CN106256764B - A kind of method for preparing the molecular sieve molded object of nanoscale sodalite - Google Patents
A kind of method for preparing the molecular sieve molded object of nanoscale sodalite Download PDFInfo
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Abstract
The invention discloses a kind of methods for preparing the molecular sieve molded object of nanoscale sodalite, can prepare the pure molecular sieve molded object of nanoscale sodalite under the conditions of without existing for any organic additive and structure directing agent.Step includes：1) solid phase silicon source and solid phase silicon source are uniformly mixed, add in the first alkaline aqueous solution, stir evenly and be molded to obtain molding；2) by molding in dry roasting；3) baked molding is placed in the second alkaline aqueous solution, the molecular sieve molded object of nanoscale sodalite is obtained after crystallization.
Description
Technical field
The present invention relates to a kind of methods for preparing the molecular sieve molded object of nanoscale sodalite, belong to inorganic nano material preparation
Field.
Background technology
Sodalite (SOD) is one of most traditional molecular sieve, by SOD cages (that is, the β cages, by 6 four of body-centered cubic arrangement
Round rings and 8 hexatomic ring compositions) it is formed by connecting by its four-membered ring and hexatomic ring.Sodalite has solid Im3m lattice symmetry knots
Structure, the orifice diameter about 0.28nm of hexatomic ring, a diameter of 0.63nm of skeleton maximum interspace.Due to the orifice diameter of sodalite
It is small, only allow such as He, NH3, H2O and H2Small molecule and some ions pass through, make its in small-size molecules separation storage tool
There is potential application value, such as separation is containing hydrogen mixture and hydrogen storage.Simultaneously as the β cage internal cavity volumes of sodalite are
0.150nm3, non-stoichiometric salt, metal atomic cluster (Cluster) etc. can be filled.If with the radiation of high-energy (such as electricity
Son, γ, X and ultraviolet rays) irradiation when being filled with the sodalite of non-stoichiometry alkali metal salt, can be excited to generate photochromic existing
As thus sodalite can be used as the functional materials such as potential optics.In addition, sodalite has higher ion-exchange capacity, it is
The good carrier of potential catalyst.If sodalite carrying alkali metal is good charcoal combustion catalyst, can be used to eliminate diesel oil hair
Carbon deposit in motivation.
At present, from by heat source method from the point of view of, the method for synthesizing sodalite mainly has hydrothermal synthesis method
(CN200910182050.5), ionothermal synthesis (CN201210234320.4) and microwave radiation technology addition method
(CN201110455425.8) etc..From the point of view of the approach that raw material is undergone, the method that synthesizes sodalite mainly have hydrothermal synthesis method,
Solid phase phase inversion reaction method and silica-alumina gel method.Wherein, hydrothermal synthesis method is common synthetic method.
The molecular sieve of nanocrystal since its crystallite dimension is small there is molecule to be easy to the micron orders such as diffusion and large specific surface area
The characteristics of molecular sieve does not have and attract attention.Nanoscale sodalite crystal grain is easy in organic additive and structure directing agent
In the presence of obtained with the method for hydrothermal synthesis.But the nanoscale sodalite low output that this method obtains, usually deficiency silicon source
Expect the 10% of weight.And the roasting process of removing organic formwork agent will make crystal grain reunite, and reduce crystallinity, can also change molecular sieve
Silica alumina ratio, influence its performance.For this purpose, the conventional silicon of Wei Fan et al. (Langmuir 2008,24,6952-6958)
Raw material vapor phase method SiO2With conventional aluminum feedstock sodium aluminate in the presence of no organic additive and structure directing agent, carefully have adjusted
Process conditions synthesize nanoscale sodalite crystal grain.Nanoscale sodalite is also easy to by pre-synthesis solid all-silica MFI bone
The direct phase inversion of nano molecular sieve crystal grain of frame structure obtains.In addition, during hydrothermal synthesis method, washed with alkali (such as NaOH) solution
The solution of siliceous aluminium grain is washed to remove unformed phase therein, so as to obtain the sodalite nanocrystal of reunion.
