CN109179446A - A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof - Google Patents
A kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof Download PDFInfo
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- 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
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- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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Abstract
The invention belongs to catalysis material preparation fields, and in particular to a kind of hollow nano H-type ZSM-5 molecular sieve and preparation method thereof.Na type molecular sieve is placed in inorganic alkali solution and is handled, obtains the H-type ZSM-5 molecular sieve (HZSM-5) with hollow nano structure in turn after ammonium exchange, roasting are carried out after ice water cooling, centrifuge washing, drying.Preparation method of the invention has many advantages, such as that synthesis cycle is shorter, process flow is simple, and there is mesoporous-micropore multistage hole composite construction of nanoscale using the H-type ZSM-5 molecular sieve of the method for the present invention preparation, specific surface area and external surface area are higher, can be used as catalyst or active component carrier material in a variety of catalysis reaction.
Description
Technical field
The invention belongs to catalysis material preparation fields, and in particular to a kind of hollow nano H-type ZSM-5 molecular sieve and its preparation
Method.
Background technique
ZSM-5 molecular sieve catalyst specific surface area with higher, regular cellular structure and can modulation surface acidity,
It is widely used in the fields such as oil refining, fine chemistry industry, gas separation and purification.It both can be directly as absorption or catalysis material
Material, while the carrier material that also can be used as a variety of loaded catalysts reacts such as C4 alkylation, NO for a variety of catalysisxSelection
Property catalysis reduction, VOCs catalysis oxidation etc..
In catalysis reaction, the catalytic performance of ZSM-5 molecular sieve and its crystallite dimension, specific surface area, pore structure, acidity etc.
Physico-chemical parameter is closely related；Especially in long chain alkane catalytic pyrolysis, C4 alkylation, volatile organic matter low-temperature catalytic oxidation etc.
In reaction, the service life of ZSM-5 molecular sieve is intermediate vulnerable to its surface texture, thermal stability, acidic site carbon distribution and other reactions
The influence of the factors such as species, and then the decline of its catalytic performance is caused even to inactivate.Although deactivated molecular sieve catalysis material is through height
Temperature roasting is to realize its active sites locally regenerated important means, however high-temperature roasting can equally cause molecular sieve structure and surface
The variation of property can cause especially for the process of noble metal or metal oxide supported type ZSM-5 catalyst high-temperature roasting
Reunion, the sintering of metallic particles, so that irreversible complete deactivation occurs for catalytic activity.It is being urged to strengthen ZSM-5 molecular sieve
Application in oxidation, and then need to be to its further research.
Summary of the invention
It is an object of that present invention to provide a kind of hollow nano H-type ZSM-5 molecular sieves and preparation method thereof.
To achieve the above object, the invention adopts a technical scheme as:
A kind of preparation method of hollow nano H-type ZSM-5 molecular sieve, Na type molecular sieve is placed in inorganic alkali solution
Reason obtains the H-type with hollow nano structure after carrying out ammonium exchange, roasting after ice water cooling, centrifuge washing, drying in turn
ZSM-5 molecular sieve (HZSM-5).
Further, Na type ZSM-5 powder is stirred at 30~60 DEG C in the inorganic alkali solution of 0.1~0.4mol/L
4~6h is mixed, and centrifuge washing cooling using ice water, is dried after washing after mixing, then uses the ammonium nitrate solution pair of 1mol/L
Powder after drying carries out multiple ion exchange, often inferior to 60 DEG C at stir 6h, after being centrifugated, dried after ion exchange in
450-600 DEG C of Muffle furnace roasts 6-10h, obtains the H-type ZSM-5 molecular sieve of hollow nano structure.
The inorganic alkali solution is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
The Na type ZSM-5 powder is to add by silicon source and silicon source formation clear solution soluble in water, then into clear solution
Enter organic formwork agent and stir 4-6h at 30~50 DEG C, stirs and evenly mixs and move back to Crystallizing treatment in reaction kettle, be then cooled to
Room temperature, centrifuge washing to neutrality, drying are placed in Muffle furnace, are warming up to 400~600 DEG C of 5~10h of roasting, obtain Na type
ZSM-5 powder.
The silicon source, silicon source, the molar ratio of organic formwork agent and water are 1:(0.01~0.04): (0.1~0.4): (5~
15)；Wherein, silicon source is tetraethyl orthosilicate, and silicon source is sodium metaaluminate, and organic formwork agent is tetrapropyl aqua ammonia.
