CN106430236B - The preparation method of mesoporous ZSM-5 molecular sieve - Google Patents
The preparation method of mesoporous ZSM-5 molecular sieve Download PDFInfo
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- CN106430236B CN106430236B CN201610848260.3A CN201610848260A CN106430236B CN 106430236 B CN106430236 B CN 106430236B CN 201610848260 A CN201610848260 A CN 201610848260A CN 106430236 B CN106430236 B CN 106430236B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- 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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- 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
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Abstract
The invention discloses a kind of preparation methods of 5 molecular sieves of mesoporous ZSM, are related to molecular sieve.This method is：1. a certain amount of white carbon or silica gel, 4-propyl bromide, ammonium acid fluoride and aluminum sulfate octadecahydrate are sufficiently mixed grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, under conditions of static state, 145 DEG C of crystallization 35 days；2. the product of step 1. gained is moved in beaker, adds the water of certain proportion amount, stir 12 hours；3. the product of step 2. gained is washed with deionized water, it is dry, you can to obtain mesoporous ZSM 5.This method feature forms solution simply by water and remaining raw material is added, and then manufactures the mesoporous of 5 molecular sieves of ZSM, this is both simple and economic post-processing approach；And good crystallinity and few defect are maintained, has preferable catalytic activity and longer service life.
Description
Technical field
The present invention relates to the preparation methods of molecular sieve more particularly to mesoporous ZSM-5 molecular sieve.
Background technology
ZSM-5 molecular sieve (R.J Argauer, G.R Landolt, Mobil oil corp, US3702886A, 1972),
Since it stablizes with higher silica alumina ratio, unique pore passage structure, larger specific surface area and excellent heat and hydrothermal structural
Property, it is obtained in the petrochemical process such as the shape slective cracking of hydro carbons, alkylation, isomerization, disproportionation, catalytic dewaxing and etherificate
Extremely it is widely applied.But with the increasingly reduction of petroleum resources, the increasingly increase of consumption of petroleum amount is catalyzed PETROLEUM PROCESSING
More stringent requirements are proposed for the catalytic efficiency of agent, and the aperture size of micro porous molecular sieve limits bigger molecule and enters its duct and work
Property central contact, is unfavorable for the reaction and abjection of macromolecular, therefore it is hot spot instantly to synthesize mesoporous ZSM-5 molecular sieve.Contain
There is mesoporous ZSM-5 in catalysis is reacted, there is mass transfer advantage, shorten diffusion path of the reactant molecule inside molecular sieve,
The activated centre for making it easier to touch molecular sieve inner surface, to improve the catalytic activity of material.And in traditional alkalinity
Under the conditions of during hydro-thermal gel synthetic ZSM-5 zeolite molecular sieve, bromination organic formwork agent needs to hand over using silver oxide or ion
Column is changed to be converted into hydroxide organic formwork agent, reaction cost increases；Silicon source and the silicon source hydrolytic process in alkaline solution take
Very long, efficiency is low and energy consumption is larger；Simultaneously because needing that hydrofluoric acid is added to introduce fluorine ion mineralizer, and bring to testing people
Harm in the health of member, therefore it is very to seek suitable reducing cost, improve efficiency and safer synthetic method
It is necessary
2012, Zhejiang University Xiao Fengshou professors seminar developed one kind and directly grinding solvent-free item by Solid raw materials
Method (Xiao Fengshou etc., CN102627287) of synthesis of molecular sieve this synthetic method significantly simplifies traditional hydro-thermal under part
Synthetic method improves yield, reduces production cost, has saved the energy, reduces the pollution to environment, has prodigious industry to answer
Use potentiality.
Invention content
The purpose of the present invention be that overcome the shortcomings of problems of the prior art and, provide it is a kind of reduce cost,
Improve the preparation method of efficiency and safer mesoporous ZSM-5 molecular sieve.
In order to solve the above technical problems, the solution of the present invention is：
In traditional synthetic schemes, alkaline source is provided with ammonium salt；And it is by using NH in the present invention4HF2To realize
This important synthesis path of F as mineralizer (non-alkaline synthetic method)；And water process is carried out after the completion of reaction, this
One step plays the role of the mesoporous formation of molecular sieve critically important.
Specifically, this method includes the following steps：
1. a certain amount of white carbon or silica gel, 4-propyl bromide, ammonium acid fluoride and aluminum sulfate octadecahydrate are sufficiently mixed
Grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, under conditions of static state,
145 DEG C of crystallization 3-5 days；
2. the product of step 1. gained is moved in beaker, adds the water of certain proportion amount, stir 12 hours；
3. the product of step 2. gained is washed with deionized water, it is dry, you can to obtain mesoporous ZSM-5；
The molar ratio of reaction raw materials is：
White carbon：0.25 4-propyl bromide：2.0 ammonium acid fluoride：(0.003-0.025) aluminum sulfate octadecahydrate；
Silica gel：0.25 4-propyl bromide：2.0 ammonium acid fluoride：(0.003-0.025) aluminum sulfate octadecahydrate.
