CN109384245A - A kind of macropore-micropore composite S ilicalite-1 molecule sieve and its synthetic method - Google Patents
A kind of macropore-micropore composite S ilicalite-1 molecule sieve and its synthetic method Download PDFInfo
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Abstract
The invention discloses a kind of with macropore-micropore compound pore passage structure nano-sheet Silicalite-1 molecular sieve and its synthetic method.The molecular sieve has MFI topological structure, and pattern is the shorter nano-sheet molecular sieve of b axis, and crystals are embedded with abundant macropore, and nanometer sheet thickness and macropore diameter can regulate and control in a wider range.Its synthetic method is using the mesoporous silicon oxide of urea, organic amine or inorganic base and ammonium salt dipping as presoma, and being prepared out using steam auxiliary crystallization method has macropore-micropore compound pore passage structure Silicalite-1 molecular sieve nanometer sheet.Macropore is constructed without additional secondary template agent in this synthetic method, and presoma is both synthesis of molecular sieve raw material and interim macropore template, while using urea that is cheap, being easy to get as crystal growth inhibitor, method simple possible, and synthesis cost is low.
Description
Technical field
The invention belongs to Zeolite synthesis technical fields, and in particular to a kind of new internal inlays the nanometer sheet of abundant macropore
Shape macropore-micropore composite S ilicalite-1 molecular sieve and its synthetic method.
Background technique
In numerous kinds in various and different properties porous material, zeolite molecular sieve has flourishing, orderly hole because of it
Road structure, regulatable acid and high stability, as catalyst, catalyst carrier and adsorption and separation material in petroleum
There are extremely wide application (Chem.Rev., 1997,97,2373-2419 in the fields such as chemical industry, fine chemistry industry and coal chemical industry；
Chem.Eng.,2011,118,16-20).The single microcellular structure of molecular sieve makes it encounter many in catalysis macromolecular reaction
Problem.Firstly, biggish reactant molecule can not contact the active site in molecular sieve crystal body phase, this greatly reduces molecule
The service efficiency of sieve catalyst.Secondly, lesser molecule diffusion duct also can inhibiting substances transmission process, reduce heat diffusion speed
Rate, lead to that its catalytic efficiency in practical application in industry is lower, catalytic effect is bad (Chem.Rev., 2006,106,896-
910).People have attempted many methods to improve the micropore diffusion efficiency of molecular sieve.Synthesis from molecular sieve itself is main
Two classes can be divided into, first is that construct multistage porous molecular sieve (Nano Today, 2009,4,292-301；Catal.Rev.,2003,
45,297-319), second is that reduce molecular sieve partial size (Micropor.Mesopor.Mater., 2002,55,171-179；
Micropor.Mesopor.Mater.,2004,68,91-95；Micropor.Mesopor.Mater.,2010,131,103-
114), the starting point of the two is all the diffusion path for shortening molecular sieve crystal.In addition to above-mentioned two thinkings, in microporous molecular sieve
It is constructed in system on the basis of secondary mesoporous and/or macropore, further combined with molecular sieve cellular structure feature itself, selectively
The diffusion of the preferential raising molecular sieve for shortening the crystal spread conducive to molecule axially may be more efficient, and then it is good to play its
Good catalytic capability.
The synthetic method of multistage porous molecular sieve is broadly divided into post treatment method and direct synthesis technique.Post treatment method is easy to operate,
It tells on also more apparent.Reporting for the first time from Barrer in 1964 et al. can be removed using hydrochloric acid reflux processing clinoptilolite
Skeleton aluminium atom is formed transgranular mesoporous (Can.J.Chem., 1964,6,1481-1487).Later, a series of research work are not by
Disconnected report comes out.Such as Ogura etc. handles ZSM-5 molecular sieve using sodium hydroxide solution, product surface, which is obviously etched, to be become
It is coarse, and the mesoporous formation (Chem.Lett., 2000,8,882-883) that have 4nm or so.But research finds post-processing legal system
Standby multistage porous molecular sieve may lead molecular sieve crystallinity decline, and activated centre is destroyed, and this method is only to specific knot
The molecular sieve of structure or composition is effective.Direct synthesis technique is that secondary template agent is directly added into during synthesis of molecular sieve, is utilized
Assembling forms mesoporous or macroporous structure to template simultaneously in the forming process of micro porous molecular sieve.It is continuous with Template Types
It expands, direct synthesis technique becomes prepares the more effective approach of multistage porous molecular sieve at present.Xiao et al.
