CN103801386A - Preparation method of silicalite-1/ZSM-5 composite molecular sieve - Google Patents
Preparation method of silicalite-1/ZSM-5 composite molecular sieve Download PDFInfo
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- CN103801386A CN103801386A CN201210440307.4A CN201210440307A CN103801386A CN 103801386 A CN103801386 A CN 103801386A CN 201210440307 A CN201210440307 A CN 201210440307A CN 103801386 A CN103801386 A CN 103801386A
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Abstract
The invention discloses a preparation method of a silicalite-1/ZSM-5 composite molecular sieve, which comprises the following steps: (1) dispersing a ZSM-5 molecular sieve in water under the ultrasonic action, adjusting the pH value, adding a silicon source, uniformly stirring, performing solid-liquid separation, drying to obtain the pretreated ZSM-5 molecular sieve; (2) adding the pretreated ZSM-5 molecular sieve obtained in step (1) into a mixed solution containing a template, sodium hydroxide and water, then additionally adding the silicon source, uniformly stirring, putting the mixture in a reaction vessel, performing crystallization, cooling, washing, and drying to obtain the silicalite-1/ZSM-5 composite molecular sieve.
Description
Technical field
The invention belongs to Zeolite synthesis field, specifically relate to a kind of preparation method of Silicalite-1/ZSM-5 composite molecular screen.
Background technology
At present, composite molecular screen obtains increasing researcher's concern.Various composite molecular screens are constantly synthesized out.MCM-41/ZSM-5 composite molecular screen as disclosed in CN1208718, disclosed micro porous molecular sieve (the ZSM-5 of CN1597516, β zeolite, modenite, zeolite L, MCM-22, ZSM-35) with mesopore molecular sieve (MCM-41) composite molecular screen, the disclosed ZSM-22/ZSM-23 composite molecular screen of CN1686800, the disclosed ZSM-35/MCM-22 composite molecular screen of CN101003379, the disclosed ZSM-5/ mordenite composite molecular sieve of CN101091920, the disclosed ZSM-5/SAPO-5(of CN101279288 or AlPO4-5) composite molecular screen, (Chem Mater 2006, 18, the composite molecular screen Silicalite-1/MFI of the nucleocapsid structure of 4959-4966) reporting etc.Different composite molecular screens has different character and serviceability, and its synthetic method is not identical yet.Wherein, the Silicalite-1/ZSM-5 composite molecular screen that has a nucleocapsid structure has received more concern because of it in the potential using value aspect alkylation of toluene methanol.Because Silicalite-1 and ZSM-5 molecular sieve have identical topological structure, by synthetic method, Silicalite-1 is covered to ZSM-5 surface, acid site by ZSM-5 molecular sieve surface has covered, prevent the generation of side reaction, do not affect again selective to paraxylene of ZSM-5 pore passage structure simultaneously.Therefore in preparation process, can Silicalite-1 cover ZSM-5 surface completely, and the thickness that can each ZSM-5 crystal grain surface be covered and Silicalite-1 covers ZSM-5 surface can directly affect the catalytic performance of molecular sieve.
(the Journal of Cataiysis such as D.Van Vu, 2006,243,389-394) report that one prepares Silicalite-1/H-ZSM-5 compound molecule screen method: first synthesize ZSM-5 molecular sieve, then by ion-exchange, molecular sieve has been converted into HZSM-5 molecular sieve.Then HZSM-5 molecular sieve is joined to TEOS-TPAOH-EtOH-H
2in O system, (TEOS is ethyl orthosilicate, TPAOH is TPAOH, EtOH is ethanol), the molecular sieve adding and the mass ratio of system are 1:15, obtained by intermediate water thermal synthesis the Silicalite-1/H-ZSM-5 composite molecular screen that Silicalite-1 covers, this molecular sieve can improve Shape-selective.
In sum, the synthetic method of existing Silicalite-1/H-ZSM-5 composite molecular screen all in various degree exist parcel incomplete shortcoming.Because these do not wrap up crystal completely, reduce the catalytic effect of composite molecular screen in course of reaction and selected type effect.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of Silicalite-1/ZSM-5 composite molecular screen.Composite molecular screen prepared by the method, Silicalite-1 covers completely at ZSM-5 outer surface, even thickness.
A preparation method for Silicalite-1/ZSM-5 composite molecular screen, comprises the steps:
(1) ZSM-5 molecular sieve is dispersed in water under ultrasonication, regulates pH value, add silicon source, stir, Separation of Solid and Liquid, dry, obtain pretreated ZSM-5 molecular sieve;
(2) pretreatment ZSM-5 molecular sieve step (1) being obtained joins in the mixed solution that contains template, NaOH and water, then adds silicon source, stirs, pack in reactor, crystallization, cooling, washing, dry, obtain Silicalite-1/ZSM-5 composite molecular screen.
