CN103449464A - Preparation method of mesoporous zeolite molecular sieve - Google Patents
Preparation method of mesoporous zeolite molecular sieve Download PDFInfo
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- CN103449464A CN103449464A CN2012101703185A CN201210170318A CN103449464A CN 103449464 A CN103449464 A CN 103449464A CN 2012101703185 A CN2012101703185 A CN 2012101703185A CN 201210170318 A CN201210170318 A CN 201210170318A CN 103449464 A CN103449464 A CN 103449464A
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Abstract
The invention provides a preparation method of mesoporous zeolite by utilizing a polyelectrolyte-surfactant composite as a template, and belongs to the technical field of organic chemistry, physical chemistry, and catalytic chemistry. The preparation method comprises following steps: utilizing conventional silicon source and aluminum source, taking a low cost anion polyelectrolyte-surfactant composite as a template, adopting an one-pot method, hydrothermally crystallizing at the temperature of 140 DEG C, and burning at the temperature of 550 DEG C for 6 hours so as to obtain mesoporous silicalite-1 and mesoporous ZSM-5. The preparation method utilizes the polyelectrolyte (polyacrylic acid PAA)-surfactant (cetyl trimethyl ammonium bromide CTAB) composite as the template to prepare mesoporous zeolite with hole sizes of 5 to 20 nm, mesoporous ZSM-5 has a high catalytic activity in catalytic reactions; the adding sequence of NaCl is changed so as to synthesize mesoporous silicalite-1 with a hole size of about 3 nm, furthermore, the mesopores are smaller and the array of mesopores is tighter; mesoporous silicalite-1 can also be prepared from another polyelectrolyte (polyacrylic acid PAA)-surfactant (cetyl pyridinium chloride) composite, indicating that the method of synthesizing mesoporous zeolite by utilizing a polyelectrolyte-surfactant composite as the template can be widely popularized, and has a potential application value in the field of catalysis.
Description
Technical field
The invention belongs to inorganic chemistry, physical chemistry, materials chemistry, catalytic chemistry, specially refer to the technology of preparing of the synthetic mesoporous zeolite of template.
Background technology
Zeolitic material, because it has good hydrothermal stability, strongly-acid and shape selectivity, is widely used in the fields [seeing Corma A.Chem.Rev., 1997,97,2373-2419.] such as catalysis, absorption and ion-exchange.But the micropore canals of zeolite molecular sieve very little (being generally less than 1 nanometer), and be unfavorable for the diffusion of reactant.In order to address this problem, the mesoporous material with regular pore canal and high-ratio surface that the MCM-41 of take is representative arise at the historic moment [Kresge C T, Leonowicz M E, Roth W J.Nature, 1992,359,710-712.].But because the hydrothermal stability of this class mesoporous material is not strong, acid little, still can not be widely used in the Industrial Catalysis field at present.Therefore, the Mesoporous Zeolite Materials that preparation has zeolite and mesoporous material advantage, become the emphasis that current scientific circles pay close attention to.
The method of synthesising mesoporous zeolite has a lot, comprises soft template method, hard template method and alkaline purification method, and in document, the general cationic polymers that uses adds in the synthetic system of zeolite molecular sieve, as mesoporous template.This is that the silicate presoma is with negative charge because the Zeolite synthesis system is alkalescence, can with anionic polymer generation electrostatic interaction.If the use anionic polymer, electrostatic interaction can not occur, so not yet had in document and introduce the Zeolite synthesis system with anionic polymer and form mesoporous report.This patent, by utilizing polyelectrolyte-tensio-active agent to form the characteristic of mixture, using anionic polymer as mesoporous template, is incorporated in the zeolite molecular sieve synthetic system, successfully synthesizes with enriching the mesoporous molecular screen material of intracrystalline.The contrast cationic polymers, anionic polymer toxicity is little, and kind is many, the characteristics that price is low, so the described preparation method of this patent has important value in synthesising mesoporous zeolite molecular sieve field.
Summary of the invention
The technical problem to be solved in the present invention is, utilizing anionic polyelectrolyte and surfactant complex cheaply is template, synthesizes to contain and enriches the mesoporous Mesoporous Zeolite Materials of intracrystalline, makes it show higher catalytic activity in catalyzed reaction.
The anionic polyelectrolyte that the present invention uses is polyacrylic acid, and cats product is cetyl trimethylammonium bromide or chloro-hexadecane yl pyridines.
