CN106256764A - A kind of method preparing the molecular sieve molded thing of nanoscale sodalite - Google Patents
A kind of method preparing the molecular sieve molded thing of nanoscale sodalite Download PDFInfo
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- CN106256764A CN106256764A CN201510347592.9A CN201510347592A CN106256764A CN 106256764 A CN106256764 A CN 106256764A CN 201510347592 A CN201510347592 A CN 201510347592A CN 106256764 A CN106256764 A CN 106256764A
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- sodalite
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Abstract
The invention discloses a kind of method preparing the molecular sieve molded thing of nanoscale sodalite, it is possible under conditions of existing without any organic additive and structure directing agent, prepare the pure molecular sieve molded thing of nanoscale sodalite.Step includes: 1) by solid phase silicon source and solid phase aluminum source mix homogeneously, adds the first alkaline aqueous solution, stirs and molding obtains article shaped；2) by article shaped in dry roasting；3) baked article shaped is placed in the second alkaline aqueous solution, after crystallization, obtains the molecular sieve molded thing of nanoscale sodalite.
Description
Technical field
The present invention relates to a kind of method preparing the molecular sieve molded thing of nanoscale sodalite, belong to inorganic nano material
Preparation field.
Background technology
Sodalite (SOD) is one of the most traditional molecular sieve, body-centered cubic the SOD cage that arranges (that is β
Cage, is made up of 6 four-membered rings and 8 hexatomic rings) it is formed by connecting by its four-membered ring and hexatomic ring.Sodalite has
Having three-dimensional Im3m lattice symmetry structure, the orifice diameter of its hexatomic ring about 0.28nm, skeleton maximum interspace is a diameter of
0.63nm.Owing to the orifice diameter of sodalite is little, only allow such as He, NH3, H2O and H2Little molecule and
Some ions pass through so that it is the storage that separates in small-size molecules has potential using value, as hydrogeneous in separated
Mixture and hydrogen storage.Simultaneously as the β cage internal cavity volume of sodalite is 0.150nm3, can fill and non-chemically count
The salt of amount, metal atomic cluster (Cluster) etc..If with high-octane radiation (such as electronics, γ, X and ultraviolet rays)
When irradiating the sodalite being filled with non-stoichiometry alkali metal salt, can be excited to produce photochromism, thus side
Sodium stone can be as functional materials such as potential optics.Additionally, sodalite has higher ion-exchange capacity, for
The good carrier of potential catalyst.If sodalite carrying alkali metal is good charcoal combustion catalyst, can be used to disappear
Except the carbon deposit on Diesel engine.
At present, from by heat source method from the point of view of, synthesis sodalite method mainly have hydrothermal synthesis method
(CN200910182050.5), ion full-boiled process (CN201210234320.4) and microwave-assisted addition method
(CN201110455425.8) etc..From the point of view of the approach that raw material is experienced, the method for synthesis sodalite mainly has
Hydrothermal synthesis method, solid phase phase inversion reaction method and silica-alumina gel method.Wherein, hydrothermal synthesis method is conventional synthesis side
Method.
The molecular sieve of nanocrystal is little due to its crystallite dimension, has molecule and is prone to diffusion and specific surface area is big etc. micro-
Nanoscale molecule sieve does not has the special feature that and receives publicity.Nanoscale sodalite crystal grain be prone at organic additive and
Obtain by the method for Hydrothermal Synthesis in the presence of structure directing agent.But the nanoscale sodalite that this method obtains
Yield poorly, the 10% of the most not enough silicon source material weight.And the roasting process of removing organic formwork agent will make grain colony
Poly-, reduce crystallinity, also can change the silica alumina ratio of molecular sieve, affect its serviceability.To this end, Wei Fan
Et al. (Langmuir 2008,24,6952-6958) with conventional silicon raw material vapor phase method SiO2With conventional aluminum feedstock aluminic acid
Sodium, in the presence of without organic additive and structure directing agent, carefully have adjusted process conditions and synthesizes nanoscale side
Sodium stone crystal grain.Nanoscale sodalite is also easy to be divided by the nanometer of pre-synthesis solid all-silica MFI framing structure
The son sieve direct phase inversion of crystal grain obtains.Additionally, during hydrothermal synthesis method, wash with alkali (such as NaOH) solution
Wash the solution of silicon-aluminum containing crystal grain to remove unformed phase therein, thus obtain the sodalite nanocrystal of reunion.
