CN105858683A - Preparing method for rapidly synthesizing ZSM-11 molecular sieve - Google Patents
Preparing method for rapidly synthesizing ZSM-11 molecular sieve Download PDFInfo
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- CN105858683A CN105858683A CN201610428831.8A CN201610428831A CN105858683A CN 105858683 A CN105858683 A CN 105858683A CN 201610428831 A CN201610428831 A CN 201610428831A CN 105858683 A CN105858683 A CN 105858683A
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- zsm
- molecular sieve
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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
- C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
The invention belongs to a synthesis method for a molecular sieve, and particularly discloses a method for rapidly synthesizing a ZSM-11 molecular sieve. The method includes the steps that deionized water, a template agent, an aluminum source and a silicon source are sequentially mixed to be even to prepare gel, FeSO4.7H2O solids and H2O2 solutions are added into the prepared gel, an alkali source is finally added, initial gel is prepared, the initial gel is crystallized, then the solids are separated from mother liquid and dried, and a hydrogen-type ZSM-11 molecular sieve is obtained. According to the method, a fenton agent is led into the synthesis process of an existing ZSM-11 molecular sieve, the effect of the fenton agent is similar to that of a biological enzyme, raw material species in the agglomeration state can be depolymerized and reset under the mild condition, the formed time of a secondary structure unit is greatly shortened accordingly, crystallization time is greatly shortened, and the crystallinity degree of the final synthesis ZSM-11 molecular sieve is high. In addition, the method is easy and convenient to operate and easy to industrially apply.
Description
Technical field
The present invention relates to the synthetic method of a kind of molecular sieve, a kind of method of fast synthesis of ZSM-5-11 molecular sieve.
Background technology
ZSM-11 molecular sieve is to be synthesized first in 20 century 70s by Mobil oil company, belongs to together with ZSM-5 molecular sieve
Pentasil type molecular sieve.The two similarity is all to contain two kinds of cross one another ten-ring pore canal system, shows similar
Catalytic performance；Difference shows pore structure aspect, the ten-ring duct being parallel to (100) crystal face of ZSM-5 molecular sieve
Become S type, and the two of ZSM-11 molecular sieve set holes are straight hole road, are allowed to show different spies in some catalytic reaction
Point.
Research for ZSM-11 molecular sieve at present mostly concentrates on the novel template of searching and optimum synthesis technique side
Face.US4941962 use bi-quaternary ammonium salt (butyl pyrrolidine) as template, at crystallization temperature 60～250 DEG C, crystallization time 1
～under conditions of 30 days, synthesize ZSM-11 molecular sieve；US6444191 does template with 3,5-dimethyl-N, N-parvoline
Agent, crystallization 2～the most successfully synthesize the ZSM-11 molecular sieve of pure phase under the conditions of 20 days at temperature 140～200 DEG C；
CN103663488A uses TBAH and 1, and 8-octamethylenediamine is composite mould plate agent, at high temperature crystallization 1～synthesis in 2 days
Going out the ZSM-11 molecular sieve of pure phase, technique is simple, and synthetic sample sodium content is low.CN101531376A uses microwave synthesis process,
Obtain the ZSM-11 molecular sieve that degree of crystallinity is high, crystalline phase is pure, granularity is controlled and scope is wider.On the whole, synthesis is reported at present
All there is the problem that generated time is relatively long in the building-up process of ZSM-11 molecular sieve, it is generally required at least 24 hours so that point
Relatively time-consuming power consumption during sub-sieve series is standby.
Summary of the invention
For the deficiencies in the prior art, it is an object of the invention to provide a kind of described fast synthesis of ZSM-5-11 molecular sieve
Preparation method, shortens crystallization time greatly, and the degree of crystallinity of the ZSM-11 molecular sieve of final synthesis is high.
The preparation method of described fast synthesis of ZSM-5-11 molecular sieve of the present invention, successively by deionized water, template
Gel is prepared after agent, aluminum source and silicon source mix homogeneously, it is characterised in that: in prepared gel, add FeSO4·7H2O solid
And H2O2Solution, being eventually adding alkali source is worth Primogel, and Primogel is after crystallization, and solid separates with mother solution, and solid is dried
Hydrogen ZSM-11 molecular sieve.
One or more in aluminum sulfate, boehmite, aluminium hydroxide, aluminium oxide or aluminum isopropylate. of aluminum source.
One or more in Ludox, silica gel, tetraethyl orthosilicate or white carbon of silicon source.
Template is tetrabutyl ammonium bromide or TBAH.
Described alkali source is sodium hydroxide.
Described acid is one or more in sulphuric acid, hydrochloric acid, nitric acid or perchloric acid.
