CN1506308A - Process of preparing hollow zeolite microsphere - Google Patents
Process of preparing hollow zeolite microsphere Download PDFInfo
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- CN1506308A CN1506308A CNA021511810A CN02151181A CN1506308A CN 1506308 A CN1506308 A CN 1506308A CN A021511810 A CNA021511810 A CN A021511810A CN 02151181 A CN02151181 A CN 02151181A CN 1506308 A CN1506308 A CN 1506308A
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Abstract
The present invention relates to the preparation process of hollow zeolite microsphere. Nano zeolite colloid solution is used as adsorbing and depositing solution and hollow silica microsphere through soaking in polycation electrolyte solution as template agent to deposit nano zeolite onto the hollow silica microsphere by means of the electrostatic attraction between nano zeolite and polycation electrolyte. Through subsequent gas-solid phase treatment with ammonia or organic amine and water vapor, the inside hollow silica microsphere is converted into zeolite crystal. The present invention is superior to available technology in that it is relatively simple and has less crushing of synthesized hollow microsphere, so that it may be used in the industrial preparation of hollow zeolite microsphere.
Description
Technical field
The present invention relates to prepare the method for zeolite hollow microsphere, particularly prepare the method for zeolite hollow microsphere about a kind of mesopore silicon oxide microsphere of handling zeolite seed crystal parcel mutually by gas-solid.
Background technology
Tiny balloon is the material of the special nucleocapsid structure of a class, has all shown important use value in the protective of the design of the embedding of medicine and slowly-releasing, artificial cell, bioactive agents and special catalyst assembling design.Zeolite is that a class has and enriches micropore, good molecular screening performance and the good heat and the crystalline material of hydrothermal stability, in catalysis, absorption with the field such as separate purposes is widely arranged, be the research focus in material field in recent years and how to synthesize the tiny balloon that is built into by zeolitic material.
At present, synthetic layer laminate (Layer-by-Layer) method (X.D.Wang, W.L.Yang, Y.Tang, Y.J.Wang, S.K.Fu and Z.Gao, Chem.Commun., 2000,2161 of mainly depending on of hollow zeolite microballoon; K.H.Rhodes, S.A.Davis, F.Caruso, B.Zhang, S.Mann, Chem.Mater., 2000,12,2832.).This method is to be template with the polystyrene microsphere, under polyelectrolyte helps, the surface that zeolite nano particle multilayer is adsorbed on polystyrene microsphere by electrostatic adsorption forms the mixture of nuclear-shell, removes the microsphere of zeolite that wherein polystyrene core can obtain hollow structure by the method for roasting or chemical corrosion then.This method can be regulated the thickness and the composition of zeolite shell easily; but operation steps is comparatively loaded down with trivial details; because in the multiple adsorb process; unnecessary zeolite microparticles or polyelectrolyte all will be removed by the method for high speed centrifugation and washing; and roasting or the chemical corrosion process of removing polystyrene core can cause the contraction (usually greater than 20%) of shell and break, and is unfavorable for the practical application of hollow ball.
Summary of the invention
Technical problem to be solved by this invention is to overcome to have complex operation in the conventional art, and the synthetic tiny balloon is easy disruptive problem in removing the process of polystyrene core, and a kind of new method for preparing zeolite hollow microsphere is provided.This method has simple to operate, and synthetic zeolite hollow microsphere material is even, fine and close, physical strength is high, is difficult for the disruptive characteristics.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method for preparing zeolite hollow microsphere, with weight percent concentration is 0.05～20%, pH value is 9.5～14, grain-size be 1～300 nanometer the nano zeolite glue as absorption deposit fluid, to handle through the polycation electrolyte solution soaking, diameter is that 1～8 micron mesopore silicon oxide microsphere is as template core, at first in the absorption deposit fluid, nano zeolite is deposited on the mesopore silicon oxide microsphere, get nano zeolite/mesopore silicon oxide complex microsphere, it is 100～240 ℃ in temperature then, pressure is under the autogenous pressure condition, with ammonia or the relative nano zeolite with the water vapor gas-solid of organic amine/mesopore silicon oxide complex microsphere carries out gas-solid handles mutually, treatment time is 1 hour to 20 days, under the effect of nano zeolite crystal seed, the silicon source of the mesopore silicon oxide microsphere of inside is converted into zeolite crystal, through washing, dry and roasting gets zeolite hollow microsphere.