The silicon raw material of synthesis nano sodalite often uses waterglass and silica gel, the most also has gas phase SiO2Report
Road.Occur in that in recent years with unconventional solid silicon feedstock synthesis sodalite (CN201310641923.0) such as bentonite.
But aluminum source used is also conventional use of aluminium hydroxide, sodium metaaluminate and aluminium glue in that patent.Unconventional solid
The useful boehmite of report and the Kaolin of aluminum feedstock synthesis sodalite close in the presence of super alkali as aluminum source
One-tenth stock size sodalite (Fudan Journal (natural science edition), 1994, volume 33, the 1st phase, 17-21 page)
Report；The most useful boehmite synthesize in the presence of template sodalite (J.Chem.Soc.Fraday Trans,
Nineteen ninety-five, volume 91 7 phase, 1147～1154).
What existing synthetic method often prepared is powdered product.As article shaped used in advance silicon raw material molding
Carrier immerse crystallization (Chem.Mater.2010, volume 22,4,123 4125) in the alkaline solution containing aluminum, or
Selecting a kind of solid matter insoluble in alkaline solution in silicon raw material and aluminum feedstock, another kind of use is alkali-soluble
Material, after the two molding again crystallization thus obtain sodalite article shaped (Materials Letters, 2014,132
Volume, pp259～262).But directly with solid silicon source and the molding of aluminum source, crystallization is the report of sodalite the most again
Yet there are no.
Small crystal grain molecular sieve, owing to having shorter micropore diffusion orifice throat length and bigger outer surface, improves point
The properties of son sieve, shows the advantage of uniqueness in application process.But molecular sieve is undersized, in reality
Border is very inconvenient in applying, and there is the weakness such as difficult recovery, easy in inactivation and reunion.Additionally, forming process needs
Add binding agent.On the one hand result makes effective ratio area reduce, and on the other hand plugs molecular sieve pore passage unfavorable
In the diffusion of molecule, thus reduce using effect.So occurring in that Adhesive-free Molecular Sieve.
Summary of the invention
The invention provides a kind of method preparing the molecular sieve molded thing of nanoscale sodalite, it is possible to having without any
Under conditions of machine additive and structure directing agent exist, prepare the pure molecular sieve molded thing of nanoscale sodalite, and not
Any binding agent must be added.
For achieving the above object, technical scheme is as follows:
(1) by solid phase silicon source and solid phase aluminum source mix homogeneously, add the first alkaline aqueous solution, stir and obtain
Obtaining homogenizing paste or dough, further molding obtains article shaped；(2) by described article shaped dry roasting；
(3) baked article shaped is placed in the second alkaline aqueous solution, after crystallization, obtains nanoscale sodalite
Molecular sieve molded thing.
According to the present invention, molding described in step (1) can pass through distinct methods, as extrusion obtains strip molding
Thing.
According to the present invention, the purpose being dried described in step (2) is to remove water too much in article shaped, preferably
Condition is 70～150 DEG C and is dried 1～5h；The purpose of described roasting is to obtain stable material composition, including removing
Remove the impurity in article shaped；Forming macropore and mesopore orbit in article shaped, optimum condition is 550～750 DEG C simultaneously
Roasting 2～8h.
According to the present invention, described in step (3), crystallization is also called hydrothermal crystallization method, is usually special close
Close in reactor (autoclave), use aqueous solution as reaction medium, by reactor is heated, create one
Individual high temperature, reaction under high pressure environment so that generally indissoluble or insoluble material dissolve and recrystallization is to form dispersion
The method of nanocrystal, to realize the growth of crystal.Directly carry out aging after crystallization terminates, it is therefore an objective to make
Nucleus further growth is crystal grain, and promotes that product is changed to crystalline state by amorphous state, and optimum condition is 70～200 DEG C
Crystallization 1～5 hours.