The crystallization is that will stir and evenly mix rear solution and be transferred in the reaction kettle containing polytetrafluoroethyllining lining, first 100~
140 DEG C of 2~4h of crystallization, then the crystallization 18-24h at 170~200 DEG C, then cools to room temperature.
Advantage for present invention:
The present invention first synthesizes the nanoscale ZSM-5 molecular sieve of pure phase, then by it is carried out alkali process, high-temperature roasting,
The mode of recrystallization forms it into the hollow structure for having the compound multistage hole characteristic of micropore-mesopore, and then effectively increases
The performance parameters such as specific surface area, external surface area and the mesoporous hole appearance of ZSM-5 molecular sieve.And improve its suction to reactant molecule
Attached characteristic, effectively solve the problems, such as the easy carbon distribution in acidic zeolite position this, intensified response mass-transfer efficiency；It is used as carrier material simultaneously
Noble metal or transition metal active component are loaded on hollow molecules sieve, the dispersibility of metallic particles is can be improved, seals simultaneously
Metal nanoparticle inside hollow structure can to avoid under high temperature sintering, grow up, or even reduce with react in it is toxic
The contact of Harmful species improves the whole catalytic stability of loaded catalyst.
Detailed description of the invention
Fig. 1 is the XRD spectra of hollow nano H-type ZSM-5 molecular sieve prepared by embodiment 1；
Fig. 2 is the transmission electron microscope photo of hollow nano H-type ZSM-5 molecular sieve prepared by embodiment 1；
Fig. 3 is the stereoscan photograph of hollow nano H-type ZSM-5 molecular sieve prepared by embodiment 1；
Fig. 4 is the N of hollow nano H-type ZSM-5 molecular sieve prepared by embodiment 12Adsorption-desorption isothermal curve figure；
Fig. 5 is hollow nano H-type ZSM-5 molecular sieve graph of pore diameter distribution prepared by embodiment 1；
Fig. 6 is hollow nano H-type ZSM-5 molecular sieve temperature programming oxygen desorption curve figure prepared by embodiment 1.
Specific embodiment
Explanation that the present invention will be further explained with reference to the accompanying drawings and examples.
The preparation method of hollow nano H-type ZSM-5 molecular sieve, sequentially includes the following steps:
1, using tetraethyl orthosilicate as silicon source, sodium metaaluminate is silicon source, and tetrapropyl aqua ammonia is as organic formwork agent；Its
Middle silicon source, silicon source, the molar ratio of organic formwork agent and water are 1:(0.01~0.04): (0.1~0.4): (5~15).
2. tetraethyl orthosilicate, sodium metaaluminate, which are dissolved in deionized water, forms clear solution, it is slowly added into the solution
Tetrapropylammonium hydroxide stirs 4-6h at 30-50 DEG C.
3, above-mentioned solution is transferred in the reaction kettle containing polytetrafluoroethyllining lining, first in 100~140 DEG C of 2~4h of crystallization,
Then the crystallization 18-24h at 170~200 DEG C, then cools to room temperature, centrifuge washing to neutrality, after 100 DEG C of oven dryings
It is placed in Muffle furnace, is warming up to 400~600 DEG C of 5~10h of roasting, obtains Na type ZSM-5 powder；
4, above-mentioned powder is put into the inorganic alkali solution of 0.1~0.4mol/L and in 30~60 DEG C of 4~6h of stirring, used
After the cooling simultaneously centrifuge washing of ice water, dried in 80 DEG C of baking ovens；
5, ion exchange is carried out three times to the powder after drying using the ammonium nitrate solution of 1mol/L, is often inferior at 60 DEG C and stirs
6h is mixed, 550 DEG C of Muffle furnace roasts 8h after being centrifuged, drying, and obtains the H-type ZSM-5 molecular sieve of hollow nano structure.
Preparation method of the invention has many advantages, such as that synthesis cycle is shorter, process flow is simple, and uses the method for the present invention
The H-type ZSM-5 molecular sieve of preparation has mesoporous-micropore multistage hole composite construction, specific surface area and outer surface of nanoscale
Product is higher, can be used as catalyst or active component carrier material in a variety of catalysis reaction.
Embodiment 1
The preparation method of hollow nano H-type ZSM-5 molecular sieve, sequentially includes the following steps:
1. weighing tetraethyl orthosilicate 15.6g, the tetrapropyl aqua ammonia of sodium metaaluminate 0.123g, mass fraction 25% are molten
Liquid 12.18g, deionized water 7g.