The silicon raw material of synthesis nano sodalite often using waterglass and silica gel, also there is gas phase SiO sometimes2Report.
Occur in recent years with the unconventional solid silicon feedstock synthesis sodalite (CN201310641923.0) such as bentonite.But in the patent
In silicon source used also be conventional use of aluminium hydroxide, sodium metaaluminate and aluminium glue.Unconventional solid aluminium Material synthesis sodalite
Report that useful boehmite and kaolin synthesize stock size sodalite (Fudan Journal as silicon source in the presence of super alkali
(natural science edition), 1994, volume 33, the 1st phase, 17-21 pages) report；Also useful boehmite is in the presence of template
Synthesis sodalite (J.Chem.Soc.Fraday Trans, nineteen ninety-five, the phase of volume 91 7,1147~1154).
What existing synthetic method was often prepared is powdered product.Molding is such as used into the molding load of silicon raw material in advance
Body immerses in the alkaline solution containing aluminium crystallization (Chem.Mater.2010, volume 22,4123-4125) or in silicon raw material and aluminium original
Select a kind of solid matter insoluble in alkaline solution in material, another kind uses alkali-soluble substance, crystallization again after the two molding
So as to obtain sodalite molding (Materials Letters, 2014, volume 132, pp259~262).But directly use solid
Silicon source and silicon source molding, then crystallization yet there are no for the report of sodalite again.
Small crystal grain molecular sieve improves molecular sieve due to having shorter micropore diffusion orifice throat length and larger outer surface
Properties, show unique advantage in application process.But molecular sieve is undersized, it is very not square in practical applications
Just, there are the weakness such as difficult recycling, easy in inactivation and reunion.In addition, it needs to add in binding agent in forming process.As a result on the one hand make to have
It imitates specific surface area to reduce, the diffusion that molecular sieve pore passage is unfavorable for molecule is on the other hand plugged, so as to reduce using effect.Therefore
And there is Adhesive-free Molecular Sieve.
Invention content
The present invention provides a kind of method for preparing the molecular sieve molded object of nanoscale sodalite, organic can add without any
Under the conditions of adding agent and structure directing agent existing, the pure molecular sieve molded object of nanoscale sodalite is prepared, and needn't be added any viscous
Mixture.
To achieve the above object, technical scheme is as follows：
(1) solid phase silicon source and solid phase silicon source are uniformly mixed, add in the first alkaline aqueous solution, stirred evenly and obtain homogeneous cream
Shape or dough, further molding obtain molding；(2) by the molding dry roasting；
(3) baked molding is placed in the second alkaline aqueous solution, nanoscale sodalite molecular sieve is obtained after crystallization
Molding.
According to the present invention, molding described in step (1) can obtain strip molding by distinct methods, such as extrusion.
According to the present invention, dry purpose described in step (2) is to remove water excessive in molding, optimum condition 70
~150 DEG C of dry 1~5h；The purpose of the roasting is to obtain stable material composition, including removing the impurity in molding；Together
When macropore and mesopore orbit are formed in molding, optimum condition is 550~750 DEG C of 2~8h of roasting.
According to the present invention, crystallization described in step (3) is also known as hydrothermal crystallization method, usually in special closed reactor
In (autoclave), using aqueous solution as reaction medium, by being heated to reactor, a high temperature, reaction under high pressure environment are created,
So that usual indissoluble or insoluble substance dissolve and recrystallize the method to form the nanocrystal disperseed, to realize crystal
Growth.Aging is directly carried out after crystallization, it is therefore an objective to make nucleus further growth for crystal grain, and promote product by amorphous state
Change to crystalline state, optimum condition is 70~200 DEG C of crystallization 1~5 hour.
In one particular embodiment of the present invention, the solid phase silicon source in the step (1) is silica.Its source can
Think silica containing natural minerals, such as bentonite；Or for silica containing industrial waste, such as coal ash powder；It can also
For artificial synthesized silicon dioxide powder.The high substance of dioxide-containing silica may be incorporated for the present invention after high-temperature roasting.