In one particular embodiment of the present invention, the solid phase silicon source in described step (1) is silicon dioxide.
Its source can be silica containing natural minerals, such as bentonite；Or it is silica containing industrial waste,
Such as coal ash powder；It can also be the silicon dioxide powder of synthetic.After high-temperature roasting, dioxide-containing silica is high
Material may be incorporated for the present invention.
In one particular embodiment of the present invention, the solid phase aluminum source in described step (1) be aluminium oxide and/or
Boehmite.Its source can be salic natural minerals, such as bentonite；Or it is industrial waste,
Such as coal ash powder；Can also be alumina powder and/or the boehmite of synthetic.
In one particular embodiment of the present invention, the article shaped in described step (1) can be strip, ring
Shape, spherical or trilobes, according to concrete application it needs to be determined that.
In one particular embodiment of the present invention, the first alkaline aqueous solution of described step (1) and step (3)
The second alkaline aqueous solution in alkali identical or different, be selected from alkali metal hydroxide, preferably sodium hydroxide.
In an embodiment of the present invention, by the consumption in solid phase silicon source with SiO2Meter, the consumption in solid phase aluminum source is with Al2O3
Meter, the consumption of alkali is with M2O counts, and M is alkali metal, and each material mol ratio is SiO2: Al2O3: M2O:
H2O=1:(0.14～1): (10～60): (40～150), preferably 1:(0.16～1): (10～20):
(40～100), wherein, M is alkali metal.
Preferably, in the first alkaline aqueous solution of the second alkaline aqueous solution of described step (3) and step (1)
The mol ratio of alkali be 2.2～10.6:1, the mol ratio of water is 1.5～11.5:1.
The molecular sieve molded thing of sodalite that the present invention prepares, sodalite therein is that particle diameter is less than 1 micron
The spherical deposit that tablet is formed.By controlling reaction condition, can be by the top layer of unformed article shaped, portion
Divide or be completely converted into sodalite.
The present invention is with the essential distinction of prior art, uses solid unconventional silicon source and unconventional aluminum source,
Without being directly synthesized the molecular sieve molded thing of nanoscale sodalite in the presence of any organic additive.
Accompanying drawing explanation
Fig. 1 is XRD (X-ray diffraction) spectrogram of the molecular sieve molded thing of sodalite of embodiment 1 preparation；
Fig. 2 is SEM (the scanning electricity of the sodalite molecular sieve molded thing cross-sectional edge part of embodiment 1 preparation
Mirror) figure；
Fig. 3 is the SEM figure of the sodalite molecular sieve molded thing surface portion of embodiment 1 preparation；
Fig. 4 is the SEM figure of the sodalite molecular sieve molded thing cross-section center part of embodiment 2 preparation.
Detailed description of the invention
Embodiment 1
(1) by 7.4 grams of solid silicas and 7.4 grams of aluminium oxide mix homogeneously, 22 milliliter of 26.2% (matter is added
Amount) NaOH aqueous solution, it is evenly stirred until agglomerating, then obtains strip by the orifice plate extrusion of a diameter of 2 millimeters
Thing；
(2) by bar at 120 DEG C of dry 2h, then at 650 DEG C of roasting 4h；
(3) baked bar is put in crystallizing kettle, add the NaOH of 94 milliliter 26.2% (quality)
Aqueous solution, 70 DEG C of crystallization 4 hours；
(4) by the NaOH solution washing of the bar 0.01M after crystallization, then deionized water wash
To neutral, it be dried 3 hours at 70 DEG C, obtain the molecular sieve molded thing of nanoscale sodalite.
The formula that feeds intake is SiO2: Al2O3: Na2O:H2O=1:0.5:12.3:52.3.