The mesoporous zeolite of indication of the present invention refers to mesoporous silicalite-1 and mesoporous ZSM-5.
A kind of polyelectrolyte surfactant complexes is the synthetic mesoporous zeolite of template, it is characterized in that this mesoporous zeolite contains abundant intracrystalline mesoporous.
The preparation method of mesoporous zeolite of the present invention is to take tetraethoxy (TEOS) as the silicon source, with sodium metaaluminate (NaAlO
2) be the aluminium source, take polyelectrolyte surfactant complexes as template, organic ammonium salt is that micropore template and parents' silane are the auxiliary template agent, the synthesising mesoporous silicalite-1 of hydrothermal method and mesoporous ZSM-5.It is characterized in that: anionic polyelectrolyte (polyacrylic acid PAA)-cats product (cetyl trimethylammonium bromide CTAB) mixture of take is template, or to take other polyelectrolyte (polyacrylic acid PAA)-tensio-active agent (cetyl pyridinium CPC) mixture be template; Subsequently, add sodium-chlor, organic amine template, ,Lv source, silicon source, after stirring, in closed reactor, 90-160 ℃ of hydrothermal crystallizing is 2～10 days; Products therefrom obtains the mesoporous zeolite molecular sieve in 1～6 hour 350～600 ℃ of roastings.
The mesoporous ZSM-5 that removes template is first used to 1M NH
4nO
3exchange 100 ℃ of backflows three times.Then 550 ℃ of degree roasting 2h are by Na
+the ZSM-5 of type is transformed into H
+type, make it there is acidity in catalyzed reaction.
Method of the present invention is compared with background technology, utilizes first anionic polyelectrolyte-cats product mixture for the synthesising mesoporous zeolite of template, has a large amount of intracrystallines mesoporous, shows higher catalytic activity in catalyzed reaction.
The accompanying drawing explanation
Fig. 1: the XRD figure of mesoporous silicalite-1 sample and nitrogen adsorption desorption isotherm and graph of pore diameter distribution
Fig. 2: the SEM figure of mesoporous silicalite-1 sample
Fig. 3: the TEM figure of mesoporous silicalite-1 sample and corresponding high resolution thereof
Fig. 4: after add XRD figure and nitrogen adsorption desorption and the graph of pore diameter distribution of the synthesising mesoporous silicalite-1 of NaCl
Fig. 5: after add SEM figure and the TEM figure (d figure is the high resolution that c is corresponding) thereof of the synthesising mesoporous silicalite-1 of NaCl
Figure: 6: the XRD figure of mesoporous ZSM-5 and nitrogen adsorption desorption isotherm and graph of pore diameter distribution thereof
Fig. 7: the SEM figure of mesoporous ZSM-5 and TEM figure thereof
Fig. 8: the nuclear-magnetism (NMR) of mesoporous ZSM-527 Al MAS figure before and after roasting
Embodiment
Embodiment 1: take polyelectrolyte surfactant complexes as the synthesising mesoporous silicalite-1 of template
Synthesis material: polyacrylic acid (PAA), cetyl trimethylammonium bromide (CTAB), TPAOH (TPAOH), tetraethoxy (TEOS), sodium-chlor (NaCl), octadecyl dimethyl [trimethoxy silicon propyl group] ammonium chloride (TPOAc).
Synthetic ratio: 10SiO
2: 3.6TPAOH: 0.08TPOAc: 360H
2o: 4.2NaCl
Synthesis step: a certain amount of NaCl is dissolved in the deionized water of 5ml, adds 25% TPAOH to form settled solution.This solution is joined in advance synthetic CTAB and PAA mixture, stir 20min.TEOS and a small amount of TPOAc (50% methanol solution) join in this solution under agitation condition.Last stirring at room 2h obtains the mixed emulsion of homogeneous.Be put in reactor 140 ℃ of crystallization 6d of hydro-thermal.The product suction filtration obtained, washing, 80 ℃ of dryings, 550 ℃ of roasting 6h.
Take polyelectrolyte surfactant complexes as template has synthesized mesoporous silicalite-1.(Fig. 1 a) shows XRD, is typical MFI structure.
Nitrogen adsorption-desorption graphic representation (Fig. 1 b) shows, at P/P
0the hop at ≈ 0.2 place is N
2the mutually transformation of absorption molecule in micropore; At relative pressure, be 0.4<P/P
0the hop at<0.9 place, be only real mesoporous existence and cause, and corresponding pore size distribution is at 5～20nm.