In the inventive method, the ultrasonic dispersion of ZSM-5 molecular sieve hyperacoustic power used is 100 ~ 2500W, and hyperacoustic frequency is 40 ~ 60KHz.Hyperacoustic power density is 0.1 ~ 100W/g material.
In the inventive method, the described ZSM-5 molecular sieve particle size of step (1) is 50 ~ 500nm, and silica/alumina molar ratio is 25-300.
In the inventive method, it is 8 ~ 13 that step (1) adds NaOH and/or ammoniacal liquor to regulate pH value.
In the inventive method, in step (1), mixing speed is 100 ~ 500 revs/min, and mixing time is 2 ~ 4 hours.
In the inventive method, the described silicon source of step (1) is one or more in tetramethoxysilance, tetraethoxysilance and positive silicic acid the third fat; Silicon source (take silica) is 0.1 ~ 3 with the mass ratio of ZSM-5 molecular sieve.
In the inventive method, the baking temperature of step (1) is 40 ~ 120 ℃.
In the inventive method, in step (2), template is 4-propyl bromide (TPABr) or TPAOH (TPAOH).
In the inventive method, template in step (2): NaOH: water: pretreatment ZSM-5: the mass ratio in silicon source is: 0.5 ~ 3:0.05 ~ 0.2:1 ~ 10:1:0.1 ~ 3, wherein template is with TPA
+meter, silicon source is in silica.
In the inventive method, the silicon source of adding in step (2) is one or more in tetraethoxysilance, Ludox or white carbon.
In the inventive method, the crystallization condition in step (2) is: crystallization temperature is 130-180 ℃, and crystallization time is 12-36 hour.
In the inventive method, in Silicalite-1/ZSM-5 composite molecular screen, the thickness of Silicalite-1 molecular sieve shell can regulate between 10 ~ 200nm.
The inventive method is utilized and ultrasonic ZSM-5 molecular sieve is disperseed completely, regulates applicable mixing speed, and silicon source is mixed with ZSM-5 molecular sieve, guarantees can not come off at the silicon ion of ZSM-5 molecular sieve surface attachment simultaneously.Silicon ion carries out self assembly at ZSM-5 molecular sieve particle surface, has formed have certain thickness, uniform amorphous silica shell on ZSM-5 molecular sieve surface.By adding part silicon source, under the condition of Hydrothermal Synthesis, make up the defect that crystallization produces, guarantee to form on ZSM-5 molecular sieve surface continuity and the integrality of Silicalite-1 molecular sieve shell, ZSM-5 molecular sieve has been formed completely and covered.Core-shell structure compound molecular sieve prepared by the method has potential using value in alkylation of toluene methanol, xylene isomerization reaction.
Accompanying drawing explanation
Fig. 1 is the XRD diffraction pattern of the embodiment of the present invention 4 sinteticses.
Fig. 2-A is the stereoscan photograph of the ZSM-5 molecular sieve that adopts in the embodiment of the present invention.
Fig. 2-B is the stereoscan photograph of the embodiment of the present invention 4 sinteticses.
Fig. 2-C is the transmission electron microscope photo of the embodiment of the present invention 4 sinteticses.
Fig. 2-D is the stereoscan photograph of comparative example sintetics of the present invention.
The specific embodiment
Further illustrate preparation process of the present invention below in conjunction with embodiment.
the pretreatment of molecular sieve
Embodiment 1
Be 40KHz by 200 grams of ZSM-5 molecular sieves in supersonic frequency, power is to be dispersed in water under 360W ultrasonication, be under the condition of 25 ℃ at bath temperature, then regulating pH value with ammoniacal liquor is 11, adding ethyl orthosilicate, is to react 4 hours under the condition of 200 revs/min the mixture low whipping speed obtaining, and separates, dry at 80 ℃ of temperature, obtain pretreated ZSM-5 molecular sieve A1.
ZSM-5 molecular sieve grain diameter size is 200nm; Silica/alumina molecule mol ratio is 27; Ethyl orthosilicate (take silica) is 0.5:1 with the mass ratio of ZSM-5 molecular sieve.
Be 60KHz by 200 grams of ZSM-5 molecular sieves in supersonic frequency, power is to be dispersed in water under 800W ultrasonication, be under the condition of 35 ℃ at bath temperature, then regulating pH value with ammoniacal liquor is 10, adding ethyl orthosilicate, is to react 4 hours under the condition of 300 revs/min the mixture low whipping speed obtaining, and separates, dry at 60 ℃ of temperature, obtain pretreated ZSM-5 molecular sieve A2.