End product is characterized, XRD characterization result as it is shown in figure 1, figure intermediate cam mark the peak side of being sodium
The characteristic peak of stone, the most unreacted aluminium oxide and the peak of silicon oxide, illustrate that synthetic product has SOD
Structure, shows have sodalite molecular sieve to be formed in strip article shaped.The SEM table of bar cross-sectional edge
Levy result as in figure 2 it is shown, explanation only defines one layer of fine and close crystal at strip article shaped edge.Bar table
The SEM characterization result in face is as shown in Figure 3, it can be seen that strip article shaped surface is by by the spherical accumulation of nanoscale
Thing is covered.Specifically, described article shaped is less than, by particle diameter, the spherical accumulation that the lamellar sodalite of 1 micron is formed
Thing forms.
Embodiment 2
(1) 7.0 grams of solid silicas and 7.2 grams of boehmites are stirred, add 26 milliliter 18.0%
The NaOH aqueous solution of (quality), is evenly stirred until agglomerating, then obtains by the orifice plate extrusion of a diameter of 8 millimeters
To bar；
(2) by bar at 70 DEG C of dry 8h, then 680 DEG C of roasting 4h；
(3) baked bar is put in crystallizing kettle, add the NaOH of 94 milliliter 20.5% (quality)
Aqueous solution, 80 DEG C of crystallization 4 hours；
(4) by the NaOH solution washing of the bar 0.01M after crystallization, then deionized water wash
To neutral.It is dried 3 hours at 70 DEG C, obtains the molecular sieve molded thing of nanoscale sodalite.
The formula that feeds intake is SiO2: Al2O3: Na2O:H2O=1:0.4:10.4:66.7.
The same Fig. 1 of XRD characterization result.The SEM characterization result of bar cross-section center as shown in Figure 4, can
Find out and also create plate flower crystal form at the center of bar.Also has part unreacted sial amorphous article simultaneously.
It should be noted that, embodiment described above is only used for explaining the present invention, it is not intended that the present invention's
Any restriction.By referring to exemplary embodiments, invention has been described, it should be appreciated that used by wherein
Word is descriptive and explanatory vocabulary rather than limited vocabulary.Can be by regulation in the claims in the present invention
In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention, the present invention is carried out
Revision.Although the present invention described in it relates to specific method, material and embodiment, it is not intended that
The present invention is limited to wherein disclosed particular case, and on the contrary, the present invention can be extended to other and all has identical function
Methods and applications.
Claims (10)
1. the method preparing the molecular sieve molded thing of nanoscale sodalite, step includes:
(1) by solid phase silicon source and solid phase aluminum source mix homogeneously, add the first alkaline aqueous solution, stir and obtain
Obtaining homogenizing paste or dough, further molding obtains article shaped；
(2) by described article shaped dry roasting；
(3) baked article shaped is placed in the second alkaline aqueous solution, after crystallization, obtains described nanoscale side
The molecular sieve molded thing of sodium stone.
Method the most according to claim 1, it is characterised in that the solid phase silicon source in described step (1)
For silicon dioxide.
Method the most according to claim 1 and 2, it is characterised in that the solid phase in described step (1)
Aluminum source is aluminium oxide and/or boehmite.
The most according to the method in any one of claims 1 to 3, it is characterised in that described step (2)
In roasting condition be 550～750 DEG C of roastings 2～8h.
Method the most according to any one of claim 1 to 4, it is characterised in that described step (3)
In crystallization condition be 70～200 DEG C of crystallization 1～5 hours.
Method the most according to any one of claim 1 to 5, it is characterised in that described step (1)
The first alkaline aqueous solution identical or different with the alkali in the second alkaline aqueous solution of step (3), be selected from alkali
Metal hydroxides.
Method the most according to claim 6, it is characterised in that the first alkaline water of described step (1)
Solution and be sodium hydroxide with the alkali in the second alkaline aqueous solution of step (3).