Ionized water, template, aluminum source and silicon source are uniform by following mixed in molar ratio: SiO2/Al2O3=45～100, template
Agent/SiO2=0.05～0.5, H2O/SiO2=15～50, OH-/SiO2=0.1～0.6.
FeSO4·7H2O solid and H2O2The addition of solution is FeSO in molar ratio4·7H2O/SiO2=0.00001～
0.0001、H2O2/SiO2=0.0005～0.002.
Comprise the following steps:
(1) successively that water, template, silicon source and aluminum source is uniform by following mixed in molar ratio, stir 10～30min, obtain solidifying
Glue；
(2) being added dropwise over acid in gel and regulating its pH value is 2～6, is sequentially added into FeSO to it4·7H2O solid and
H2O2Solution, stirs 30min；It is eventually adding alkali source, stirs 0.5～1h, obtain Primogel；
(3) by above-mentioned Primogel in confined conditions in 160～190 DEG C of crystallization 2～10h, solid separates with mother solution, warp
Deionized water wash, to pH=8～9, is dried in 100～120 DEG C, obtains ZSM-11 molecular screen primary powder.
In sum, the invention have the advantages that
The present invention introduces fenton reagent in existing ZSM-11 sieve synthesis procedure, and fenton reagent can utilize
Fe2+It is catalyzed H in acid condition2O2Decomposing and produce hydroxyl radical free radical (OH), the similar enzyme of its effect, at relatively mild bar
Contribute to being in the raw material species depolymerization of aggregating state and rearrangement under part, thus be greatly shortened formed secondary structure unit time
Between, shortening crystallization time greatly, the degree of crystallinity of the ZSM-11 molecular sieve of final synthesis is high.Additionally, the present invention is easy and simple to handle,
It is prone to industrializing implementation.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of ZSM-11 molecular sieve synthesized by comparative example 1.
Fig. 2 is the X-ray diffraction illustrated example of ZSM-11 molecular sieve synthesized by comparative example 2 and embodiment 2,3,4.
Fig. 3 is the X-ray diffractogram of ZSM-11 molecular sieve synthesized by embodiment 1.
Detailed description of the invention
In order to make those skilled in the art be better understood from the present invention, below in conjunction with specific embodiment, the present invention is done into one
The explanation of step, but protection domain not thereby limiting the invention.
The relative crystallinity of gained sieve sample is with synthesis of molecular sieve and 2 θ in ZSM-11 molecular sieve standard specimen spectrogram
The ratio of two characteristic diffraction peak peak area sums between 22.5～25.0 represents with percent.
ZSM-11 molecular sieve is prepared as standard specimen, degree of crystallinity location 100% according to the method in this patent embodiment 2.
Comparative example 1
According to synthesis mol ratio SiO2:Al2O3:TBABr:NaOH:H2O=1:0.015:0.22:0.46:25, first will
Tetrabutyl ammonium bromide (99wt%) joins in deionized water that (wherein the consumption of tetrabutyl ammonium bromide is 0.06 mole, following
The consumption of individual raw material all adds according to aforementioned proportion), stir to all dissolving, be then sequentially added into acidic silicasol (pH=
4.0；SiO225wt%), aluminum sulfate solution (Al2O37.16wt%) with sodium hydroxide solution (NaOH 47.3wt%), fully stir
Mix to obtain Primogel, be sealed against in 200ml band teflon-lined rustless steel high pressure crystallizing kettle, brilliant at 170 DEG C
Changing 24h, crystallizing kettle is lowered the temperature rapidly after taking out, and sucking filtration obtains solid product, and is washed till neutrality with its ionized water, and 110 DEG C of dry 12h are i.e.
Obtaining ZSM-11 molecular screen primary powder, check unformed material through X-ray diffraction (XRD), the X ray diffracting spectrum of sample is shown in accompanying drawing 1,
Degree of crystallinity is 0.
Comparative example 2
Repeating the operating procedure of embodiment 1, difference is Primogel crystallization 48h at 170 DEG C of preparation, synthesis
ZSM-11 molecular sieve verifies as pure phase ZSM-11 molecular sieve through X-ray diffraction (XRD), and the X ray diffracting spectrum of sample is shown in accompanying drawing
2, degree of crystallinity is set to 100%.
