CN104261427A - Preparation method of house-of-cards-like hierarchical porous ZSM-5 molecular sieve - Google Patents
Preparation method of house-of-cards-like hierarchical porous ZSM-5 molecular sieve Download PDFInfo
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- CN104261427A CN104261427A CN201410520157.7A CN201410520157A CN104261427A CN 104261427 A CN104261427 A CN 104261427A CN 201410520157 A CN201410520157 A CN 201410520157A CN 104261427 A CN104261427 A CN 104261427A
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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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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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- 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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- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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Abstract
The invention belongs to the technical field of synthesis of inorganic porous materials and particularly relates to a preparation method of a house-of-cards-like hierarchical porous ZSM-5 molecular sieve which is low in cost, environment-friendly and fast. The preparation method comprises the following steps: adding an inorganic alkali source and an aluminum source into deionized water, and adding a proper amount of N-methyl-2-pyrrolidone (NMP); then, slowly adding a silicon source; fully and uniformly stirring; and synthesizing a house-of-cards-like hierarchical porous HCL-ZSM-5 molecular sieve by a one-step hydrothermal method. The molecular sieve has remarkable hierarchical porous structural characteristics, is large in external surface area, strong in acidity and good in stability, and has wide application prospects in the fields of catalysis, adsorption, separation and the like. In an alkaline ZSM-5 synthetic system without an organic template, by using non-toxic and cheap NMP as a structural guiding agent which is used for replacing an expensive macromolecular organic template, the method is an economic, efficient and environment-friendly synthetic method which is expected to be applied to large-scale commercial production.
Description
Technical field
The invention belongs to the preparing technical field of inorganic porous material, be specifically related to the preparation method of a kind of low cost, green, fast " plug-in card " type multi-stage porous ZSM-5 molecular sieve.
Background technology
1972, Mobil company of the U.S. (USP3702886) reported first a kind of high-silica zeolite with three-dimensional straight pore passage structure--ZSM-5 zeolite molecular sieve, unique and homogeneous duct structure gives its good shape selective catalysis effect, is widely used in the catalytic fields such as refining of petroleum, Coal Chemical Industry and fine chemistry industry.
But the micropore canals that ZSM-5 is tediously long and narrow and small, be unfavorable for macromolecular fast transportation in catalytic process, often cause the problems such as duct is blocked, catalytic efficiency is low, catalyst deactivation.For this reason, people attempt in ZSM-5 molecular sieve, introduce mesoporous (or macropore) structure, prepare multi-stage porous ZSM-5 molecular sieve.Multi-stage porous molecular sieve had both retained the skeleton property (as good stability, acid strong) of micro porous molecular sieve, had again the advantages such as duct that is mesoporous and/or large pore material is open, rapid mass transfer, became the focus of academia and industry member research gradually.
At present, the preparation method of common multi-stage porous ZSM-5 molecular sieve comprises: soft template method, hard template method, post treatment method etc.Such as, patent CN103449466 is open a kind of with four-head rigidity Bola type tensio-active agent (C
6-6-mbr
4, m=6,8,10,12) and prepare the method for hierarchical pore MFI molecular sieve for mesoporous template, presoma after 5 ~ 9 days in 140 ~ 150 DEG C of hydrothermal crystallizings, is obtained and has middle microporous sheet structure MFI molecular sieve; The people such as Jacobsen (C.J.H.Jacobsen, C.Madsen, J.Houzvicka, I.Schmidt and A.Carlsson.J.Am.Chem.Soc., 2000,122,7116-7117) adopt nano active carbon to be hard template, successfully preparation has the ZSM-5 molecular sieve of micro-composite mesoporous structure; Patent CN102689911 A adopts microwave alkaline purification method corrosion nano level ZSM-5 molecular sieve, the multi-stage porous ZSM-5 molecular sieve nanometer ball that preparation aperture is adjustable between 30 ~ 150nm.
2012, the people such as A.Inayat (A.Inayat, I.Knoke, E.Spiecker, and W.Schwieger.Angew.Chem.Int.Ed., 2012, 51, 1962-1965) in the preparation system of X zeolite molecular sieve, add long chain organic silanes tensio-active agent [3-(trimethoxy is silica-based) propyl group] hexadecyldimethyl benzyl ammonium ammonium chloride (3-(trimethoxysilyl) propyl hexadecyl dimethyl ammonium chloride, TPHAC) preparation has the multi-stage porous X zeolite molecular sieve of special " plug-in card " (house-of-cards-like) structure first, its basic construction unit is X zeolite nanometer sheet, nanometer sheet is intersected mutually, crisscross stacking goes out triangle quadratic duct.