2. tetraethyl orthosilicate, sodium metaaluminate, which are dissolved in deionized water, by above-mentioned weighed amount forms clear solution, to this
It is slowly added into tetrapropylammonium hydroxide in solution, stirs 6h at 30 DEG C.
3, step 2) acquired solution is transferred in the reaction kettle containing polytetrafluoroethyllining lining, first in 120 DEG C of crystallization 2h, so
Crystallization for 24 hours, then cools to room temperature at 170 DEG C afterwards, is centrifuged and is washed with deionized into using 6000r/min centrifuge
Property, it is placed in Muffle furnace in 100 DEG C of oven dryings, is warming up to 550 DEG C of roasting 6h, obtain Na type ZSM-5 powder；
4, above-mentioned powder is put into the potassium hydroxide solution of 0.2mol/L and in 50 DEG C of stirring 5h, it is cold using 0 DEG C of ice water
But it is centrifuged and is washed with deionized under the conditions of 6000r/min after, dried in 80 DEG C of baking ovens；
5, ion exchange is carried out three times to the powder after drying using the ammonium nitrate solution of 1.0mol/L, be often inferior at 60 DEG C
6h is stirred, the Muffle kiln roasting 6h under 6000r/min centrifugal condition after separation, 100 DEG C of oven dryings at 500 DEG C is obtained
The H-type ZSM-5 molecular sieve of hollow nano structure (referring to Fig. 1-5 and table 1).
The relevant parameter of 1. hollow nano H-type ZSM-5 molecular sieve of table
It infuses, is by the specific surface area that the molecular sieve is calculated in Brunauer-Eminett-Teuer (BET) method
431m2/ g, it is 133m that its external surface area, which is calculated, by t-plot method2/ g, Micropore volume 0.12cm3/ g, passes through
Its mesoporous Kong Rongwei 0.27cm is calculated in Barrett-Joyner-Halenda (BJH) method3/g
As shown in above-mentioned Fig. 1 XRD spectra, resulting ZSM-5 molecular sieve is prepared with typical MFI topological structure, crystal phase
It is single, pure and formed without other split-phases；Again as shown in Fig. 2 transmission electron microscope photo, having for ZSM-5 molecular sieve is typical hollow
Structure, the global sections diameter of molecular sieve are about 200nm, wall thickness about 15-20nm；And shown in Fig. 3 stereoscan photograph, ZSM-
5 molecular sieve uniform particle sizes and well dispersed are circular platform type nano particle, and diameter of section is in 200nm or so.
Simultaneously as shown in Fig. 4 nitrogen adsorption-desorption isotherm, molecular sieve is in relative pressure p/p0Have when close to 0 biggish
Adsorbance shows the presence of a large amount of micropores in molecular sieve；In addition occur between 0.4~1.0 in relative pressure apparent stagnant
Ring afterwards illustrates that there are a certain number of meso-hole structures in the molecular sieve.
In addition, it is the micropore of 0.4~0.7nm that hollow ZSM-5 molecular sieve, which had both had aperture, as shown in Fig. 5 graph of pore diameter distribution,
Having aperture simultaneously is the mesoporous of 3.8~8.5nm, is typical hierarchical porous structure.
Embodiment 2: present embodiment difference from Example 1 be only that silicon source in step 2, silicon source, template it is mixed
Conjunction mixing time is 6h.
Embodiment 3: present embodiment difference from Example 1 is only that in step 3 crystallization under conditions of 120 DEG C
2h。
Embodiment 4: present embodiment difference from Example 1 be only that in step 3 100~140 DEG C of crystallization 2~
After 4h 170 DEG C of continuation crystallization for 24 hours.
Embodiment 5: present embodiment difference from Example 1 is only that in step 4 that inorganic base is sodium hydroxide, hydrogen-oxygen
Change potassium or ammonium hydroxide.
Embodiment 6: present embodiment difference from Example 1 is only that the concentration that inorganic alkali solution is used in step 4
For 0.2mol/L.
Effect shown in Fig. 1-5 can be reached by preparing according to the various embodiments described above.
The hollow nano HZSM-5 molecular sieve that the solid molecular sieve of nanometer and above-described embodiment are obtained using chemical adsorption instrument
The absorption property test for carrying out oxygen, referring to Fig. 6, hollow nano molecular sieve has oxygen it can be seen from oxygen desorption signal
There is higher adsorption capacity.