In one particular embodiment of the present invention, the solid phase silicon source in the step (1) for aluminium oxide and/or intends thin water
Aluminium stone.Its source can be salic natural minerals, such as bentonite；Or for industrial waste, such as coal ash powder；Or
Artificial synthesized alumina powder and/or boehmite.
In one particular embodiment of the present invention, the molding in the step (1) can be strip, it is ring-type, 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 the step (1) and the second of step (3)
Alkali in alkaline aqueous solution is identical or different, is selected from alkali metal hydroxide, preferably sodium hydroxide.
In an embodiment of the present invention, by the dosage of solid phase silicon source with SiO2Meter, the dosage of solid phase silicon source is with Al2O3Meter, alkali
Dosage with M2O is counted, and M is alkali metal element, 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 element.
Preferably, the second alkaline aqueous solution of the step (3) and the alkali in the first alkaline aqueous solution of step (1) rub
You are than being 2.2~10.6:1, the molar ratio of water is 1.5~11.5:1.
The molecular sieve molded object of sodalite that the present invention is prepared, sodalite therein are less than 1 micron of sheet for grain size
The spherical deposit that object is formed.It, can be by the surface layer of unformed molding, be partly or entirely converted by controlling reaction condition
Sodalite.
The essential distinction of the present invention and the prior art are, using the unconventional silicon source of solid and unconventional silicon source, in nothing
The molecular sieve molded object of direct synthesis nano sodalite in the presence of any organic additive.
Description of the drawings
Fig. 1 is XRD (X-ray diffraction) spectrogram of the molecular sieve molded object of sodalite prepared by embodiment 1；
Fig. 2 is SEM (scanning electron microscope) figure of the molecular sieve molded object cross-sectional edge part of sodalite prepared by embodiment 1；
Fig. 3 is the SEM figures of the molecular sieve molded object surface portion of sodalite prepared by embodiment 1；
Fig. 4 is the SEM figures of the molecular sieve molded object cross-section center part of sodalite prepared by embodiment 2.
Specific embodiment
Embodiment 1
(1) 7.4 grams of solid silicas with 7.4 grams of aluminium oxide are uniformly mixed, added in 22 milliliter 26.2% (quality)
NaOH aqueous solutions, are evenly stirred until agglomerating, then obtain bar with a diameter of 2 millimeters of orifice plate extrusion；
(2) by bar in 120 DEG C of dry 2h, 4h then are roasted at 650 DEG C；
(3) baked bar is put into crystallizing kettle, adds in the NaOH aqueous solutions of 94 milliliter 26.2% (quality),
70 DEG C of crystallization 4 hours；
(4) bar after crystallization is washed with the NaOH aqueous solutions of 0.01M, then deionized water is washed to neutrality,
70 DEG C of dryings 3 hours, obtain the molecular sieve molded object of nanoscale sodalite.
Formula feed intake as SiO2：Al2O3：Na2O：H2O=1：0.5：12.3：52.3.
Final product is characterized, the results are shown in Figure 1 for XRD characterization, and the peak of figure intermediate cam mark is the spy of sodalite
Levy peak, while the peak of also unreacted aluminium oxide and silica illustrates that synthetic product has SOD structures, show strip into
There is sodalite molecular sieve to be formed on type object.The SEM characterization results of bar cross-sectional edge are as shown in Fig. 2, illustrate only in strip
Molding edge forms one layer of fine and close crystal.The SEM characterization results of bar surface are as shown in Figure 3, it can be seen that strip
Molding surface is covered by the spherical deposit of nanoscale.Specifically, the molding is less than 1 micron of sheet side by grain size
The spherical deposit composition that sodium stone is formed.