In the technique scheme, by weight percentage, the concentration preferable range of nano zeolite glue is 0.1～10% in the absorption deposit fluid, and the pH value preferable range of nano zeolite glue is 9.5～12, and the grain-size preferable range of nano zeolite glue is 60～300 nanometers.The polycation electrolyte preferred version is the poly dimethyl allyl ammonia chloride, polycation electrolyte solution weight percentage concentration preferable range is 0.1～5%, and the time preferable range of polycation electrolyte solution soaking mesopore silicon oxide microsphere is 0.1～24 hour.It is 120～200 ℃ that nano zeolite/mesopore silicon oxide complex microsphere is carried out the temperature preferable range that gas-solid handles mutually, and the treatment time preferable range is 6 hours～10 days.The organic amine preferred version is for being selected from C
nH
2n+1NH
2, the primary amine of n=0～5, C
nH
2n+1C
mH
2m+1NH, n, m are respectively 0～5 secondary amine or C
nH
2n+1C
mH
2m+1C
iH
2i+1N, n, m, i are respectively 0～5 tertiary amine, and more preferably scheme is to be selected from least a in n-Butyl Amine 99, Tri N-Propyl Amine, quadrol or the triethylamine.The zeolite preferred version is Silicalite-1 or ZSM-5 zeolite.
The absorption deposit fluid can be prepared by the synthetic zeolite crystallite is dispersed in the salts solutions such as water or sodium-chlor among the present invention.The preparation of mesopore silicon oxide microsphere is with reference to Schult-Ekloff, G.; Rathousky, J.; Zukal, A.Int.J.Inorg.Mater.1999,1,97.
Concrete operations are:
With 1.0～3.0 gram CTAB (cetyl trimethylammonium bromide), 1.5～4.0 gram Na
2SiO
39H
2O and 10～20 gram distilled water mix, stir under the room temperature, then 1.0～3.0 milliliters of ethyl acetate are injected above-mentioned solution, stop after 30 seconds stirring, the mixed solution that room temperature was left standstill after 5 hours heated 50 hours in 90 ℃ oil bath, product is filtered and obtains silicon oxide microsphere with the distilled water wash clean.Mesopore silicon oxide microsphere surface is cleaned by available distilled water after the polycation electrolyte solution-treated; Mesopore silicon oxide microsphere after the modification behind the deposition certain hour, can take out with adsorbing the nano zeolite colloid again after distilled water or weak acid or the weak alkaline aqueous solution washing in the absorption deposit fluid.Absorption deposition after product can dry at 40～180 ℃; Can be for the template of removing in the zeolite micropore with zeolite hollow microsphere roasting in air atmosphere, the temperature of roasting is 200～1000 ℃.
The present invention is by adopting glue with nano zeolite as the absorption deposit fluid, with modification mesopore silicon oxide microsphere as template core, utilize the electrostatic attraction between nano zeolite and the polyelectrolyte, nano zeolite is deposited on the mesopore silicon oxide microsphere effectively, handle mutually by gas-solid then, under the effect of nano zeolite crystal seed, silicon source with inner mesopore silicon oxide microsphere transforms for zeolite crystal effectively, make the entire operation technology easier, the zeolite hollow microsphere that this in addition method makes is owing to be by natural formation, therefore have the spherical shell of even compact and high physical strength, the percentage of damage of product is low, less than 5%, both improved preparation efficiency, guarantee quality product and yield rate again, obtained better technical effect
Description of drawings
Fig. 1 is mesopore silicon oxide microsphere A
1The SEM photo.
Fig. 2 is nano zeolite/mesopore silicon oxide complex microsphere B
1The SEM photo.
Fig. 3 is product D
1SEM photo (insertion portion is the SEM photo of high multiple among the figure).
Fig. 4 is product D
1The TEM photo.