SEM (Fig. 2) shows that this sample is comprised of raphioid fiber, and granular size is at 20-30 μ m.
TEM (Fig. 3) shows, intracrystalline is mesoporous high-visible, and high-resolution-ration transmission electric-lens and corresponding electron diffraction show, this sample be highly crystalline and be monocrystalline.
Embodiment 2: after add the synthesising mesoporous silicalite-1 of NaCl
Synthesis material: polyacrylic acid (PAA), cetyl trimethylammonium bromide (CTAB), TPAOH (TPAOH), tetraethoxy (TEOS), sodium-chlor (NaCl), octadecyl dimethyl [trimethoxy silicon propyl group] ammonium chloride (TPOAc).
Synthesis step: in CTAB and PAA mixture, directly add 25% TPAOH, stir 20min, solution remains oyster white.TEOS and a small amount of TPOAc (50% methanol solution) join in this solution under agitation condition, stir 30min.Finally a certain amount of NaCl is dissolved in the water of 5ml, and it is joined in above-mentioned solution.Room temperature mechanical stirs 2h, obtains the emulsion of thickness.Be put in reactor 140 ℃ of crystallization 6d of hydro-thermal.The product suction filtration obtained, washing, 80 ℃ of dryings, 550 ℃ of roasting 6h.
Take polyelectrolyte surfactant complexes as template, after add NaCl and synthesized mesoporous silicalite-1.(Fig. 4 a) shows XRD, is typical MFI structure.
Nitrogen adsorption-desorption graphic representation (Fig. 4 b) shows, is 0.4<P/P at relative pressure
0the hop at<0.8 place, corresponding pore size distribution is at 3nm.
Shown in SEM figure (Fig. 5 a, b), what pattern was surface irregularity is spherical, and granular size is in the 20um left and right.TEM figure (Fig. 5 a, b) shows mesoporous less, arranges more tight.Its high-resolution-ration transmission electric-lens shows that this sample is monocrystalline.
Embodiment 3: take other polyelectrolyte surfactant complexes as the synthesising mesoporous silicalite-1 of template
Synthesis material: polyacrylic acid (PAA), chloro-hexadecane yl pyridines (CPC), TPAOH (TPAOH), tetraethoxy (TEOS), sodium-chlor (NaCl), octadecyl dimethyl [trimethoxy silicon propyl group] ammonium chloride (TPOAc).
Synthesis step: with the step of embodiment 1 intermediary hole silicalite-1, only cats product is become to chloro-hexadecane yl pyridines (CPC).
Sign in the final effect of the mesoporous silicalite-1 that utilizes this method to be synthesized and embodiment 1 does not have large difference.
Embodiment 4: take polyelectrolyte surfactant complexes as the synthesising mesoporous ZSM-5 of template
Synthesis material: polyacrylic acid (PAA), cetyl trimethylammonium bromide (CTAB), TPAOH (TPAOH), tetraethoxy (TEOS), sodium-chlor (NaCl), sodium metaaluminate (NaAlO
2) octadecyl dimethyl [trimethoxy silicon propyl group] ammonium chloride (TPOAc).
Synthetic ratio: 100SiO
2: Al
2o
3: 36TPAOH: 0.8TPOAc: 3600H
2o: 42NaCl
Synthesis step: a certain amount of NaCl and aluminium source (NaAlO
2) be dissolved in the deionized water of 5ml, 25% TPAOH joins in solution and forms solution.This solution is joined in advance synthetic CTAB and PAA mixture, stir 20min.TEOS and a small amount of TPOAc (50% methanol solution) mix in advance, under agitation condition, join in this solution.The mol ratio that sial feeds intake is 100SiO
2: Al
2o
3.The last mixing solutions that at room temperature stirs 2h acquisition homogeneous.This solution is put in reactor to 140 ℃ of crystallization of hydro-thermal 6 days.The product suction filtration obtained, washing, 80 ℃ of dryings, 550 ℃ of roasting 6h.
Take polyelectrolyte surfactant complexes as template has synthesized mesoporous ZSM-5.(Fig. 6 a) shows XRD, is typical MFI structure.
Nitrogen adsorption-desorption graphic representation (Fig. 6 b) shows, is 0.4<P/P at relative pressure
0the hop at<0.9 place, corresponding pore size distribution is at 5～20nm.