Method the most according to any one of claim 1 to 7, it is characterised in that by the use in solid phase silicon source
Amount is with SiO2Meter, the consumption in solid phase aluminum source is with Al2O3Meter, the consumption of alkali is with M2O counts, each material mol ratio
For SiO2: Al2O3: M2O:H2O=1:(0.14～1): (10～60): (40～150), preferably SiO2:
Al2O3: M2O:H2O=1:(0.16～1): (10～20): (40～100), wherein, M is alkali metal unit
Element.
Method the most according to any one of claim 1 to 8, it is characterised in that described step (3)
The second alkaline aqueous solution and step (1) the first alkaline aqueous solution in the mol ratio of alkali be 2.2～10.6:1,
The mol ratio of water is 1.5～11.5:1.
10. the molecular sieve molded thing of nanoscale sodalite, according to any one of claim 1 to 9
Method prepares, and sodalite therein is the spherical deposit that particle diameter is less than that the tablet of 1 micron is formed.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381591A (en) * | 2017-08-14 | 2017-11-24 | 许昌学院 | A kind of preparation method of the sodalite of petal-shaped at room temperature |
| CN110040740A (en) * | 2019-05-09 | 2019-07-23 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite |
| WO2020250985A1 (en) * | 2019-06-14 | 2020-12-17 | 国立研究開発法人科学技術振興機構 | Sheet-like particles of zeolite and method for producing same |
| CN112919488A (en) * | 2019-12-05 | 2021-06-08 | 中国科学院深圳先进技术研究院 | Improved silicon source of zeolite molecular sieve prepared by enhanced dissolution method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173433A (en) * | 2011-03-09 | 2011-09-07 | 南京理工大学 | Process for synthesizing single-phase sodalite from fly ash |
| CN103787363A (en) * | 2013-12-17 | 2014-05-14 | 西安建筑科技大学 | Method for synthesizing Na-X and hydroxysodalite form coal ash filter cake by adopting dry method |
-
2015
- 2015-06-19 CN CN201510347592.9A patent/CN106256764B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102173433A (en) * | 2011-03-09 | 2011-09-07 | 南京理工大学 | Process for synthesizing single-phase sodalite from fly ash |
| CN103787363A (en) * | 2013-12-17 | 2014-05-14 | 西安建筑科技大学 | Method for synthesizing Na-X and hydroxysodalite form coal ash filter cake by adopting dry method |
Non-Patent Citations (2)
| Title |
|---|
| SUNG-REOL LEE ET AL.: "Nanocrystalline Sodalite from Al2O3 Pillared Clay by Solid-Solid Transformation", 《CHEMISTRY OF MATERIALS》 * |
| WEI FAN ET AL.: "Synthesis of Nanometer-Sized Sodalite Without Adding Organic Additives", 《LANGMUIR》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107381591A (en) * | 2017-08-14 | 2017-11-24 | 许昌学院 | A kind of preparation method of the sodalite of petal-shaped at room temperature |
| CN110040740A (en) * | 2019-05-09 | 2019-07-23 | 嘉兴学院 | The method that crystal seed is oriented to method synthesis total silicon SOD zeolite |
| WO2020250985A1 (en) * | 2019-06-14 | 2020-12-17 | 国立研究開発法人科学技術振興機構 | Sheet-like particles of zeolite and method for producing same |
| JPWO2020250985A1 (en) * | 2019-06-14 | 2020-12-17 | ||
| JP7290230B2 (en) | 2019-06-14 | 2023-06-13 | 国立研究開発法人科学技術振興機構 | Sheet-like particles of zeolite and method for producing the same |
| US11873226B2 (en) | 2019-06-14 | 2024-01-16 | Japan Science And Technology Agency | Sheet-like particles of zeolite and method for producing same |
| CN112919488A (en) * | 2019-12-05 | 2021-06-08 | 中国科学院深圳先进技术研究院 | Improved silicon source of zeolite molecular sieve prepared by enhanced dissolution method |
| CN112919488B (en) * | 2019-12-05 | 2022-08-05 | 中国科学院深圳先进技术研究院 | Improved silicon source of zeolite molecular sieve prepared by enhanced dissolution method |
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