Fig. 5 is a product F
1The SEM photo.
Fig. 6 is product D
1The XRD figure spectrum of SEM.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
With 1.96 gram cetyl trimethylammonium bromides (CTAB), 2.32 gram Na
2SiO
39H
2O and 17 gram distilled water mix, stir under the room temperature, then 1.75 milliliters of ethyl acetate are injected above-mentioned solution, stop after 30 seconds stirring, the mixed solution that room temperature was left standstill after 5 hours heated 50 hours in 90 ℃ oil bath, product is filtered and obtains silicon oxide microsphere A with the distilled water wash clean
1
[embodiment 2]
Tetraethoxy-silicane, TPAOH and distilled water are mixed according to 25: 9: 480 mole proportioning, vigorous stirring is 1 day under the room temperature, in the 373K oil bath, refluxed 18～36 hours, obtain nanometer Silicalite-1 (MFI skeleton structure) zeolite glue, again with the colloid centrifugation repeatedly that obtains, again be dispersed in the distilled water after the washing, obtaining pH is 9.5, and weight percent is 4% Silicalite-1 zeolite glue (the zeolite particle diameter is 60 nanometers).Be that 0.3% polycation electrolyte Poly Dimethyl Diallyl Ammonium Chloride (PDDA) carries out pre-treatment to mesopore silicon oxide microsphere surface with weight concentration earlier before the deposition zeolite, adsorption time is about 1 hour, fully soaks, washs with deionized water after the absorption.The mesopore silicon oxide microsphere of modification is immersed in (about adjusting pH to 9.5) in the nano zeolite glue that concentration is 1% (weight), Static Adsorption 1 hour.After finishing, absorption, can obtain nano zeolite/mesopore silicon oxide complex microsphere B with the room temperature airing
1
[embodiment 3]
Experimentizing with the method identical with embodiment 2, but use the zeolite of different-grain diameter to be building block, is respectively the Silicalite-1 zeolite glue of 150 nanometers and 300 nanometers with particle diameter; Obtain nano zeolite/mesopore silicon oxide complex microsphere, be designated as B respectively
2, B
3
[embodiment 4]
Experimentize with the method identical, but change the type of employed nano zeolite,, obtained nano zeolite/mesopore silicon oxide microsphere complex microsphere C by ZSM-5 nano zeolite (the zeolite particle diameter is 150 nanometers) with embodiment 2
1
[embodiment 5]
With 0.2 gram sample B
1Place reactor porous plate top.Inject 2 gram quadrols with syringe to reactor bottom, the mixture of triethylamine and distilled water (mol ratio is 2: 9: 6) was 140 ℃ of following crystallization 2 days, and product takes out the back and promptly gets hollow microsphere of zeolite D with distilled water wash
1After 393K dries 12 hours directly in air atmosphere in 823K roasting 8 hours, promptly obtain hollow zeolite micro-sphere material E
1
[embodiment 6]
Experimentize with the method identical with embodiment 5, but handle the mesopore silicon oxide microsphere of ZSM-5 nano zeolite parcel, the hollow zeolite micro-sphere material that obtains is designated as F
1
[embodiment 7～10]
Experimentize with the method identical, but change gas-solid phase treatment temp with embodiment 5, respectively at 120 ℃, 160 ℃, handled two days for 180 ℃ and 200 ℃, obtain the hollow zeolite micro-sphere material, be designated as D respectively
2, D
3, D
4, D
5
[embodiment 11～13]
Experimentize with the method identical with embodiment 5, but change crystallization time, through 1 day, 5 days and 8 days crystallization obtained the hollow zeolite micro-sphere material, are designated as D respectively
6, D
7, D
8
[embodiment 14～18]
Experimentize with the method identical with embodiment 5, but change the mole proportioning of used organic amine, change the mixture quadrol, the mol ratio of triethylamine and distilled water is 1: 0: 3,1: 0: 6,6: 0: 1,1: 9: 6,0: 9: 6, obtain the hollow zeolite micro-sphere material, be designated as D respectively
9, D
10, D
11, D
12, D
13
[embodiment 19～21]
Experimentize with the method identical, but change the kind of used organic amine, the triethylamine in the mixture is replaced with ammonia, butylamine or Tri N-Propyl Amine, obtain the hollow zeolite micro-sphere material, be designated as D respectively with embodiment 5
14, D
15, D
16