Claims (7)
1. a kind of preparation method of hollow nano H-type ZSM-5 molecular sieve, it is characterised in that: Na type molecular sieve is placed in inorganic base
It handles in solution, is obtained in turn with hollow nano knot after ammonium exchange, roasting are carried out after ice water cooling, centrifuge washing, drying
The H-type ZSM-5 molecular sieve (HZSM-5) of structure.
2. the preparation method of hollow nano H-type ZSM-5 molecular sieve according to claim 1, it is characterised in that: by Na type ZSM-
5 powders stir 4~6h in the inorganic alkali solution of 0.1~0.4mol/L at 30~60 DEG C, cooling simultaneously using ice water after mixing
Centrifuge washing is dried after washing, then carries out multiple ion exchange to the powder after drying using the ammonium nitrate solution of 1mol/L,
It is often inferior at 60 DEG C and stirs 6h, the Muffle furnace after being centrifugated, dried after ion exchange in 450-600 DEG C roasts 6-10h, obtains
To the H-type ZSM-5 molecular sieve of hollow nano structure.
3. pressing the preparation method of hollow nano H-type ZSM-5 molecular sieve as claimed in claim 1 or 2, it is characterised in that: described inorganic
Aqueous slkali is sodium hydroxide, potassium hydroxide or ammonium hydroxide.
4. by the preparation method of hollow nano H-type ZSM-5 molecular sieve described in claim 2, it is characterised in that: the Na type ZSM-
5 powders be by silicon source and silicon source formation clear solution soluble in water, then be added into clear solution organic formwork agent and in 30~
4-6h is stirred at 50 DEG C, stirs and evenly mixs and moves back to Crystallizing treatment in reaction kettle, be then cooled to room temperature, centrifuge washing to neutrality,
Drying is placed in Muffle furnace, is warming up to 400~600 DEG C of 5~10h of roasting, is obtained Na type ZSM-5 powder.
5. by the preparation method of hollow nano H-type ZSM-5 molecular sieve described in claim 4, it is characterised in that: the silicon source, aluminium
The molar ratio in source, organic formwork agent and water is 1:(0.01~0.04): (0.1~0.4): (5~15)；Wherein, silicon source is positive silicon
Sour tetra-ethyl ester, silicon source are sodium metaaluminate, and organic formwork agent is tetrapropyl aqua ammonia.
6. by the preparation method of hollow nano H-type ZSM-5 molecular sieve described in claim 4, it is characterised in that: the crystallization is will
It stirs and evenly mixs rear solution to be transferred in the reaction kettle containing polytetrafluoroethyllining lining, first in 100~140 DEG C of 2~4h of crystallization, then exist
Crystallization 18-24h, then cools to room temperature at 170~200 DEG C.
7. a kind of hollow nano H-type ZSM-5 molecular sieve described in claim 1, it is characterised in that: according to claim 1
Preparation method has the H-type ZSM-5 molecular sieve (HZSM-5) of the hollow nano structure of the compound multistage hole characteristic of micropore-mesopore.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586179A (en) * | 2019-08-23 | 2019-12-20 | 西北大学 | Catalyst with high selectivity on low-carbon olefin and preparation method thereof |
| CN112279268A (en) * | 2020-08-06 | 2021-01-29 | 中国石油大学胜利学院 | Preparation method and application of hierarchical pore ZSM-5 nano lamellar zeolite |
| CN113716576A (en) * | 2021-07-29 | 2021-11-30 | 浙江工业大学 | Method for preparing hollow spherical zeolite by using natural zeolite |
| CN114931969A (en) * | 2022-06-08 | 2022-08-23 | 青岛科技大学 | Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof |
| CN115106100A (en) * | 2022-06-08 | 2022-09-27 | 青岛科技大学 | Pt-Ni alloy porous carbon composite material and preparation method and application thereof |
| CN115770609A (en) * | 2022-11-17 | 2023-03-10 | 华电电力科学研究院有限公司 | Preparation method of fly ash-based Fe/ZSM-5 mesoporous molecular sieve catalyst |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491366A (en) * | 2011-12-05 | 2012-06-13 | 大连理工大学 | Method for preparing hollow zeolite socony mobil-5 (ZSM-5) nanometer zeolite |
