CN107032368A - A kind of MTW Zeolitic NanoRods with symbiotic structure and preparation method thereof - Google Patents
A kind of MTW Zeolitic NanoRods with symbiotic structure and preparation method thereof Download PDFInfo
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- CN107032368A CN107032368A CN201710239017.6A CN201710239017A CN107032368A CN 107032368 A CN107032368 A CN 107032368A CN 201710239017 A CN201710239017 A CN 201710239017A CN 107032368 A CN107032368 A CN 107032368A
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- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7034—MTW-type, e.g. ZSM-12, NU-13, TPZ-12 or Theta-3
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- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
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- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2004/60—Particles characterised by their size
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- C01P2006/16—Pore diameter
Abstract
The invention discloses a kind of MTW Zeolitic NanoRods with symbiotic structure and preparation method thereof, MTW Zeolitic NanoRods have microporous mesoporous macropore hierarchical porous structure, and MTW Zeolitic NanoRods average diameter is 40 50nm.First by the way that Bola type quaternary ammonium salt structures directed agents, alkali to be added to the water and to form mixed solution in the MTW Zeolitic NanoRods preparation process, silicon source, silicon source are added under the conditions of 40 DEG C again, crystallization in ptfe autoclave is finally transferred to, MTW Zeolitic NanoRods are prepared by carrying out roasting under high temperature to the sample obtained after filtering, wash, drying.MTW Zeolitic NanoRods disclosed by the invention have symbiotic structure, to 1,3, the cracking reaction of 5 triisopropylbenzenes has higher catalytic activity, and preparation method preparation efficiency disclosed by the invention is high, and yield is more than 90%, preparation method is simple, and cost is low, with industrial application value.
Description
Technical field
Received the present invention relates to a kind of molecular sieve and preparation method thereof, more particularly to a kind of MTW zeolites with symbiotic structure
Rice rod and preparation method thereof.
Background technology
The well-regulated pore canal system of zeolitic molecular sieve, very high hydrothermal stability, extremely strong adsorption capacity and ion are handed over
The advantages of transducing power, thus catalyst is widely used in, adsorbent, ion-exchanger etc., but the pore size of zeolite
Generally less than 2nm, therefore limit its application in catalytic field.Introduce mesoporous in zeolitic frameworks, can efficiently solve
The problem of molecule spreads in zeolite cavity and mass transfer is difficult, hard template method, soft template method and amphiphilic are directly directed to close
Method into mesoporous zeolite is suggested respectively.But, cumbersome last handling process and higher template synthesis cost limitation
The applications of these methods in the industry.It is smaller and the nano molecular sieve with symbiotic structure is due to its unique pore size
Crystallite dimension, relatively simple structure directing agent etc. not only shortens transmission range of the molecule in zeolite cavity, improves
Aligning between catalytic efficiency, and nano particle forms hierarchical porous structure, the catalytic reaction for being conducive to macromolecular to participate in,
The presence of symbiotic structure simultaneously causes zeolite to have unique pore canal system, therefore with huge potential using value.Nearly ten
Nian Lai, hierarchical pore MFI zeolite and FAU zeolites with symbiotic structure are reported in succession.But, it there is no in current document report
The report of multi-stage porous MTW zeolite of the synthesis with symbiotic structure.
In summary, zeolite due to only existed in its structure micropore (<2nm), the less aperture of size limits macromolecular
Entrance and transmission, so as to limit its application in catalytic field, drawn by hard template method or soft template method in zeolite
Enter mesoporous (2-50nm) or macropore (>50nm), it is necessary to undergo synthesis and removing or the organic mould of multiple steps synthesis of hard template
This complicated processes of plate agent, time-consuming, cost high, and commercial introduction application value is low, passes through having for being chemically synthesized at present
The multistage porous molecular sieve of symbiotic structure is confined to both zeolite types of MFI and FAU, available few.
The content of the invention
In view of the drawbacks described above of prior art, the technical problems to be solved by the invention are to be directed to hard template method, soft mode
Plate method and amphiphilic are directly directed to last handling process cumbersome present in the method for synthesising mesoporous zeolite and higher
Template synthesis cost problem, develop a kind of zeolite molecular sieve, the zeolite molecular sieve can be widely applied to catalyst,
Pore size with uniqueness, less crystallite dimension, relatively simple structure directing agent etc., it can not only shorten molecule in boiling
Transmission range in stone duct, can also improve catalytic efficiency, with huge industrial application value.
To achieve the above object, the invention provides a kind of with the MTW Zeolitic NanoRods of symbiotic structure and its preparation side
Method.Concrete technical scheme is as follows：
The invention discloses a kind of MTW Zeolitic NanoRods with symbiotic structure, the MTW Zeolitic NanoRods have symbiosis knot
Structure.