[embodiment 22]
Experimentize with the method identical, but change the kind of mesopore silicon oxide microsphere with embodiment 5, utilize cetylamine for the mesopore silicon oxide microsphere of template preparation as template core, the hollow zeolite micro-sphere material that obtains is designated as G
1
The stereoscan photograph of the said products (SEM) all absorbs on Philips XL30 D6716 instrument, and lens photo (TEM) absorbs on JEOL JEM-2010 instrument.Fig. 1-the 5th, the electromicroscopic photograph of sample segment, the electromicroscopic photograph of all the other samples is similarly.With XRD (on Rigaku D/Max-IIA type X-ray diffractometer, carry out, see Fig. 6) the hollow zeolite micro-sphere material is characterized.As can be seen from Figure 6, show the characteristic peak of high-crystallinity MFI structural zeolite in the XRD of the product hollow zeolite micro-sphere material that the obtains spectrum, show that unformed mesopore silicon oxide microsphere is clean by digestion fully after handling mutually through gas-solid.Clean by digestion fully after also all as can be seen mesopore silicon oxide microsphere is handled mutually through gas-solid on SEM photo from Fig. 3 and the TEM photo of Fig. 4, product be have hollow structure microballoon.As can be seen, the nano zeolite particle of beginning is long, and its size is 100～200 nanometers in order to have the zeolite crystal of corner angle on the SEM photo that amplifies from spherical shell surface, and this shows that interior oxidation silicon nuclear is to be used for the growth of nano zeolite particulate as the silicon source.The silicon oxide microsphere diameter of the size of tiny balloon and beginning is approaching, and spherical shell is made of the zeolite crystal that intersection is grown up uniformly, and its thickness is 200～300 nanometers.The thickness of zeolite spherical shell can be regulated by initial nano zeolite particulate size, and the nano zeolite particle of beginning is big more, and the thickness of spherical shell is just thick more in the product.In addition, fine and close zeolite shell makes tiny balloon have higher physical strength, and (50kHz, 120 W) can keep about 10 minutes and can not destroy in ultrasound bath.
Because such zeolite hollow microsphere material has even, fine and close zeolite spherical shell and high physical strength, might be at the embedding and the slowly-releasing of medicine, make the most of the advantage in senior catalysis and the absorption; In addition, because used silicon oxide microsphere has abundant central hole structure, the mode of guest species by pre-implantation can be embedded in the mesopore, handle by this method then, when silicon oxide microsphere consumes, the pre-object species of implanting will be incorporated into hollow zeolite microballoon inside easily, thereby with the further functionalization of tiny balloon.
Claims (7)
1, a kind of method for preparing zeolite hollow microsphere, with weight percent concentration is 0.05～20%, pH value is 9.5～14, grain-size be 1～300 nanometer the nano zeolite glue as absorption deposit fluid, to handle through the polycation electrolyte solution soaking, diameter is that 1～8 micron mesopore silicon oxide microsphere is as template core, at first in the absorption deposit fluid, nano zeolite is deposited on the mesopore silicon oxide microsphere, get nano zeolite/mesopore silicon oxide complex microsphere, it is 100～240 ℃ in temperature then, pressure is under the autogenous pressure condition, with ammonia or the relative nano zeolite with the water vapor gas-solid of organic amine/mesopore silicon oxide complex microsphere carries out gas-solid handles mutually, treatment time is 1 hour to 20 days, under the effect of nano zeolite crystal seed, the silicon source of the mesopore silicon oxide microsphere of inside is converted into zeolite crystal, through washing, dry and roasting gets zeolite hollow microsphere.
2, according to the described method for preparing zeolite hollow microsphere of claim 1, it is characterized in that by weight percentage, the concentration of nano zeolite glue is 0.1～10% in the absorption deposit fluid, and the pH value of nano zeolite glue is 9.5～12, and the grain-size of nano zeolite glue is 60～300 nanometers.
