamines and deionized water mixing, obtain 1 after dissolving, the 6 hexanediamine aqueous solution, the tetraethoxy taken by step a and deionized water are mixed to form suspension liquid;
C, the aluminum sulfate aqueous solution obtained by step b join in potassium hydroxide aqueous solution, and stirring 5 ~ 10min obtains solution A under the rotating speed of 400 ~ 600r/min;
D, 1, the 6 hexanediamine aqueous solution obtained by step b add in the obtained solution A of step c, and stir 5 ~ 10min under the rotating speed of 400 ~ 600r/min, obtain mixture B;
E, the suspension liquid obtained in step b to be added in mixture B, and stir 2 ~ 4h at 300 ~ 600r/min and obtain mixed gel C;
F, the mixed gel C obtained by step e are placed in the stainless steel closed reactor with polytetrafluoroethyllining lining pad, and crystallization 0.5 ~ 7h under the condition of temperature 150 ~ 170 DEG C, obtains prefabricated crystal seed after being cooled to room temperature;
Tetraethoxy wherein described in step a and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.028 ~ 0.045); Described tetraethoxy and 1, the mass ratio of 6 hexanediamines is 1:(0.162 ~ 0.216); Described tetraethoxy and the mass ratio of potassium hydroxide are 1:(0.085 ~ 0.11);
Two, the preparation of mixed gel:
G, take aluminum sulfate octadecahydrate, silicon sol, potassium hydroxide and deionized water as raw material;
H, the potassium hydroxide taken in step g to be mixed with deionized water, potassium hydroxide aqueous solution is obtained after dissolving, the aluminum sulfate octadecahydrate taken in step g is mixed with deionization, obtain aluminum sulfate aqueous solution after dissolving, after being mixed with deionized water by the silicon sol taken in step g, obtain the suspension liquid of silicon-dioxide;
I, the aluminum sulfate aqueous solution obtained in step h to be joined in potassium hydroxide aqueous solution, and under the rotating speed of 400 ~ 600r/min, stir 5 ~ 10min obtain solution D;
J, the suspension liquid of the silicon-dioxide obtained in step h to be joined in solution D, and under the rotating speed of 700 ~ 1000r/min, stir 1 ~ 2h obtain mixed gel E;
Silicon sol wherein described in step g and the mass ratio of aluminum sulfate octadecahydrate are 1:(0.022 ~ 0.042); Described silicon sol and the mass ratio of potassium hydroxide are 1:(0.083 ~ 0.128);
Three, crystallization and roasting: prefabricated crystal seed step one obtained directly joins in the mixed gel E that step 2 obtains, 10 ~ 30min is stirred under the rotating speed of 700 ~ 1200r/min, then the stainless steel closed reactor with polytetrafluoroethyllining lining pad is placed in, take out after crystallization 10h ~ 72h under the condition of temperature 140 ~ 180 DEG C, be cooled to room temperature, carry out again centrifugal, washing 3 ~ 4 times, retort furnace is put into after drying treatment, at the roasting temperature 3 ~ 20h of 500 ~ 700 DEG C, obtain ZSM-22 molecular sieve.
2. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, is characterized in that tetraethoxy in step one described in step a is with SiO
2the massfraction of meter is 28%.
3. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 2, is characterized in that the mass ratio of tetraethoxy in step one described in step a and deionized water is 1:(3.1 ~ 5.0).
4. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, is characterized in that step f crystallization 2 ~ 5h under the condition of temperature 155 ~ 165 DEG C in step one.
5. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, is characterized in that silicon sol described in step 2 step g is with SiO
2the massfraction of meter is 25.9%.
6. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 5, is characterized in that the mass ratio of silicon sol described in step 2 step g and deionized water is 1:(2 ~ 3.15).
7. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, puts into retort furnace after it is characterized in that step 3 drying treatment, is warming up to 500 ~ 700 DEG C in 2 ~ 4h.
8. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, put into retort furnace after it is characterized in that step 3 drying treatment, 3h is warming up to 550 DEG C of roasting 18h.
9. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, is characterized in that step 3 crystallization 30h ~ 40h under the condition of temperature 150 ~ 170 DEG C.
10. the preparation method of a kind of ZSM-22 molecular sieve nanometer sheet according to claim 1, is characterized in that the add-on of the prefabricated crystal seed of step 3 is 5 ~ 20wt.% of mixed gel E quality.
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| CN105129814A (en) * | 2015-09-06 | 2015-12-09 | 太原理工大学 | Preparation method for ZSM-22 molecular sieve |
| CN106807441A (en) * | 2015-11-27 | 2017-06-09 | 中国石油化工股份有限公司 | A kind of catalyst and its preparation and application that propylene is prepared for propane direct dehydrogenation |
| CN107285331A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | Mesoporous ZSM-22 molecular sieves, its synthetic method and its application |
| CN107285332A (en) * | 2016-04-12 | 2017-10-24 | 中国石油化工股份有限公司 | The synthetic method of ZSM-22 molecular sieves and its ZSM-22 molecular sieves of synthesis |
| 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 |
| US10843930B1 (en) | 2019-11-13 | 2020-11-24 | Saudi Arabian Oil Company | Systems and methods for synthesis of ZSM-22 zeolite |
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| US11618013B2 (en) | 2021-03-19 | 2023-04-04 | Saudi Arabian Oil Company | Systems and methods for the synthesizing ZSM-22 zeolites |
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| CN113233472A (en) * | 2021-06-11 | 2021-08-10 | 福州大学 | Synthesis method of nano small-grain ZSM-22 molecular sieve |
| CN115872415A (en) * | 2023-02-17 | 2023-03-31 | 河北鑫鹏新材料科技有限公司 | Nano ZSM-5 molecular sieve and preparation method thereof |
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