Further, MTW Zeolitic NanoRods have micropore-mesopore-macropore hierarchical porous structure, and wherein micropore size is less than
2nm, mesoporous pore size is 2-50nm, and macropore diameter is more than 50nm.
Further, MTW Zeolitic NanoRods average diameter is 40-50nm.
Acquisition is made by the steps in MTW Zeolitic NanoRods disclosed by the invention with symbiotic structure：
Step one, Bola type quaternary ammonium salt structures directed agents, alkali are added to the water, control Bola types quaternary ammonium salt structure is oriented to
The mol ratio of agent, alkali and water is 2-3：6：700-800, is stirred dissolving, obtains the first mixed solution.
Further, Bola types quaternary ammonium salt structure directed agents pass through the organic conjunction of a step by using Bola type quaternary ammoniums molecules of salt
Into preparation.
Further, alkali is sodium hydroxide.
Further, Bola types quaternary ammonium salt structure directed agents are bromination Isosorbide-5-Nitrae-two (1- methylpyrroles alkyl) butane, bromination
Any of (the 1- methylpyrroles alkyl) pentanes of 1,5- bis- and bromination 1,6- bis- (1- methylpyrroles alkyl) hexane.
Step 2, adds silicon source, silicon source, control silicon source, silicon source and Bola under the conditions of 40 DEG C into the first mixed solution
The mol ratio of type quaternary ammonium salt structure directed agents is 0.17-0.25：20：2-3, then stirs 3h, obtains the second mixed solution.
Further, silicon source feed postition is dropwise addition.
Further, silicon source is Patent alum.
Further, silicon source is the aqueous silica solution of 30% mass fraction.
Step 3, ptfe autoclave is transferred to by the second mixed solution, the crystallization in homogeneous reactor, crystallization temperature
For 160 DEG C, crystallization time is 70-100h, is then filtered, washed successively, dried, finally obtaining sample.
Step 4, sample is calcined under the conditions of 550 DEG C, has deviate from template, MTW Zeolitic NanoRods are prepared, system
Standby obtained MTW Zeolitic NanoRods have symbiotic structure, and with micropore-mesopore-macropore hierarchical porous structure, average diameter is 40-
50nm。
Further, the micropore size is less than 2nm, and the mesoporous pore size is 2-50nm, and the macropore diameter is more than
50nm。
Further, roasting time is 5-7h.
Zeolite with symbiotic structure has special catalytic performance, the present invention due to its unique pore canal system structure
Disclosed technical scheme is intended to by a kind of simple porous zeotile of the method synthesis with symbiotic structure.Utilize Bola types point
Son is oriented to synthesis with symbiotic structure MFI zeolites and also located it has been reported that still being prepared in the MTW Zeolitic NanoRods of symbiotic structure
In blank stage.
The present invention is on preparation principle, by using Bola type molecules, have chosen the comparatively cheap reaction of relative price former
Material, prepares lower structure directing agent, the structural formula of structure directing agent is BA-CnH2n-AB by a step organic synthesis：
Wherein B is Br-, A isAny of, n is 4-6.
It should be noted that A is selectedThan A selectionsCorresponding structure directing agent is oriented to MTW nanometers of symbiosis
The guidance capability of rod is poor.
On this basis, by controlling synthetic ratio and condition, the MTW zeolites nanometer synthesized with symbiotic structure is prepared
Rod.
In technical scheme disclosed by the invention, using Bola types structure directing agent for synthesizing the zeolite with symbiotic structure
Nanometer rods have vital effect.
In technical scheme disclosed by the invention, the consumption of the proportioning of synthesis of molecular sieve, especially structure directing agent is influence
The key factor of the final appearance structure of zeolite.
In technical scheme disclosed by the invention, the selection of crystallization temperature and crystallization time is weighed very much in preparation process three
Will, crystallization temperature is too low, will cannot get the multi-stage porous MTW Zeolitic NanoRods of this symbiotic structure.
Technical scheme disclosed by the invention has following advantageous effects：
1st, MTW Zeolitic NanoRods have micropore-mesopore-macropore hierarchical porous structure, efficiently solve zeolite in terms of mass transfer
Defect.
2nd, design synthesis simple structure directed agents, are oriented to the synthesis of hierarchical porous structure zeolite, it is to avoid the removing of template or
The high cost caused during the complicated organic formwork agent of person's synthesis.
3rd, preparation process is simple, and cost is small, and the MTW Zeolitic NanoRods prepared have symbiotic structure and hierarchical porous structure,
With good industrial application value.
4th, the MTW Zeolitic NanoRods yields with symbiotic structure prepared by the present invention are up to more than 90%.