3, according to the described method for preparing zeolite hollow microsphere of claim 1, it is characterized in that polycation electrolyte is the poly dimethyl allyl ammonia chloride, polycation electrolyte solution weight percentage concentration is 0.1～5%, and the time of polycation electrolyte solution soaking mesopore silicon oxide microsphere is 0.1～24 hour.
4, according to the described method for preparing zeolite hollow microsphere of claim 1, it is characterized in that it is 120～200 ℃ that nano zeolite/mesopore silicon oxide complex microsphere carries out the temperature that gas-solid handles mutually, the treatment time is 6 hours～10 days.
5, according to the described method for preparing zeolite hollow microsphere of claim 1, it is characterized in that organic amine is selected from C
nH
2n+1NH
2, the primary amine of n=0～5, C
nH
2n+1C
mH
2m+1NH, n, m are respectively 0～5 secondary amine or C
nH
2n+1C
mH
2m+1C
iH
2i+1N, n, m, i are respectively 0～5 tertiary amine.
6,, it is characterized in that organic amine is selected from least a in n-Butyl Amine 99, Tri N-Propyl Amine, quadrol or the triethylamine according to the described method for preparing zeolite hollow microsphere of claim 5.
7,, it is characterized in that zeolite is Silicalite-1 or ZSM-5 zeolite according to the described method for preparing zeolite hollow microsphere of claim 1.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006050638A1 (en) * | 2004-11-11 | 2006-05-18 | Institute Of Chemistry, Chinese Academy Of Science | The method for preparation of hollow spheres and composite hollow spheres with template |
| CN103979570A (en) * | 2014-05-14 | 2014-08-13 | 武汉理工大学 | Synthetic method of novel ordered macroporous-mesoporous-microporous hierarchical porous silicon-aluminium molecular sieve |
| CN105712374A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hollow USY molecular sieve |
| CN105712375A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | USY molecular sieve and preparation method thereof |
| CN106185981A (en) * | 2016-07-16 | 2016-12-07 | 太原理工大学 | A kind of preparation method of hollow ZSM 5 microsphere of zeolite |
| CN110342533A (en) * | 2018-04-02 | 2019-10-18 | 国家能源投资集团有限责任公司 | Molecular sieve and its preparation method and application |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357186C (en) * | 2006-01-26 | 2007-12-26 | 徐志兵 | Zinc oxide hollow microsphere preparation method |
-
2002
- 2002-12-11 CN CN 02151181 patent/CN1211280C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006050638A1 (en) * | 2004-11-11 | 2006-05-18 | Institute Of Chemistry, Chinese Academy Of Science | The method for preparation of hollow spheres and composite hollow spheres with template |
| CN103979570A (en) * | 2014-05-14 | 2014-08-13 | 武汉理工大学 | Synthetic method of novel ordered macroporous-mesoporous-microporous hierarchical porous silicon-aluminium molecular sieve |
| CN103979570B (en) * | 2014-05-14 | 2016-01-06 | 武汉理工大学 | The synthetic method of a kind of novel ordered big hole-mesoporous-micropore multi-stage porous Si-Al molecular sieve |
| CN105712374A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | Preparation method of hollow USY molecular sieve |
| CN105712375A (en) * | 2014-12-04 | 2016-06-29 | 中国石油化工股份有限公司 | USY molecular sieve and preparation method thereof |
| CN105712375B (en) * | 2014-12-04 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of USY molecular sieve and preparation method thereof |
| CN106185981A (en) * | 2016-07-16 | 2016-12-07 | 太原理工大学 | A kind of preparation method of hollow ZSM 5 microsphere of zeolite |
| CN110342533A (en) * | 2018-04-02 | 2019-10-18 | 国家能源投资集团有限责任公司 | Molecular sieve and its preparation method and application |
| CN110342533B (en) * | 2018-04-02 | 2021-08-03 | 国家能源投资集团有限责任公司 | Molecular sieve and preparation method and application thereof |
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| CN1211280C (en) | 2005-07-20 |
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