The present invention has following advantages and good effect：
1. using 4-propyl bromide organic formwork agent, hydrogen-oxygen need not be converted into using silver oxide or ion exchange column
Change organic formwork agent, reactant cost reduction；
2. hydrofluoric acid need not be added to introduce fluorine ion mineralizer, reduce to the harm in experimenter's health；
3. simply by water and remaining raw material formation solution is added, and then manufacturing the mesoporous of ZSM-5 molecular sieve, this is both
Simple and economic post-processing approach obtains mesopore molecular sieve；
4. the mesoporous ZSM-5 zeolite molecular sieve that the present invention obtains maintains good crystallinity and few defect, so
Have preferable catalytic activity and longer service life.
Description of the drawings
Fig. 1 a are the XRD spectra (silicon source is white carbon, silica alumina ratio 50) of this method sintetics,
Fig. 1 b are the XRD spectra (silicon source is white carbon, silica alumina ratio 100) of this method sintetics,
Fig. 1 c be this method sintetics XRD spectra (silicon source is silica gel, silica alumina ratio be 50),
Fig. 1 d be this method sintetics XRD spectra (silicon source is silica gel, 100) silica alumina ratio is；
Fig. 2 a are the SEM photograph (silicon source is white carbon, silica alumina ratio 50) of this method sintetics,
Fig. 2 b are the SEM photograph (silicon source is white carbon, silica alumina ratio 100) of this method sintetics,
Fig. 2 c are the SEM photograph (silicon source is silica gel, silica alumina ratio 50) of this method sintetics,
Fig. 2 d are the SEM photograph of this method sintetics (silicon source is silica gel, silica alumina ratio 100).
Abbreviation
XRD：X-ray diffraction；
SEM：Scanning electron microscope.
Specific implementation mode
It is described in detail below in conjunction with the accompanying drawings with embodiment：
Embodiment 1：4-propyl bromide is directed agents, and silica gel is silicon source, and sial rate of charge is 50, and solventless method solid phase is closed
At ZSM-5 molecular sieve
1. weighing 1.2g silica gel, 1.33g 4-propyl bromides, 2.28g ammonium acid fluorides, 0.133g aluminum sulfate octadecahydrates successively
It is sufficiently mixed grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, in static state
Under the conditions of, 145 DEG C of crystallization 3 days；
2. 1. product that step is walked to gained moves in beaker, add the water of 50ml, stirs 12 hours；
3. by step, 2. products therefrom is washed with deionized water, dry, you can to obtain mesoporous ZSM-5；
The molar ratio of reaction raw materials is：
Silica gel：0.25 4-propyl bromide：2.0 ammonium acid fluoride：0.01 aluminum sulfate octadecahydrate.
Through X-ray diffraction analysis, its structure is ZSM-5 zeolite molecular sieve, and be can be seen that by stereoscan photograph
To be typical ZSM-5 patterns crystal grain, such as Fig. 1 a, Fig. 2 a.
Embodiment 2：4-propyl bromide is directed agents, and silica gel is silicon source, and sial rate of charge is 100, solventless method solid phase
Synthesize ZSM-5 molecular sieve
1. weighing 1.2g silica gel, 1.33g 4-propyl bromides, 2.28g ammonium acid fluorides, 0.066g aluminum sulfate octadecahydrates successively
It is sufficiently mixed grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, in static state
Under the conditions of, 145 DEG C of crystallization 3 days；
2. 1. product that step is walked to gained moves in beaker, add the water of 50ml, stirs 12 hours；
3. by step, 2. products therefrom is washed with deionized water, dry, you can to obtain mesoporous ZSM-5；Reaction raw materials
Molar ratio be：
Silica gel：0.25 4-propyl bromide：2.0 ammonium acid fluoride：0.005 aluminum sulfate octadecahydrate.
Through X-ray diffraction analysis, its structure is ZSM-5 zeolite molecular sieve, and be can be seen that by stereoscan photograph
To be typical ZSM-5 patterns crystal grain, such as Fig. 1 b, Fig. 2 b.