5th, structure directing used in the present invention can carry out a step organic synthesis by raw material to prepare, and raw material is relatively simple
Single, compared with traditional hard template method and soft template method, cost reduction is a lot.
6th, cracking of the MTW Zeolitic NanoRods with symbiotic structure prepared by the present invention to 1,3,5- triisopropylbenzenes is anti-
There should be higher catalytic activity.
The technique effect of the design of the present invention, concrete structure and generation is described further below with reference to accompanying drawing, with
It is fully understood from the purpose of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is MTW Zeolitic NanoRods scanning electron microscope (SEM) photograph (5 μ with symbiotic structure prepared by present pre-ferred embodiments
m)；
Fig. 2 is the MTW Zeolitic NanoRods scanning electron microscope (SEM) photographs with symbiotic structure prepared by present pre-ferred embodiments
(200nm)；
Fig. 3 is the MTW Zeolitic NanoRods transmission electron microscope pictures with symbiotic structure prepared by present pre-ferred embodiments
(200nm)；
Fig. 4 is the MTW Zeolitic NanoRods transmission electron microscope pictures with symbiotic structure prepared by present pre-ferred embodiments
(20nm)；
Fig. 5 is the MTW Zeolitic NanoRods Fourier diffraction figures with symbiotic structure prepared by present pre-ferred embodiments；
Fig. 6 is the MTW Zeolitic NanoRods X-ray diffraction spectrograms with symbiotic structure prepared by present pre-ferred embodiments；
Fig. 7 is the MTW Zeolitic NanoRods N with symbiotic structure prepared by present pre-ferred embodiments2Adsorption-desorption is bent
Line.
Embodiment
Below in conjunction with the accompanying drawings and the present invention is described in further detail in specific embodiment.It should be understood that embodiment is to be
The present invention is illustrated, rather than limits the scope of invention in any form.
Technical scheme disclosed by the invention is broadly divided into two when the MTW Zeolitic NanoRods with symbiotic structure are prepared
The individual stage.
First stage：MTW Zeolitic NanoRods prepare before preparing.
Bola type directed agents preparation principles：By using Bola type molecules, the comparatively cheap reaction of relative price have chosen
Raw material, prepares lower structure directing agent, the structural formula of structure directing agent is BA-C by a step organic synthesisnH2n-AB：
Wherein B is Br-, A isAny of, n is 4-6.
It should be noted that A is selectedThan A selectionsCorresponding structure directing agent is oriented to MTW nanometers of symbiosis
The guidance capability of rod is poor.
In the stage, bromination Isosorbide-5-Nitrae-two is prepared by a step organic synthesis using Bola type directed agents preparation principle
(1- methylpyrroles alkyl) butane, regard it as the Bola type directed agents in second stage preparation work.
Second stage：Prepared by MTW Zeolitic NanoRods, the preparation flow in the stage is divided into four steps.
Step one, bromination Isosorbide-5-Nitrae-two (1- methylpyrroles alkyl) butane, sodium hydroxide are added to the water, control bromination Isosorbide-5-Nitrae-
The mol ratio of two (1- methylpyrroles alkyl) butane, sodium hydroxide and water is 2：6：750,2h is at the uniform velocity stirred, fully shape after dissolving
Into mixed solution.
Step 2, the mixed solution formed under the conditions of 40 DEG C into step one adds Patent alum, and 40
The aqueous silica solution of 30% mass fraction is added dropwise under the conditions of DEG C, Patent alum and 30% mass point added is controlled
Several aqueous silica solution quality so that Patent alum, the aqueous silica solution of 30% mass fraction and bromination
1,4- bis- (the 1- methylpyrroles alkyl) mol ratio of butane in mixed solution is 2：200：25, at the uniform velocity stir 3h.
Step 3, is transferred to ptfe autoclave, in homogeneous reactor by the mixed solution obtained after the completion of step 2
Middle crystallization, crystallization temperature is 160 DEG C, and crystallization time is 96h, is then filtered, washed successively, dried, obtaining the sample of solid-state
Product.
Step 4, the solid sample that step 3 is obtained is calcined 6h under the conditions of 550 DEG C, has deviate from template, is prepared into
To MTW Zeolitic NanoRods materials.
The MTW Zeolitic NanoRods prepared by the present embodiment have micropore-mesopore-macropore hierarchical porous structure, wherein
Micropore size is less than 2nm, and mesoporous pore size is 2-50nm, and macropore diameter is more than 50nm；The MTW Zeolitic NanoRods have symbiosis knot
Structure, average diameter is 40-50nm.