(Angew.Chem.Int.Ed.,2006,45,3090-3093；Ind.Eng.Chem.Res.,2014,53,13903-13909；
Chin.J.Catal., 2011,32,1656-1661) it is realized using the mixed templates of cationic polymer and conventional quaternary ammonium salt
The synthesis of multi-stage porous Beta, ZSM-5 and TS-1.Ryoo seminar with the polyquaternium of different number quaternary ammonium group then to close
At multistage porous molecular sieve (Nat.Mater., 2006,5,718-723；Nature,2009,461,246-250；Science,
2011,333,328-332).Secondary template agent described above is more difficult to get mostly, before synthesizing multistage porous molecular sieve, needs to throw
Enter more man power and material and synthesize secondary template, so that the production cost that direct synthesis technique prepares multistage porous molecular sieve is higher.Separately
On the one hand, above-mentioned synthetic method products obtained therefrom is nanocrystal aggregates mostly, and average molecular sieves monocrystalline, and stability is poor.
Silicalite-1 molecular sieve thermal stability with higher and suitable ten-ring hole with MFI topological structure
Road structure is suffered from and is widely applied in Industrial Catalysis and UF membrane field.There are two types of mutually hand over for Silicalite-1 molecular sieve
The pore canal system of fork, a kind of line style ellipse duct being parallel to b axis direction, another kind are parallel to ten yuan of " Z " font of a axis
Annular distance road (Micropor.Mesopor.Mater., 2000,38,3-24).Guest molecule is different in Silicalite-1 molecular sieve
The mass transport process of orientation is different, and such as along c-axis direction, guest molecule needs to leapfrog in two kinds of ducts repeatedly, and diffusion length is long,
Mass-transfer efficiency is low, and along b axis direction diffusion when, guest molecule is only needed through straight hole road, and mass transfer rate is most fast.Therefore, difference takes
To dominant growth Silicalite-1 molecular sieve its catalysis, separation and other effects difference.Compared to the Silicalite- of conventional pattern
1 molecular sieve, the lesser laminated structure molecular sieve of b axis direction size are more advantageous to the diffusion of guest molecule, thus have excellent
Catalytic performance and carbon accumulation resisting ability are the oriented crystal growth modes of highly desirable acquisition.
The common method of synthesizing flaky MFI molecular sieve can be divided into three classes at present, and one is by means of organic macromolecule mould
The Long carbon chain of plate agent inhibits crystal along the growth of b axis direction.The multi-quaternary ammonium salt surface-active that Ryoo et al. is synthesized with designed, designed
The structure directing agent of agent molecule combination micro porous molecular sieve has synthesized the Silicalite-1 molecular sieve nanometer sheet of 2nm thickness.Also there is text
Report is offered using dodecyl trimethyl ammonium bromide, cetyl trimethylammonium bromide and Cetyltrimethylammonium bromide conduct
Amphiphilic cationic surfactant has synthesized the aggregation (CN106006666A) of nanoscale twins ZSM-5 molecular sieve.It is another
It is phyllosilicate stripping method, phyllosilicate Na-kenyaite is carried out with polar molecule cetyl trimethylammonium bromide
Intercalation, then MFI molecular sieve is synthesized by template of tetra-alkyl ammonium hydroxide, products therefrom delamination is handled to obtain laminar MFI
Molecular sieve crystal.In the above work, stripping method prepares sheet MFI molecular sieve complicated steps and complex processes.And use organosilan
When for sheet Molecular Sieves as Template agent, it usually needs spend more time and efforts to synthesize the certain moduli plate agent, it is expensive,
Production cost is higher, still has a certain distance apart from industrial applications.
Currently, the synthesis of multistage porous molecular sieve has been achieved for biggish progress, a variety of synthetic methods are reported out
Come, and there has also been certain Research foundations in terms of controlling molecular sieve crystal appearance structure.But develop a kind of novel molecular sieve
The advantages of material can be in combination with the two is still faced with great challenge.