Embodiment 3：4-propyl bromide is directed agents, and white carbon is silicon source, and sial rate of charge is 50, solventless method solid phase
Synthesize ZSM-5 molecular sieve
1. weighing 1.2g white carbons, 1.33g 4-propyl bromides, 2.28g ammonium acid fluorides, 0.133g 18 water sulfuric acid successively
Aluminium is sufficiently mixed grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, in static state
Under conditions of, 145 DEG C of crystallization 3 days
2. the product of step 1. gained is moved in beaker, adds 50ml water, stir 12 hours
3. by step, 2. products therefrom is washed with deionized water, dry, you can to obtain mesoporous ZSM-5, reaction raw materials
Molar ratio be：
White carbon：0.25 4-propyl bromide：2.0 ammonium acid fluoride：0.01 aluminum sulfate octadecahydrate.
Through X-ray diffraction analysis, its structure is ZSM-5 zeolite molecular sieve, and be can be seen that by stereoscan photograph
To be typical ZSM-5 patterns crystal grain, such as Fig. 1 c, Fig. 2 c.
Embodiment 4：4-propyl bromide is directed agents, and white carbon is silicon source, and sial rate of charge is 100, and solventless method is solid
It is combined to ZSM-5 molecular sieve
1. weighing 1.2g white carbons, 1.33g 4-propyl bromides, 2.28g ammonium acid fluorides, 0.066g 18 water sulfuric acid successively
Aluminium is sufficiently mixed grinding, then the mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron, in static state
Under conditions of, 145 DEG C of crystallization 3 days
2. the product of step 1. gained is moved in beaker, adds the water of 50ml, stir 12 hours
3. by step, 2. products therefrom is washed with deionized water, dry, you can to obtain mesoporous ZSM-5 reaction raw materials
Molar ratio is：
SiO2(white carbon)：0.25 4-propyl bromide：2.0 ammonium acid fluoride：0.005 aluminum sulfate octadecahydrate
Through X-ray diffraction analysis, its structure is ZSM-5 zeolite molecular sieve, and be can be seen that by stereoscan photograph
To be typical ZSM-5 patterns crystal grain, such as Fig. 1 d, Fig. 2 d.
Claims (1)
1. a kind of preparation method of mesoporous ZSM-5 molecular sieve, it is characterised in that include the following steps：
1. a certain amount of white carbon or silica gel, 4-propyl bromide, ammonium acid fluoride and aluminum sulfate octadecahydrate are sufficiently mixed grinding,
The mixture material after grinding is put into polytetrafluoroethyllining lining stainless steel cauldron again, under conditions of static state, 145 DEG C of crystalline substances
Change 3-5 days；
2. the product of step 1. gained is moved in beaker, adds the water of certain proportion amount, stir 12 hours；
3. the product of step 2. gained is washed with deionized water, it is dry, you can to obtain mesoporous ZSM-5；
The molar ratio of reaction raw materials is：
White carbon：0.25 4-propyl bromide：2.0 ammonium acid fluoride：(0.003-0.025) aluminum sulfate octadecahydrate；
Silica gel：0.25 4-propyl bromide：2.0 ammonium acid fluoride：(0.003-0.025) aluminum sulfate octadecahydrate.
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| CN107349957A (en) * | 2017-08-23 | 2017-11-17 | 重庆工业职业技术学院 | A kind of preparation method of copper-based micro- mesoporous catalyst |
| CN112456509A (en) * | 2020-12-10 | 2021-03-09 | 汕头大学 | Method for synthesizing ZSM-5 molecular sieve in one step in solid phase system |
| CN115784253B (en) * | 2022-11-30 | 2024-03-15 | 中国科学院青岛生物能源与过程研究所 | Aluminum-rich ZSM-5 zeolite molecular sieve microsphere, and method and application for synthesizing same in one step in high-fluorine system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN102674392A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Hollow capsule nano ZSM-5 molecular sieve and preparation method thereof |
| CN102992343A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Method for synthesizing zeolite molecular sieve via solid phase method without organic template |
| CN104418356A (en) * | 2013-09-06 | 2015-03-18 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 molecular sieve |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102627287A (en) * | 2012-04-20 | 2012-08-08 | 浙江大学 | Method for synthesizing molecular sieve under solvent-free condition through grinding solid phase raw materials |
| CN102674392A (en) * | 2012-05-16 | 2012-09-19 | 上海师范大学 | Hollow capsule nano ZSM-5 molecular sieve and preparation method thereof |
| CN102992343A (en) * | 2012-12-09 | 2013-03-27 | 浙江大学 | Method for synthesizing zeolite molecular sieve via solid phase method without organic template |
| CN104418356A (en) * | 2013-09-06 | 2015-03-18 | 中国石油化工股份有限公司 | Method for preparing ZSM-5 molecular sieve |
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