ZSM-5 molecular sieve grain diameter size is 500nm; Silica/alumina molecule mol ratio is 80; Ethyl orthosilicate (take silica) is 0.4:1 with the mass ratio of ZSM-5 molecular sieve.
Embodiment 3
Be 40KHz by 40 grams of ZSM-5 molecular sieves in supersonic frequency, power is to be dispersed in water under 2000W ultrasonication, be under the condition of 35 ℃ at bath temperature, then regulating pH value with ammoniacal liquor is 12, adding methyl silicate, is to react 3.5 hours under the condition of 250 revs/min the mixture low whipping speed obtaining, and separates, dry at 100 ℃ of temperature, obtain pretreated ZSM-5 molecular sieve A3.
ZSM-5 molecular sieve grain diameter size is 100nm; Silica/alumina molecule mol ratio is 80; Methyl silicate (take silica) is 0.6:1 with the mass ratio of ZSM-5 molecular sieve.
synthesizing of composite molecular screen
Embodiment 4
A1 is joined in the solution that contains NaOH, 4-propyl bromide and water, add ethyl orthosilicate, after stirring, pack in enclosed high pressure still, at 140 ℃ of temperature, crystallization 18 hours, cooling, washing, dry, obtain Silicalite-1/ZSM-5 composite molecular screen.
4-propyl bromide: NaOH: water: pretreated ZSM-5(A1): the mass ratio in silicon source is: 0.63:0.15:5:1:0.5, wherein 4-propyl bromide is with TPA
+meter, silicon source is in silica.
Embodiment 5
A2 is joined in the solution that contains NaOH, 4-propyl bromide and water, add Ludox, after stirring, pack in enclosed high pressure still, at 140 ℃ of temperature, crystallization 24 hours, cooling, washing, dry, obtain Silicalite-1/ZSM-5 composite molecular screen.
4-propyl bromide: NaOH: water: pretreated ZSM-5(A2): the mass ratio in silicon source is: 0.55:0.18:8:1:0.4, wherein 4-propyl bromide is with TPA
+meter, silicon source is in silica.
Embodiment 6
A3 is joined in the solution that contains NaOH, TPAOH and water, add Ludox, after stirring, pack in enclosed high pressure still, at 160 ℃ of temperature, crystallization 24 hours, cooling, washing, dry, obtain Silicalite-1/ZSM-5 composite molecular screen.
TPAOH: NaOH: water: pretreated ZSM-5(A3): the mass ratio in silicon source is: 0.78:0.12:4:1:1.3, wherein TPAOH is with TPA
+meter, silicon source is in silica.
Comparative example 1
3.6 NaOH are joined in 25g deionized water, taking 4-propyl bromide 16g joins in sodium hydroxide solution, taking until completely dissolved 10g ZSM-5 molecular sieve joins in solution, after stirring half an hour, add 60g Ludox, after stirring, pack in stainless steel crystallizing kettle 140 ℃ of crystallization 18 hours into, then, washing, dry, roasting obtain composite molecular screen.
Claims (12)
1. a preparation method for Silicalite-1/ZSM-5 composite molecular screen, is characterized in that comprising following content:
(1) ZSM-5 molecular sieve is dispersed in water under ultrasonication, regulates pH value, add silicon source, stir, Separation of Solid and Liquid, dry, obtain pretreated ZSM-5 molecular sieve;
(2) pretreatment ZSM-5 molecular sieve step (1) being obtained joins in the mixed solution that contains template, NaOH and water, then adds silicon source, stir, and crystallization, washing, dry, obtain Silicalite-1/ZSM-5 composite molecular screen.
2. method according to claim 1, is characterized in that: the ultrasonic dispersion of ZSM-5 molecular sieve hyperacoustic power used is 100 ~ 2500W, and hyperacoustic frequency is 40 ~ 60KHz.
3. method according to claim 1, is characterized in that: the described ZSM-5 molecular sieve particle size of step (1) is 50 ~ 500nm, and silica/alumina molar ratio is 25-300.
4. method according to claim 1, is characterized in that: it is 8 ~ 13 that step (1) adds NaOH and/or ammoniacal liquor to regulate pH value.
5. method according to claim 1, is characterized in that: in step (1), mixing speed is 100 ~ 500 revs/min, and mixing time is 2 ~ 4 hours.
6. method according to claim 1, is characterized in that: the described silicon source of step (1) is one or more in tetramethoxysilance, tetraethoxysilance and positive silicic acid the third fat; The mass ratio of silicon source and ZSM-5 molecular sieve is 0.1:1 ~ 3:1, and wherein silicon source is in silica.