In the technical solution of this patent under the premise of not introducing complicated, expensive secondary template agent, with mesoporous dioxy
SiClx is silicon source and urea is organic additive, using steam auxiliary crystallization method, in unbodied presoma to macropore-micropore
In composite S ilicalite-1 molecular sieve conversion process, plays urea and inhibit the effect of crystal growth, while shortening the axis side crystal b
To size.This method products obtained therefrom has the excellent stability and macropore-micropore compound pore passage structure good diffusion of monocrystalline
The diameter of performance, the lamellar spacing of crystal grain and transgranular macropore can controllable adjustment in a wider range.
Summary of the invention
The novel nano sheet macropore-micropore for inlaying macropore the purpose of the present invention is to provide a kind of crystals is compound
Silicalite-1 molecular sieve and its synthetic method.
The present invention, using steam auxiliary crystallization method, is urinated using the mesoporous silicon oxide of specific morphology as presoma by introducing
Element and controlling crystallizing condition, have synthesized the nano-sheet Silicalite-1 molecular sieve that crystal is embedded with abundant macropore.
Present invention innovation is: using the mesoporous silicon oxide of specific morphology as presoma, being closed by steam auxiliary crystallization method
At molecular sieve, while transgranular macropore abundant is constructed in crystal, inhibit crystal along the growth of b axis direction.The synthetic method
It does not need to introduce macropore template, by controlling crystallizing condition, such as the dosage of water and alkali, and binding crystal growth inhibitor is urinated
The use of element, successfully synthesizes nano-sheet macropore-micropore composite S ilicalite-1 molecular sieve.In addition, passing through appropriate modulation
It is compound that the partial size of presoma silica and the introduction volume of urea can further control nano-sheet macropore-micropore
The diameter macropores and b axis direction size of Silicalite-1 molecular sieve.
An aspect of of the present present invention provides a kind of Silicalite-1 molecular sieve, the Silicalite-1 molecular sieve it is micro-
Hole crystals are inlaid with macropore abundant, and with the compound structure of macropore-micropore, and the b axis direction of the crystal has
Short size.
In a preferred embodiment, the pore diameter range of the macropore of the Silicalite-1 molecular sieve is 50 to 800 to receive
Rice.
In a preferred embodiment, the aperture of the macropore is 50 to 500 nanometers.
In a preferred embodiment, the size of the b axis direction of the Silicalite-1 molecular sieve crystal is 20 to 700
Nanometer.
In a preferred embodiment, the size of the b axis direction of the Silicalite-1 molecular sieve crystal be 100 to
500 nanometers.
Another aspect provides a kind of preparation method of Silicalite-1 molecular sieve, the method is at least wrapped
Include following steps:
(1) organic amine template, urea, alkali source and water are uniformly mixed, obtain mixed solution A；
(2) it contacts the mixed solution A with mesoporous silicon oxide, obtains having the initial synthesis of following molar ratio to mix
Object B:
SiO2:xM2O:yR:zUrea:mH2O, in which: M2O is alkali source, and R is template, and Urea is urea, x=0~
0.15, y=0.05~0.2, z=0~1.5, m=0.5~5；
(3) the mixture B is subjected to crystallization by steam auxiliary crystallization method；
(4) after the completion of the step (3) crystallization, by solid product through centrifugation, washing, drying to get nanometer
Silicalite-1 molecular sieve.
In a preferred embodiment, the crystallization is 100~200 DEG C in temperature, 12~50 hours items of crystallization time
It is carried out under part.
In a preferred embodiment, the template R is tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrapropyl
At least one of ammonium bromide and 4-propyl ammonium chloride.
In a preferred embodiment, the alkali source is sodium hydroxide, potassium hydroxide, tetraethyl ammonium hydroxide and tetrapropyl
At least one of ammonium hydroxide.
In a preferred embodiment, the shape of the mesoporous silicon oxide is spherical or elliposoidal.
In a preferred embodiment, the average grain diameter of the mesoporous silicon oxide is 0.05~2 micron；
In a preferred embodiment, the average grain diameter is 0.1~1 micron.
In a preferred embodiment, the Silicalite-1 molecular sieve is with macropore-micro-pore composite structure point
Son sieve.