Embodiment 2
(1) 7.0 grams of solid silicas and 7.2 grams of boehmites are stirred evenly, adds in 26 milliliter of 18.0% (matter
Amount) NaOH aqueous solutions, be evenly stirred until agglomerating, then obtain bar with a diameter of 8 millimeters of orifice plate extrusion；
(2) by bar in 70 DEG C of dry 8h, then 680 DEG C of roasting 4h；
(3) baked bar is put into crystallizing kettle, adds in the NaOH aqueous solutions of 94 milliliter 20.5% (quality),
80 DEG C of crystallization 4 hours；
(4) bar after crystallization is washed with the NaOH aqueous solutions of 0.01M, then deionized water is washed to neutrality.
70 DEG C of dryings 3 hours, obtain the molecular sieve molded object of nanoscale sodalite.
Formula feed intake as SiO2：Al2O3：Na2O：H2O=1：0.4：10.4：66.7.
The same Fig. 1 of XRD characterization result.The SEM characterization results of bar cross-section center are as shown in Figure 4, it can be seen that in strip
The center of object also creates plate flower crystalline form.The also unreacted sial amorphous article in part simultaneously.
It should be noted that embodiment described above is only used for explaining the present invention, do not form to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that word used in it is descriptive
With explanatory vocabulary rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
It changes and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it relates to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (9)
1. a kind of method for preparing the molecular sieve molded object of nanoscale sodalite, step include：
(1) solid phase silicon source and solid phase silicon source are uniformly mixed, add in the first alkaline aqueous solution, stir evenly obtain homogeneous paste or
Dough, further molding obtain molding；
(2) by the molding dry roasting；
(3) baked molding is placed in the second alkaline aqueous solution, the nanoscale sodalite molecular sieve is obtained after crystallization
Molding；
By the dosage of solid phase silicon source with SiO2Meter, the dosage of solid phase silicon source is with Al2O3Meter, the dosage of alkali is with M2O is counted, each substance mole
Than for SiO2：Al2O3：M2O：H2O=1：(0.14~1)：(10~60)：(40~150) wherein, M is alkali metal element；
The spherical deposit that sodalite therein is formed for tablet of the grain size less than 1 micron.
2. according to the method described in claim 1, it is characterized in that, the solid phase silicon source in the step (1) is silica.
3. method according to claim 1 or 2, which is characterized in that the solid phase silicon source in the step (1) is aluminium oxide
And/or boehmite.
4. method according to claim 1 or 2, which is characterized in that the roasting condition in the step (2) is 550~750
DEG C roasting 2~8h.
5. method according to claim 1 or 2, which is characterized in that the crystallization condition in the step (3) is 70~200
DEG C crystallization 1~5 hour.
6. method according to claim 1 or 2, which is characterized in that the first alkaline aqueous solution and step of the step (1)
(3) the alkali in the second alkaline aqueous solution is identical or different, is selected from alkali metal hydroxide.
7. according to the method described in claim 6, it is characterized in that, the first alkaline aqueous solution and and step of the step (1)
(3) the alkali in the second alkaline aqueous solution is sodium hydroxide.
8. method according to claim 1 or 2, which is characterized in that by the dosage of solid phase silicon source with SiO2Meter, solid phase silicon source
Dosage with Al2O3Meter, the dosage of alkali is with M2O is counted, and each material mol ratio is SiO2：Al2O3：M2O：H2O=1:(0.16~1)：
(10~20)：(40~100), wherein, M is alkali metal element.
9. method according to claim 1 or 2, which is characterized in that the second alkaline aqueous solution and step of the step (3)
(1) molar ratio of the alkali in the first alkaline aqueous solution is 2.2~10.6:1, the molar ratio of water is 1.5~11.5:1.
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| CN107381591B (en) * | 2017-08-14 | 2020-05-08 | 许昌学院 | Preparation method of petal-shaped sodalite 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 |
| 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 |
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 |
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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 |
|---|
| Nanocrystalline Sodalite from Al2O3 Pillared Clay by Solid-Solid Transformation;Sung-Reol Lee et al.;《Chemistry of Materials》;20031119;第15卷(第25期);第4844页右栏第1-16行以及图6 * |
| Synthesis of Nanometer-Sized Sodalite Without Adding Organic Additives;Wei Fan et al.;《Langmuir》;20080529;第24卷;第6952-6958页 * |
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