Embodiment 1
According to synthesis mol ratio SiO2:Al2O3:TBABr:NaOH:FeSO4:H2O2:H2O=1:0.015:0.22:
0.46:3.7×10-5:1.0×10-3: 25, first tetrabutyl ammonium bromide (99wt%) is joined in deionized water (wherein four
The consumption of butylammonium bromide is 0.06 mole, and the consumption of each raw material all adds according to aforementioned proportion below), stirring is to the most molten
Solve, be then sequentially added into acidic silicasol (pH=4.0；SiO225wt%), aluminum sulfate solution (Al2O37.16wt%), stirring
30min, adds nitric acid (HNO afterwards325wt%) slurry pH value is adjusted to 2.0, under stirring, is sequentially added into FeSO4·
7H2O solid and H2O2Solution (30wt%), stirs 30min, is eventually adding sodium hydroxide solution (NaOH 47.3wt%), fully
Stir to obtain Primogel, be sealed against in 200ml band teflon-lined rustless steel high pressure crystallizing kettle, at 190 DEG C
Crystallization 2h, lowers the temperature rapidly after crystallizing kettle taking-up, and sucking filtration obtains solid product, and is washed till pH=8 with its ionized water, 110 DEG C of dry 12h
Obtain ZSM-11 molecular screen primary powder, verify as pure phase ZSM-11 molecular sieve, the X-ray diffractogram of sample through X-ray diffraction (XRD)
Spectrum is shown in accompanying drawing 1, and degree of crystallinity is 78%.
Embodiment 2
Repeating the operating procedure of embodiment 2, difference is Primogel crystallization 6h at 170 DEG C of preparation, synthesis
ZSM-11 molecular sieve verifies as pure phase ZSM-11 molecular sieve through X-ray diffraction (XRD), and the X ray diffracting spectrum of sample is shown in accompanying drawing
2, degree of crystallinity is set to 108%.
Embodiment 3
According to synthesis mol ratio SiO2:Al2O3:TBABr:NaOH:FeSO4:H2O2:H2O=1:0.02:0.1:0.6:
1.0×10-5:5.0×10-4: 50, first TBAH (99wt%) is joined (the wherein tetrabutyl in deionized water
The consumption of ammonium bromide is 0.01 mole, and the consumption of each raw material all adds according to aforementioned proportion below), stir to all dissolving,
Then tetraethyl orthosilicate (SiO it is sequentially added into225wt%), boehmite (Al2O365wt%), stir 30min, add afterwards
Enter hydrochloric acid solution (HCl 18wt%) and slurry pH value is adjusted to 3.0, under stirring, be sequentially added into FeSO4·7H2O solid and
H2O2Solution (30wt%), stirs 30min, is eventually adding sodium hydroxide solution (NaOH 47.3wt%), is sufficiently stirred for initially
Gel, is sealed against in 200ml band teflon-lined rustless steel high pressure crystallizing kettle, crystallization 10h at 160 DEG C, brilliant
Changing after still takes out and lower the temperature rapidly, sucking filtration obtains solid product, and is washed till pH=9 with its ionized water, and 100 DEG C of dry 12h i.e. obtain ZSM-
11 molecular screen primary powders, verify as pure phase ZSM-11 molecular sieve through X-ray diffraction (XRD), and the X ray diffracting spectrum of sample is shown in accompanying drawing
Shown in 2, degree of crystallinity is 102%.
Embodiment 4
According to synthesis mol ratio SiO2:Al2O3:TBAOH:NaOH:FeSO4:H2O2:H2O=1:0.01:0.48:0.1:
1.0×10-4:2.0×10-3: 21.8, first by white carbon (SiO288.6wt%) join TBAH (TEAOH
In 25wt%) (wherein the consumption of white carbon is 0.12 mole, and the consumption of each raw material all adds according to aforementioned proportion below), stir
Mix to all dissolving, be subsequently adding aluminum hydroxide solid (Al2O365wt%), stir 30min, add sulfuric acid solution afterwards
(H2SO425wt%) slurry pH value is adjusted to 6.0, under stirring, is sequentially added into FeSO4·7H2O solid and H2O2Solution
(30wt%), stir 30min, be eventually adding sodium hydroxide solution (NaOH 47.3wt%), be sufficiently stirred for obtaining Primogel, will
It is sealed in 200ml band teflon-lined rustless steel high pressure crystallizing kettle, crystallization 6h at 170 DEG C, and crystallizing kettle takes out
Rear cooling rapidly, sucking filtration obtains solid product, and is washed till pH=8 with its ionized water, and 120 DEG C of dry 12h i.e. obtain ZSM-11 molecular sieve
Former powder, verifies as pure phase ZSM-11 molecular sieve through X-ray diffraction (XRD), shown in the X ray diffracting spectrum of sample as accompanying drawing 2, and knot
Crystalline substance degree is 110%.