The beneficial effect that the application can generate includes:
(1) product of the invention is nano-sheet macropore-micropore composite S ilicalite- that abundant macropore is inlayed in crystal
1 molecular sieve, the macropore diameter and crystal grain b axis direction size of molecular sieve are controllable.
(2) nano-sheet macropore-micropore composite S ilicalite-1 molecular sieve synthetic method utilizes mesoporous silicon oxide
Simultaneously as silicon source and interim macropore template, does not need to additionally introduce expensive mesoporous or macropore organic formwork agent, reduce
Nano-sheet macropore-micropore composite S ilicalite-1 molecular sieve production cost；It is simultaneously to have with urea that is cheap, being easy to get
Machine additive inhibits the growth of molecular sieve crystal b axis, lays a good foundation for large-scale industrial application.
(3) the axis straight hole road direction b of Silicalite-1 molecular sieve prepared by the present invention is main molecule diffusion path,
Relatively thin b axial thickness improves the diffuser efficiency of guest molecule, and constructing for transgranular macropore further alleviates single micropore
The defect of system.
Detailed description of the invention
Fig. 1 is that the SEM of 1 mesoporous silicon oxide of embodiment schemes.
Fig. 2 is the XRD spectra of sample HMS-Silicalite-1-1~7 prepared in embodiment 2.
Fig. 3 is the sample HMS-Silicalite-1-2 prepared in embodiment 2, and 3,4,5 respectively at low-voltage (left, 1kV)
With the SEM figure shot under high voltage (right, 15kV).
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Source chemicals used in embodiment by commercially available acquisition, are directly used without any specially treated.
Embodiment 1: mesopore silicon oxide
Used mesoporous silicon oxide pattern and performance parameter are shown in Table 1, and scanning electron microscope (SEM) photograph is shown in Fig. 1.
1 mesopore silicon oxide pattern of table and performance parameter table
Embodiment 2: prepared by sample HMS-Silicalite-1-1~7
Urea and tetrapropylammonium hydroxide are added in deionized water first, stirring and dissolving obtains mixed solution A.It takes
Solution A incipient impregnation mesoporous silicon oxide is stated, obtains solid B after for a period of time through drying at room temperature.By above-mentioned solid mixture B
It is transferred in the square position of stainless steel autoclave top, water is added in reaction kettle bottom.Stainless steel cauldron is sealed, baking oven is put into
In, 12~50h of crystallization at 100~180 DEG C.It is cooling rapidly after reaction, solid product is separated, deionized water is washed,
110 DEG C of dryings simultaneously roast 6 hours to get sheet macropore-micropore composite S ilicalite-1 molecular sieve for 550 DEG C in air atmosphere.
The corresponding relationship of sample number into spectrum and preparation condition is as shown in table 2.
XRD characterization is carried out to the sample of preparation, as a result as shown in Fig. 2, the XRD of sample HMS-Silicalite-1-1~7
Map is consistent with the feature spectrogram of standard MFI molecular sieve, and diffraction peak intensity is higher, well-crystallized.
Texture property representation, sample aperture are carried out to prepared sample using Micromeritics company ASAP 2020
Distribution, average pore size and hole hold as shown in table 3, and the external surface area of sample HMS-Silicalite-1-1~7 is higher, contains macropore
Structure.
Using JSM-7800F type high resolution scanning electron microscope and TM3030 scanning electron microscope to prepared allusion quotation
Pattern product HMS-Silicalite-1-2,3,4,5 are scanned Electronic Speculum characterization, as shown in figure 3, sample is laminated structure, it is brilliant
For intragranular with the presence of macropore, grain surface is smooth without obvious macropore.
2 Zeolite synthesis ingredient of table and crystallization condition table
The 3 pore-size distribution table of sample HMS-Silicalite-1-1~7 of table
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen
Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off
In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to
Case study on implementation is imitated, is belonged in technical proposal scope.
Claims (10)
1. a kind of Silicalite-1 molecular sieve, which is characterized in that the Silicalite-1 molecular sieve has macropore-micropore multiple
Structure is closed, and the b axis direction of the crystal has short size.
2. Silicalite-1 molecular sieve according to claim 1, which is characterized in that the Silicalite-1 molecular sieve
The pore diameter range of macropore be 50 to 800 nanometers；
Preferably, the aperture of the macropore is 50 to 500 nanometers.