| 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 |
| CN104525245A (en) * | 2014-12-22 | 2015-04-22 | 中国石油大学(北京) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application |
| CN105692652A (en) * | 2014-11-28 | 2016-06-22 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN106082263A (en) * | 2016-06-08 | 2016-11-09 | 太原理工大学 | A kind of preparation method of nano-hollow ZSM 5 molecular sieve in the rich hole of shell |
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
| CN108033463A (en) * | 2017-12-31 | 2018-05-15 | 中海油天津化工研究设计院有限公司 | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system |
-
2018
- 2018-09-28 CN CN201811138214.XA patent/CN109179446A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491366A (en) * | 2011-12-05 | 2012-06-13 | 大连理工大学 | Method for preparing hollow zeolite socony mobil-5 (ZSM-5) nanometer zeolite |
| 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 |
| CN105692652A (en) * | 2014-11-28 | 2016-06-22 | 中国石油化工股份有限公司 | Preparation method of ZSM-5 molecular sieve |
| CN104525245A (en) * | 2014-12-22 | 2015-04-22 | 中国石油大学(北京) | Nanocrystalline accumulation meso-microporous ZSM-5 catalyst and preparation and application |
| CN106082263A (en) * | 2016-06-08 | 2016-11-09 | 太原理工大学 | A kind of preparation method of nano-hollow ZSM 5 molecular sieve in the rich hole of shell |
| CN106082257A (en) * | 2016-06-08 | 2016-11-09 | 清华大学 | A kind of hollow molecular sieve, preparation method and applications |
| CN108033463A (en) * | 2017-12-31 | 2018-05-15 | 中海油天津化工研究设计院有限公司 | The method that ZSM-5 molecular sieve with small crystal grains is efficiently prepared under no organic amine system |
Non-Patent Citations (6)
| Title |
|---|
| CHANGSONG MEI，等: "Regular HZSM-5 microboxes prepared via a mild alkaline treatment, Journal of Materials Chemistry", 《 JOURNAL OF MATERIALS CHEMISTRY》 * |
| J.C. GROEN，等: "Mesoporosity development in ZSM-5 zeolite upon optimized desilication conditions in alkaline medium", 《COLLOIDS AND SURFACES A: PHYSICOCHEM. ENG. ASPECTS》 * |
| JOHAN C. GROEN,等: "Creation of Hollow Zeolite Architectures by Controlled Desilication of", 《JACS》 * |
| RUIYUE QI，等: "Pore fabrication of nano-ZSM-5 zeolite by internal desilication and its influence on the", 《FUEL PROCESSING TECHNOLOGY》 * |
| TINGJUN FU，等: "Facile synthesis of nano-sized hollow ZSM-5 zeolites with rich mesopores in shell", 《MICROPOROUS AND MESPOROUS MATERIALS》 * |
| 卢永斌，等: "两段晶化法快速合成均匀单分散小晶粒ZSM-5分子筛", 《天然气化工（C1化学与化工）》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110586179A (en) * | 2019-08-23 | 2019-12-20 | 西北大学 | Catalyst with high selectivity on low-carbon olefin and preparation method thereof |
| CN112279268A (en) * | 2020-08-06 | 2021-01-29 | 中国石油大学胜利学院 | Preparation method and application of hierarchical pore ZSM-5 nano lamellar zeolite |
| CN113716576A (en) * | 2021-07-29 | 2021-11-30 | 浙江工业大学 | Method for preparing hollow spherical zeolite by using natural zeolite |
| CN114931969A (en) * | 2022-06-08 | 2022-08-23 | 青岛科技大学 | Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof |
| CN115106100A (en) * | 2022-06-08 | 2022-09-27 | 青岛科技大学 | Pt-Ni alloy porous carbon composite material and preparation method and application thereof |
| CN114931969B (en) * | 2022-06-08 | 2024-02-13 | 青岛科技大学 | Ferroferric oxide-ZSM-5 composite material and preparation method and application thereof |
| CN115770609A (en) * | 2022-11-17 | 2023-03-10 | 华电电力科学研究院有限公司 | Preparation method of fly ash-based Fe/ZSM-5 mesoporous molecular sieve catalyst |
| CN115770609B (en) * | 2022-11-17 | 2024-04-19 | 华电电力科学研究院有限公司 | Preparation method of fly ash-based Fe/ZSM-5 mesoporous molecular sieve catalyst |
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Application publication date: 20190111 |