Claims (9)
1. a preparation method for fast synthesis of ZSM-5-11 molecular sieve, successively by deionized water, template, aluminum source and silicon source, mixed
Gel is prepared after closing uniformly, it is characterised in that: in prepared gel, add FeSO4·7H2O solid and H2O2Solution, finally
Adding alkali source and prepare Primogel, Primogel is after crystallization, and solid separates with mother solution, and solid is dried to obtain Hydrogen ZSM-11 molecule
Sieve.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: aluminum source is selected from sulfur
One or more in acid aluminum, boehmite, aluminium hydroxide, aluminium oxide or aluminum isopropylate..
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: silicon source is selected from silicon
One or more in colloidal sol, silica gel, tetraethyl orthosilicate or white carbon.
The preparation method of Hydrogen ZSM-11 molecular sieve the most according to claim 1, it is characterised in that: template is the tetrabutyl
Ammonium bromide or TBAH.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: described alkali source is
Sodium hydroxide.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: described acid is sulfur
One or more in acid, hydrochloric acid, nitric acid or perchloric acid.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: ionized water, mould
Plate agent, aluminum source and silicon source are uniform by following mixed in molar ratio: SiO2/Al2O3=45～100, template/SiO2=0.05～
0.5、H2O/SiO2=15～50, OH-/SiO2=0.1～0.6.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: FeSO4·7H2O
Solid and H2O2The addition of solution is FeSO in molar ratio4·7H2O/SiO2=0.00001～0.0001, H2O2/SiO2=
0.0005～0.002.
The preparation method of fast synthesis of ZSM-5-11 molecular sieve the most according to claim 1, it is characterised in that: include following step
Rapid:
(1) successively that water, template, silicon source and aluminum source is uniform by following mixed in molar ratio, stir 10～30min, obtain gel；
(2) being added dropwise over acid in gel and regulating its pH value is 2～6, is sequentially added into FeSO to it4·7H2O solid and H2O2Molten
Liquid, stirs 30min；It is eventually adding alkali source, stirs 0.5～1h, obtain Primogel；
(3) by above-mentioned Primogel in confined conditions in 160～190 DEG C of crystallization 2～10h, solid separates with mother solution, through go from
The washing of sub-water, to pH=8～9, is dried in 100～120 DEG C, obtains ZSM-11 molecular screen primary powder.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381595A (en) * | 2017-09-06 | 2017-11-24 | 天津工业大学 | A kind of method that synthesis is sieved by potassium peroxydisulfate acceleration molecular |
| CN108940356A (en) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | A kind of preparation method of Fe@ZSM-11 mesoporous molecular sieve catalyst |
| CN110054199A (en) * | 2019-06-11 | 2019-07-26 | 兰州理工大学 | A kind of method of green energy conservation synthesis Fe-ZSM-5 molecular sieve |
| CN111017946A (en) * | 2019-12-25 | 2020-04-17 | 中国科学院大连化学物理研究所 | Preparation method of titanium-containing molecular sieve for olefin epoxidation process |
| CN114477221A (en) * | 2021-12-30 | 2022-05-13 | 廊坊市北辰创业树脂材料股份有限公司 | ZK-5 molecular sieve and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531376A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院大连化学物理研究所 | Microwave synthesis process for ZSM-11 molecular sieve |
-
2016
- 2016-06-15 CN CN201610428831.8A patent/CN105858683A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101531376A (en) * | 2008-03-12 | 2009-09-16 | 中国科学院大连化学物理研究所 | Microwave synthesis process for ZSM-11 molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| FENG, GUODONG, ET AL.: "Accelerated crystallization of zeolites via hydroxyl free radicals", 《SCIENCE》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381595A (en) * | 2017-09-06 | 2017-11-24 | 天津工业大学 | A kind of method that synthesis is sieved by potassium peroxydisulfate acceleration molecular |
| CN108940356A (en) * | 2018-05-29 | 2018-12-07 | 广东工业大学 | A kind of preparation method of Fe@ZSM-11 mesoporous molecular sieve catalyst |
| CN108940356B (en) * | 2018-05-29 | 2021-03-09 | 广东工业大学 | Preparation method of Fe @ ZSM-11 mesoporous molecular sieve catalyst |
| CN110054199A (en) * | 2019-06-11 | 2019-07-26 | 兰州理工大学 | A kind of method of green energy conservation synthesis Fe-ZSM-5 molecular sieve |
| CN111017946A (en) * | 2019-12-25 | 2020-04-17 | 中国科学院大连化学物理研究所 | Preparation method of titanium-containing molecular sieve for olefin epoxidation process |
| CN114477221A (en) * | 2021-12-30 | 2022-05-13 | 廊坊市北辰创业树脂材料股份有限公司 | ZK-5 molecular sieve and preparation method and application thereof |
| CN114477221B (en) * | 2021-12-30 | 2023-08-11 | 天津大学 | ZK-5 molecular sieve and preparation method and application thereof |
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