(it is irregular spherical that Fig. 7 a) shows to SEM, and granular size is about 10 μ m.
TEM (Fig. 7 b-7d) shows, intracrystalline is mesoporous high-visible, and high-resolution-ration transmission electric-lens and corresponding electron diffraction show, this sample be highly crystalline and be monocrystalline.
In the aldolization of pimelinketone and methyl alcohol, the ICP test analysis shows that the Si/Al ratio of mesoporous ZSM-5 is 55, and the transformation efficiency of pimelinketone is 85%, and the Si/Al of commercial ZSM-5 is 23, but the transformation efficiency of pimelinketone only has 76%, the ZSM-5 that mesoporous ZSM-5 is more traditional shows higher catalytic activity.
Claims (4)
1. the preparation method of a mesoporous zeolite molecular sieve, it is characterized in that take that anionic polyelectrolyte-cats product mixture is as mesoporous template, take tetraethoxy as the silicon source, take sodium metaaluminate as the aluminium source, organic amine is the micropore template, concrete steps are: anionic polyelectrolyte and cats product fully are dissolved in to deionized water and obtain settled solution, under constantly stirring, drip ammonia soln in above-mentioned solution, obtain the mixture of complex polyelectrolyte particle and tensio-active agent, the system proterties is milk shape white emulsion; Subsequently, add sodium-chlor, organic amine template, ,Lv source, silicon source, after stirring, in closed reactor, 90-160 ℃ of hydrothermal crystallizing is 2～10 days; Products therefrom obtains the mesoporous zeolite molecular sieve in 1～6 hour 350～600 ℃ of roastings.
2. the preparation method of material as claimed in claim 1, is characterized in that take that described anionic polyelectrolyte is as polyacrylic acid.
3. in preparation method as claimed in claim 1, cats product is the quaternary surfactant with alkyl chain.
4. the quaternary surfactant with alkyl chain as claimed in claim 3 is cetyl trimethylammonium bromide.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874420A (en) * | 2015-06-19 | 2015-09-02 | 南开大学 | Preparation method for titanium-containing hierarchical porous structure mesoporous molecular sieve catalyst |
| CN106006666A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106006667A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106179510A (en) * | 2016-07-07 | 2016-12-07 | 许昌学院 | A kind of mesoporous molecular sieve catalyst containing double acidic sites and preparation method thereof |
| CN110835115A (en) * | 2018-08-16 | 2020-02-25 | 中国石油化工股份有限公司 | Preparation method of mesoporous ZSM-5 zeolite |
| CN114772609A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of high-silicon ZSM-5 molecular sieve with mesoporous structure |
Citations (2)
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| CN1608990A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing ZSM-5 molecular sieve of nano size and containing hetero atom |
| CN102372282A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院大连化学物理研究所 | Amine-free synthesis method for ZSM5/ZSM11 co-crystallized zeolite |
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2012
- 2012-05-29 CN CN2012101703185A patent/CN103449464A/en active Pending
Patent Citations (2)
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|---|---|---|---|---|
| CN1608990A (en) * | 2004-09-16 | 2005-04-27 | 华东师范大学 | Process of preparing ZSM-5 molecular sieve of nano size and containing hetero atom |
| CN102372282A (en) * | 2010-08-18 | 2012-03-14 | 中国科学院大连化学物理研究所 | Amine-free synthesis method for ZSM5/ZSM11 co-crystallized zeolite |
Non-Patent Citations (1)
| Title |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874420A (en) * | 2015-06-19 | 2015-09-02 | 南开大学 | Preparation method for titanium-containing hierarchical porous structure mesoporous molecular sieve catalyst |
| CN106006666A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | Hierarchical pore ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106006667A (en) * | 2016-04-22 | 2016-10-12 | 宁夏大学 | ZSM-5 molecular sieve with nanosheet layer structure and synthesis method thereof |
| CN106179510A (en) * | 2016-07-07 | 2016-12-07 | 许昌学院 | A kind of mesoporous molecular sieve catalyst containing double acidic sites and preparation method thereof |
| CN110835115A (en) * | 2018-08-16 | 2020-02-25 | 中国石油化工股份有限公司 | Preparation method of mesoporous ZSM-5 zeolite |
| CN114772609A (en) * | 2022-04-22 | 2022-07-22 | 山东亮剑环保新材料有限公司 | Preparation method of high-silicon ZSM-5 molecular sieve with mesoporous structure |
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Application publication date: 20131218 |