Usually it is high to there is preparation cost in the preparation method of above-mentioned multi-stage porous molecular sieve, and the problems such as complex process is loaded down with trivial details, and environmental pollution is serious, are unfavorable for that large-scale commercial is produced.Therefore, develop a kind of nontoxic, environmental protection, the structure directing agent of low cost prepares multi-stage porous ZSM-5 molecular sieve for mass-producing important realistic meaning.
Summary of the invention
The object of the invention is to for the problem existing for above-mentioned prior art and defect, the preparation method of a kind of economy, environmental protection, fast multi-stage porous ZSM-5 molecular sieve is provided.
The present invention prepares in system at alkaline organic-free template ZSM-5, with nontoxic, cheap METHYLPYRROLIDONE for structure directing agent, replace expensive macromole organic formwork agent, be there is by one step hydro thermal method preparation the multi-stage porous ZSM-5 molecular sieve (house-of-cards-like ZSM-5, HCL-ZSM-5) of " plug-in card " structure.The primary structure units of HCL-ZSM-5 is ZSM-5 nanometer sheet, and sheet and sheet are parallel to each other, square crossing is stacked to three-dimensional " plug-in card " structure with quadrate secondary duct.HCL-ZSM-5 molecular sieve has obvious hierarchical porous structure characteristic, and outer surface area is large, and acid strong, good stability, has a wide range of applications in catalysis, absorption with in being separated etc.
For achieving the above object, the invention provides the preparation method of the ZSM-5 molecular sieve of one " plug-in card " type multi-stage porous, concrete steps are as follows:
(1) inorganic alkali source, aluminium source are joined in deionized water, stir;
(2) in step (1) solution, add METHYLPYRROLIDONE (NMP), stir;
(3) in the solution of step (2), slowly add silicon source, stir;
(4) product step (3) obtained loads in reactor, airtight, carry out thermostatic crystallization, after crystallization in spontaneous pressure, solid product is calcined in centrifugal, washing, drying, air, obtains " plug-in card " type multi-stage porous ZSM-5 molecular sieve.
In the present invention, inorganic alkali source according to reason opinion generates M
2o gauge, aluminium source generates Al by theoretical
2o
3gauge, silicon source generates SiO by theoretical
2gauge, in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:NMP=0.048 ~ 0.53:0.005 ~ 0.05:1:1.11 ~ 50.0:0.04 ~ 3.23, are preferably M
2o:Al
2o
3: SiO
2: H
2o:NMP=0.1 ~ 0.25:0.01 ~ 0.033:1:2.22 ~ 26.7:0.2 ~ 1.62.
In step (1), inorganic alkali source is one or more in sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium oxide, potassium hydroxide, salt of wormwood, saleratus, is preferably sodium hydroxide, potassium hydroxide, most preferably is sodium hydroxide.
In step (1), aluminium source is one or more in Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, pseudo-boehmite, aluminum oxide, aluminium hydroxide, aluminium carbonate, pure aluminum, aluminum isopropylate, aluminum acetate, is preferably Tai-Ace S 150.
In step (3), silicon source is one or more in white carbon black, water glass, silicon sol, tetraethoxy, silica gel, diatomite, is preferably white carbon black, silicon sol, most preferably is white carbon black.
For ensureing the homogeneity of colloid composition in step (3), step adds excessive deionized water in (1) further, excessive deionized water is used deionized water quality 0 ~ 120%, be preferably 20 ~ 60%, excessive deionized water is evaporated by the mode of uncovered stirring, vaporization temperature is 25 ~ 100 DEG C, is preferably 60 ~ 70 DEG C.
In step (4), described crystallization temperature is 90 ~ 220 DEG C, and be preferably 120 ~ 180 DEG C, crystallization time is 6 ~ 192h, is preferably 12 ~ 120h.
In step (4), described calcining temperature is 450 ~ 700 DEG C, and be preferably 500 ~ 650 DEG C, calcination time is 0.5 ~ 24h, and be preferably 2 ~ 9h, temperature rise rate is 0.2 ~ 5 DEG C of min
-1, be preferably 1 ~ 2 DEG C of min
-1.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) the present invention prepares in system at alkaline organic-free template ZSM-5, with nontoxic, cheap METHYLPYRROLIDONE for structure directing agent, replace expensive macromole organic formwork agent, by one step hydro thermal method preparation " plug-in card " type multi-stage porous ZSM-5 molecular sieve (HCL-ZSM-5), be the preparation method of a kind of economy, efficient, environmental protection, be expected to large-scale commercial and produce.