7. method according to claim 1, is characterized in that: the baking temperature of step (1) is 40 ~ 120 ℃.
8. method according to claim 1, is characterized in that: the template in step (2) is 4-propyl bromide or TPAOH.
9. method according to claim 1, is characterized in that: in step (2), and template: NaOH: water: pretreatment ZSM-5: the mass ratio in silicon source is: 0.5 ~ 3:0.05 ~ 0.2:1 ~ 10:1:0.1 ~ 3, wherein template is with TPA
+meter, silicon source is in silica.
10. method according to claim 1, is characterized in that: the silicon source of adding in step (2) is one or more in tetraethoxysilance, Ludox or white carbon.
11. methods according to claim 1, is characterized in that: the crystallization condition in step (2) is: crystallization temperature is 130-180 ℃, and crystallization time is 12-36 hour.
12. methods according to claim 1, is characterized in that: in Silicalite-1/ZSM-5 composite molecular screen, the thickness of Silicalite-1 molecular sieve shell is 10 ~ 200nm.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104415784A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of Silicalite-1/ZSM-5 composite molecular sieve |
| CN106563497A (en) * | 2016-10-26 | 2017-04-19 | 新沂市中诺新材料科技有限公司 | Preparation method for modifying ethyl alcohol to prepare olefin by adopting molecular sieve to catalyze |
| CN107758689A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The synthetic method of the core-shell type zeolite molecular sieves of ZSM 5/Silicalite 1 |
| CN108246345A (en) * | 2018-01-23 | 2018-07-06 | 湖南大学 | A kind of preparation method of oxide-molecular sieve catalyst |
| CN109529523A (en) * | 2018-11-26 | 2019-03-29 | 吉林大学 | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method |
| CN111977662A (en) * | 2020-09-02 | 2020-11-24 | 西北大学 | Core-shell heterogeneous composite framework molecular sieve and preparation method thereof |
Families Citing this family (2)
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| CN108339563A (en) * | 2018-01-23 | 2018-07-31 | 湖南大学 | A kind of preparation method of aluminium oxide-molecular sieve catalyst |
| CN108339373B (en) * | 2018-01-23 | 2020-06-16 | 湖南大学 | Application of alumina-molecular sieve catalyst in catalyzing carbon dioxide desorption |
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| CN102311124A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve |
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| CN102311124A (en) * | 2010-07-07 | 2012-01-11 | 中国石油化工股份有限公司 | Method for preparing Silicalite-1/ZSM-5 composite molecular sieve |
Non-Patent Citations (1)
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| DUNG VAN VU, ET AL.: "Selective formation of para-xylene over H-ZSM-5 coated with polycrystalline silicalite cystals", 《JOURNAL OF CATALYSIS》, vol. 243, 31 December 2006 (2006-12-31), pages 389 - 394 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104415784A (en) * | 2013-08-22 | 2015-03-18 | 中国石油化工股份有限公司 | Preparation method of Silicalite-1/ZSM-5 composite molecular sieve |
| CN104415784B (en) * | 2013-08-22 | 2016-10-19 | 中国石油化工股份有限公司 | A kind of preparation method of Silicalite-1/ZSM-5 composite molecular screen |
| CN107758689A (en) * | 2016-08-23 | 2018-03-06 | 中国石油化工股份有限公司 | The synthetic method of the core-shell type zeolite molecular sieves of ZSM 5/Silicalite 1 |
| CN107758689B (en) * | 2016-08-23 | 2020-10-16 | 中国石油化工股份有限公司 | Synthesis method of ZSM-5/Silicalite-1 core-shell zeolite molecular sieve |
| CN106563497A (en) * | 2016-10-26 | 2017-04-19 | 新沂市中诺新材料科技有限公司 | Preparation method for modifying ethyl alcohol to prepare olefin by adopting molecular sieve to catalyze |
| CN106563497B (en) * | 2016-10-26 | 2019-05-03 | 东明澳科精细化工有限公司 | The preparation method of denatured ethanol olefin hydrocarbon molecules sieve catalysis |
| CN108246345A (en) * | 2018-01-23 | 2018-07-06 | 湖南大学 | A kind of preparation method of oxide-molecular sieve catalyst |
| CN109529523A (en) * | 2018-11-26 | 2019-03-29 | 吉林大学 | Molecular sieve core-mesoporous organosilicon hollow shell multi-stage porous composite material and preparation method |
| CN111977662A (en) * | 2020-09-02 | 2020-11-24 | 西北大学 | Core-shell heterogeneous composite framework molecular sieve and preparation method thereof |
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