As shown in Figure 1-2, it is the scanning electron microscope (SEM) photograph of the MTW Zeolitic NanoRods with symbiotic structure prepared by embodiment.Such as
It is the transmission electron microscope picture of the MTW Zeolitic NanoRods with symbiotic structure prepared by embodiment shown in Fig. 3-4.Can from Fig. 1
Go out Zeolitic NanoRods and align superstructure in flakes.As can be seen from Figure 2 Zeolitic NanoRods intersect in about 66 ° of angles,
The average diameter of nanometer rods is 40-50nm, and the accumulation gap between nanometer rods is into mesoporous or macropore.Comprehensive corresponding diagram 1 and figure
3, the as can be seen from Figure 4 intersection symbiosis in two straight hole roads, two white arrows are divided to the straight hole that table illustrates two nanometer rods
Road direction, both edge (310) crystal face symbiosis.As shown in figure 5, the MTW zeolites nanometer with symbiotic structure prepared for embodiment
Point diffraction in rod Fourier diffraction figure, Fig. 5 demonstrates the presence of symbiotic structure.As shown in fig. 6, being prepared by embodiment having
The MTW Zeolitic NanoRods X-ray diffraction spectrograms of symbiotic structure, are the diffraction maximums of typical MTW zeolites.As shown in fig. 7, to implement
MTW Zeolitic NanoRods N2 adsorption-desorption curves with symbiotic structure prepared by example, it can be seen that P/P0=0.02
The presence of micropore in following adsorbance testimonial material, relative pressure P/P0=0.4-0.99 is returned in the presence testimonial material of stagnant ring
There is mesoporous and macropore presence.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound
The property made work just can make many modifications and variations according to the design of the present invention.Therefore, all technical staff in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be in the protection domain being defined in the patent claims.
Claims (10)
1. a kind of MTW Zeolitic NanoRods with symbiotic structure, it is characterised in that
The MTW Zeolitic NanoRods have micropore-mesopore-macropore hierarchical porous structure, and the micropore size is less than 2nm, given an account of
Hole aperture is 2-50nm, and the macropore diameter is more than 50nm；
The MTW Zeolitic NanoRods average diameter is 40-50nm.
2. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 1, it is characterised in that
Including following preparation process：
Step one, Bola type quaternary ammonium salt structures directed agents, alkali are added to the water, the Bola types quaternary ammonium salt structure directed agents, institute
The mol ratio for stating alkali and the water is 2-3：6：700-800, stirring and dissolving forms the first mixed solution；
Step 2, under the conditions of 40 DEG C into first mixed solution add silicon source, silicon source, source of aluminium, the silicon source with
The mol ratio of the Bola types quaternary ammonium salt structure directed agents is 0.17-0.25：20：2-3, then stirs 3h, obtains the second mixing
Solution；
Step 3, ptfe autoclave is transferred to by second mixed solution, the crystallization in homogeneous reactor, the crystallization
Temperature is 160 DEG C, and the crystallization time is 70-100h, is then filtered, washed successively, dried, finally obtaining sample；
Step 4, the sample is calcined, and prepares the MTW Zeolitic NanoRods.
3. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
The quaternary ammonium salt structures of Bola types described in step one directed agents pass through a step organic synthesis system by using Bola type quaternary ammoniums molecules of salt
It is standby.
4. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Alkali described in step one is sodium hydroxide.
5. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
The quaternary ammonium salt structures of Bola types described in step one directed agents are bromination 1,4- bis- (1- methylpyrroles alkyl) butane, bromination 1,5- bis-
Any of (1- methylpyrroles alkyl) pentane and bromination 1,6- bis- (1- methylpyrroles alkyl) hexane.
6. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Silicon source feed postition described in step 2 is dropwise addition.
7. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Silicon source described in step 2 is Patent alum.
8. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Silicon source described in step 2 is the aqueous silica solution of 30% mass fraction.
9. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Sintering temperature described in step 4 is 550 DEG C, and the time is 5-7h.
10. a kind of preparation method of the MTW Zeolitic NanoRods with symbiotic structure as claimed in claim 2, it is characterised in that
Micropore size described in step 4 is less than 2nm, and the mesoporous pore size is 2-50nm, and the macropore diameter is more than 50nm.
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| CN110042235A (en) * | 2019-04-29 | 2019-07-23 | 山东大学 | A kind of extractant and extracting process of separation gold |
| CN112939017A (en) * | 2019-12-11 | 2021-06-11 | 中国科学院大连化学物理研究所 | Synthesis method of MTW type molecular sieve |
| CN114073930A (en) * | 2020-08-19 | 2022-02-22 | 同济大学 | Zeolite/mesoporous silica composite microsphere material and preparation method thereof |
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| CN110042235A (en) * | 2019-04-29 | 2019-07-23 | 山东大学 | A kind of extractant and extracting process of separation gold |
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| CN114073930A (en) * | 2020-08-19 | 2022-02-22 | 同济大学 | Zeolite/mesoporous silica composite microsphere material and preparation method thereof |
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