(2) primary structure of the HCL-ZSM-5 molecular sieve prepared by the present invention is ZSM-5 nanometer sheet, and sheet and sheet are parallel to each other, square crossing is piled into " plug-in card " type multilevel hierarchy, and size distribution is comparatively homogeneous.
(3) the HCL-ZSM-5 molecular sieve prepared by the present invention has the abundant and specific surface area in good stability, acid strong, mesoporous (or macropore) duct and the feature such as external surface area is large, has a wide range of applications in catalysis, absorption with in being separated etc.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous ZSM-5 molecular sieve.
Fig. 2 is scanning electron microscope (SEM) picture that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous ZSM-5 molecular sieve.Wherein, Fig. 2 A is low power SEM picture, Fig. 2 B be in times SEM picture, the embedded figure in Fig. 2 B is high power SEM picture.
Fig. 3 is the N that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous ZSM-5 molecular sieve
2absorption/desorption isotherm.Wherein, curve 1 represents N
2adsorption curve, curve 2 represents N
2desorption curve.
Fig. 4 is the NLDFT graph of pore diameter distribution that the embodiment of the present invention 1 prepares " plug-in card " type multi-stage porous ZSM-5 molecular sieve.
Embodiment
In conjunction with following instance the present invention made and further describing, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
(1) 0.42g aluminum sulfate octadecahydrate, 0.4g sodium hydroxide are joined in 9g deionized water, stir to clarify solution, then it is even to add 4g deionized water and stirring;
(2) add the METHYLPYRROLIDONE of 2g to the settled solution of step (1), stir;
(3) settled solution to step (2) slowly adds 1.5g white carbon black, stirs, and makes rare colloid;
(4) rare colloid step (3) obtained low-grade fever at 60 DEG C stirs evaporation 4h (total mass reduces about 4g), obtains even wet gel;
(5) wet gel step (4) obtained loads in hydrothermal reaction kettle, 140 DEG C of crystallization 72h, after crystallization terminates, solid product is through suction filtration, washing, in 70 DEG C of baking oven constant pressure and dry 24h, more in atmosphere 550 DEG C of calcination 5h (temperature rise rate is 1 DEG C of min
-1), obtain " plug-in card " type multi-stage porous ZSM-5 molecular sieve 1.14g, productive rate is 10.1% (product accounts for the per-cent of the total mass that feeds intake (containing solvent)).
Phenetic analysis is carried out to " plug-in card " type multi-stage porous ZSM-5 molecular sieve (HCL-ZSM-5) prepared by embodiment 1.
Adopt Rigaku D/MAX-2550 type X-ray diffractometer (Japan) to carry out thing to HCL-ZSM-5 product to characterize mutually.Result as shown in Figure 1, the XRD spectra of HCL-ZSM-5 sample and the characteristic peak of standard ZSM-5 molecular sieve completely the same, show that prepared HCL-ZSM-5 sample is ZSM-5 molecular sieve pure phase, there are not other dephasigns.
JEOL JSM-6700F type scanning electronic microscope (Japan) is adopted to carry out morphology characterization to HCL-ZSM-5 product.Result as shown in Figure 2, the ZSM-5 nanometer sheet that HCL-ZSM-5 is about 100nm with thickness is basic construction unit, these nanometer sheet are parallel to each other, square crossing is stacked to three-dimensional " plug-in card " structure with quadrate secondary duct, and aggregate particle size is about 10 μm, distributes homogeneous.There is obvious hole between parallel nanofiber sheet, this is conducive to macromolecular fast transport in catalyzed reaction.
Adopt Micromeritics ASAP 2020M type N
2sorption Analyzer (U.S.) carries out microstructure analysis to HCL-ZSM-5 product.N
2as shown in Figure 3, curve shows as typical IV-type adsorption isothermal line to adsorption/desorption isothermal curve, and show that HCL-ZSM-5 has hierarchical porous structure characteristic, this is consistent with sem analysis result.413m is about by calculating its BET specific surface area
2g
-1, outer surface area is 182m
2g
-1.As shown in Figure 4, Jie-macropore diameter, roughly between 5 ~ 80nm, concentrates near 16nm the NLDFT graph of pore diameter distribution of HCL-ZSM-5.