3. Silicalite-1 molecular sieve according to claim 1, which is characterized in that the Silicalite-1 molecular sieve
The size of the b axis direction of crystal is 20 to 700 nanometers；
Preferably, the size of the b axis direction of the nano Si licalite-1 molecular sieve crystal is 100 to 500 nanometers.
4. a kind of preparation method of Silicalite-1 molecular sieve, which is characterized in that the method at least includes the following steps:
(1) organic amine template, urea, alkali source and water are uniformly mixed, obtain mixed solution A；
(2) it contacts the mixed solution A with mesoporous silicon oxide, obtains the initial synthesis mixture B with following molar ratio:
SiO2:xM2O:yR:zUrea:mH2O, in which: M2O is alkali source, and R is template, and Urea is urea, x=0~0.15, y=
0.05~0.2, z=0~1.5, m=0.5~5；
(3) the mixture B is subjected to crystallization by steam auxiliary crystallization method；
(4) after the completion of the step (3) crystallization, by solid product through centrifugation, washing, drying to get Silicalite-1 points
Son sieve.
5. the preparation method according to claim 4, which is characterized in that the crystallization is 100~200 DEG C in temperature, crystallization
It is carried out under conditions of 12~50 hours time.
6. the preparation method according to claim 4, which is characterized in that the template R is tetraethyl ammonium hydroxide, 4 third
At least one of base ammonium hydroxide, 4-propyl bromide and 4-propyl ammonium chloride.
7. the preparation method according to claim 4, which is characterized in that the alkali source is sodium hydroxide, potassium hydroxide, tetrem
At least one of base ammonium hydroxide and tetrapropylammonium hydroxide.
8. the preparation method according to claim 4, which is characterized in that the shape of the mesoporous silicon oxide is spherical or ellipse
It is spherical.
9. the preparation method according to claim 4, which is characterized in that the average grain diameter of the mesoporous silicon oxide is 0.05
~2 microns；
Preferably, the average grain diameter of the mesoporous silicon oxide is 0.1~1 micron.
10. the preparation method according to claim 4, which is characterized in that pass through the partial size of mesoporous silicon oxide described in modulation
The regulation of Silicalite-1 molecular sieve the b axis direction size and macropore diameter is realized with crystallization condition.
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Cited By (5)
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| CN112174162A (en) * | 2020-10-13 | 2021-01-05 | 天津大学 | Method for preparing Silicalite-1 molecular sieve |
| CN112607746A (en) * | 2021-01-05 | 2021-04-06 | 大连理工大学 | Method for synthesizing MFI molecular sieve with hierarchical pores and oriented growth on c axis under fluorine-free condition |
| CN112978748A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | TS-1 molecular sieve with macroporous-microporous composite pore channel structure, and preparation method and application thereof |
| CN112978756A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Flaky TS-1 molecular sieve, and preparation method and application thereof |
| CN115353120A (en) * | 2022-08-01 | 2022-11-18 | 江汉大学 | ZSM-5 zeolite molecular sieve and preparation method thereof |
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| CN112978748A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | TS-1 molecular sieve with macroporous-microporous composite pore channel structure, and preparation method and application thereof |
| CN112978756A (en) * | 2019-12-13 | 2021-06-18 | 中国科学院大连化学物理研究所 | Flaky TS-1 molecular sieve, and preparation method and application thereof |
| CN112174162A (en) * | 2020-10-13 | 2021-01-05 | 天津大学 | Method for preparing Silicalite-1 molecular sieve |
| CN112174162B (en) * | 2020-10-13 | 2022-06-07 | 天津大学 | Method for preparing Silicalite-1 molecular sieve |
| CN112607746A (en) * | 2021-01-05 | 2021-04-06 | 大连理工大学 | Method for synthesizing MFI molecular sieve with hierarchical pores and oriented growth on c axis under fluorine-free condition |
| CN112607746B (en) * | 2021-01-05 | 2022-08-19 | 大连理工大学 | Method for synthesizing MFI molecular sieve with hierarchical pores and oriented growth on c axis under fluorine-free condition |
| CN115353120A (en) * | 2022-08-01 | 2022-11-18 | 江汉大学 | ZSM-5 zeolite molecular sieve and preparation method thereof |
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Application publication date: 20190226 |