Embodiment 2
(1) 0.37g aluminum sulfate octadecahydrate, 0.4g sodium hydroxide are added in 10g deionized water, stir to clarify solution, then add 6g deionization and stir;
(2) add the METHYLPYRROLIDONE of 1g to the settled solution of step (1), stir;
(3) settled solution to step (2) slowly adds 1.5g white carbon black, stirs, and makes rare colloid;
(4) rare colloid step (3) obtained 60 DEG C of low-grade fevers stir evaporation 6h (total mass reduces about 6g), obtain even wet gel;
(5) wet gel step (4) obtained loads in hydrothermal reaction kettle, 140 DEG C of crystallization 72h, after crystallization terminates, solid product is through suction filtration, washing, in 70 DEG C of baking oven constant pressure and dry 24h, more in atmosphere 500 DEG C of calcination 4h (temperature rise rate is 1 DEG C of min
-1), obtain " plug-in card " type multi-stage porous ZSM-5 molecular sieve 1.10g, productive rate is 9.7% (product accounts for the per-cent of the total mass that feeds intake (containing solvent)).Product X RD schemes similar to Fig. 1, and peak width is slightly narrow, and scanned picture is similar to Fig. 2, and ZSM-5 sheet thickness is about 120nm.
Embodiment 3
(1) 0.42g aluminum sulfate octadecahydrate, 0.4g sodium hydroxide are added in 5.6g deionized water, stir to clarify solution, then add 4g deionization and stir;
(2) add the METHYLPYRROLIDONE of 2g to the settled solution of step (1), stir;
(3) settled solution to step (2) slowly adds 5.4g silicon sol (SiO
2mass percent be 25 ~ 30%), stir, make rare colloid;
(4) rare colloid step (3) obtained 70 DEG C of low-grade fevers stir evaporation 2h (total mass reduces about 4g), obtain even wet gel;
(5) wet gel step (4) obtained loads in hydrothermal reaction kettle, 140 DEG C of crystallization 60h, after crystallization terminates, solid product is through suction filtration, washing, in 70 DEG C of baking oven constant pressure and dry 24h, more in atmosphere 550 DEG C of calcination 6h (temperature rise rate is 1 DEG C of min
-1), obtain " plug-in card " type multi-stage porous ZSM-5 molecular sieve 1.21g, productive rate is 12.3% (product accounts for the per-cent of the total mass that feeds intake (containing solvent)).Product X RD schemes with Fig. 1 similar, and peak width is slightly narrow, and ZSM-5 sheet thickness is about 150nm.
The above is only several case study on implementation of the present invention, and not do any pro forma restriction to the present invention, protection scope of the present invention is not limited thereto.
Claims (9)
1. a preparation method for the ZSM-5 molecular sieve of " plug-in card " type multi-stage porous, its step is as follows:
(1) inorganic alkali source, aluminium source are joined in deionized water, stir;
(2) in step (1) solution, add METHYLPYRROLIDONE, stir;
(3) in the solution of step (2), slowly add silicon source, stir;
(4) product step (3) obtained loads in reactor, airtight, carry out thermostatic crystallization, after crystallization in spontaneous pressure, solid product is calcined in centrifugal, washing, drying, air, obtains the ZSM-5 molecular sieve of " plug-in card " type multi-stage porous;
Inorganic alkali source according to reason opinion generates M
2o gauge, aluminium source generates Al by theoretical
2o
3gauge, silicon source generates SiO by theoretical
2gauge, in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:NMP=0.048 ~ 0.53:0.005 ~ 0.05:1:1.11 ~ 50.0:0.04 ~ 3.23.
2. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, is characterized in that: in above-mentioned reaction system, the mol ratio of each component is M
2o:Al
2o
3: SiO
2: H
2o:NMP=0.1 ~ 0.25:0.01 ~ 0.033:1:2.22 ~ 26.7:0.2 ~ 1.62.
3. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: in step (1), inorganic alkali source is one or more in sodium oxide, sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium oxide, potassium hydroxide, salt of wormwood, saleratus.
4. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: in step (1), aluminium source is one or more in Tai-Ace S 150, sodium aluminate, aluminum nitrate, aluminum chloride, pseudo-boehmite, aluminum oxide, aluminium hydroxide, aluminium carbonate, pure aluminum, aluminum isopropylate, aluminum acetate.
5. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: in step (3), silicon source is one or more in white carbon black, water glass, silicon sol, tetraethoxy, silica gel, diatomite.
6. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: step adds excessive deionized water in (1) further, excessive deionized water is used deionized water quality 0 ~ 120%, be preferably 20 ~ 60%, unnecessary moisture content is evaporated by the mode of uncovered stirring, vaporization temperature is 25 ~ 100 DEG C, is preferably 60 ~ 70 DEG C.
7. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 6, it is characterized in that: excessive deionized water is evaporated by the mode of uncovered stirring, vaporization temperature is 25 ~ 100 DEG C.
8. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: in step (4), described crystallization temperature is 90 ~ 220 DEG C, and crystallization time is 6 ~ 192h.
9. the preparation method of the ZSM-5 molecular sieve of a kind of " plug-in card " type multi-stage porous as claimed in claim 1, it is characterized in that: in step (4), described calcining temperature is 450 ~ 700 DEG C, and calcination time is 0.5 ~ 24h, and temperature rise rate is 0.2 ~ 5 DEG C of min
-1.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107027805A (en) * | 2017-05-02 | 2017-08-11 | 长乐净能新材料科技有限公司 | A kind of modified molecular screens of nanoscale Sc SSZ 13/ZSM 5 and its application |
| CN107512728A (en) * | 2017-07-03 | 2017-12-26 | 深圳大学 | The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves |
| CN109205642A (en) * | 2018-10-25 | 2019-01-15 | 华南理工大学 | A kind of preparation method of middle micro-diplopore ZSM-5 zeolite nano flake |
| CN109694085A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet |
| CN110357123A (en) * | 2019-07-31 | 2019-10-22 | 深圳大学 | A kind of high crystalline multi-stage porous nano X-type molecular sieve and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003380A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite with multilevel pore canals |
| CN101200295A (en) * | 2007-12-11 | 2008-06-18 | 中国铝业股份有限公司 | Method for synthesizing ZSM-5 molecular sieve by directing agent process |
| CN102583434A (en) * | 2012-03-20 | 2012-07-18 | 辽宁工业大学 | Method for preparing ZSM-5 zeolite molecular sieve microspheres |
| WO2014099261A1 (en) * | 2012-12-21 | 2014-06-26 | Exxonbobil Chemical Patents Inc. | Synthesis of zsm-5 |
-
2014
- 2014-09-29 CN CN201410520157.7A patent/CN104261427B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003380A (en) * | 2006-01-19 | 2007-07-25 | 中国石油化工股份有限公司 | Method for synthesizing ZSM-5 zeolite with multilevel pore canals |
| CN101200295A (en) * | 2007-12-11 | 2008-06-18 | 中国铝业股份有限公司 | Method for synthesizing ZSM-5 molecular sieve by directing agent process |
| CN102583434A (en) * | 2012-03-20 | 2012-07-18 | 辽宁工业大学 | Method for preparing ZSM-5 zeolite molecular sieve microspheres |
| WO2014099261A1 (en) * | 2012-12-21 | 2014-06-26 | Exxonbobil Chemical Patents Inc. | Synthesis of zsm-5 |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107027805A (en) * | 2017-05-02 | 2017-08-11 | 长乐净能新材料科技有限公司 | A kind of modified molecular screens of nanoscale Sc SSZ 13/ZSM 5 and its application |
| CN107512728A (en) * | 2017-07-03 | 2017-12-26 | 深圳大学 | The preparation method of card plugging structure multi-stage porous FAU type zeolite molecular sieves |
| CN107512728B (en) * | 2017-07-03 | 2020-06-26 | 深圳大学 | Preparation method of FAU type zeolite molecular sieve with card-inserted structure and hierarchical pores |
| CN109694085A (en) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | The Template-free method synthetic method of ammonium type ZSM-5 nanometer sheet |
| CN109205642A (en) * | 2018-10-25 | 2019-01-15 | 华南理工大学 | A kind of preparation method of middle micro-diplopore ZSM-5 zeolite nano flake |
| CN109205642B (en) * | 2018-10-25 | 2022-03-25 | 华南理工大学 | Preparation method of medium-micro double-hole ZSM-5zeolite nano sheet |
| CN110357123A (en) * | 2019-07-31 | 2019-10-22 | 深圳大学 | A kind of high crystalline multi-stage porous nano X-type molecular sieve and preparation method thereof |
| CN112551542A (en) * | 2021-02-05 | 2021-03-26 | 福州大学 | Single crystal cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN112591764A (en) * | 2021-02-05 | 2021-04-02 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| CN112591764B (en) * | 2021-02-05 | 2022-05-13 | 福州大学 | Single crystal aluminum-rich cascade hole HZSM-5 molecular sieve and green preparation method thereof |
| WO2022165911A1 (en) * | 2021-02-05 | 2022-08-11 | 福州大学 | Single-crystal hierarchically porous hzsm-5 molecular sieve and green preparation method therefor |
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