CN106672991B - A kind of preparation method of nano level superfine analcime - Google Patents
A kind of preparation method of nano level superfine analcime Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of the ultra-fine analcime of nanometer.For this method using alkali source, silicon source, silicon source, water and N crassitudes as reaction raw materials, the crystallization 5 200 hours under self-generated pressure and 140 200 DEG C of hydrothermal condition obtains little crystal grain nanometer analcime.The synthetic method has the characteristics that simple for process, crystalline phase is pure, crystallinity is high, specific surface is big and inexpensive, having broad application prospects in terms of ionic adsorption, purification.
Description
Technical field
The present invention relates to a kind of preparation methods of nano level superfine analcime, belong to Zeolite synthesis technical field.
Background technology
Analcime has unique internal structure and Crystallochemical Properties, in the spy of catalysis, absorption, ion exchange etc.
Different performance.The one kind of analcime as zeolite race mineral, utilization field is boundless, and market potential value is larger.But
Natural analcime mineral have the deficiencies of impurity content height, purification difficult, larger crystal grain, and artificial synthesized analcime perfect cystal is more
With universality and controllability.
(Journal of the American Chemical Society 2007,129,13305-13312) is reported
Cubic system tetragonal trisoctahedron analcime crystal has been prepared using hydro-thermal method.It needs that surface is added in this method preparation process
Activating agent, expensive starting materials, process are complicated, products therefrom crystal grain is larger, reach 50 μm.
CN201310009800.5 discloses a kind of synthetic method of analcime.It is characterized in that technical solution includes following
Step：(1) preparation of sodium silicate solution：Si powder is added after being dissolved in distilled water in solid NaOH, and 90 DEG C of water-bath is reacted 5 hours；(2)
The preparation of sodium aluminate solution：Solid NaOH is dissolved in the Al powder being added after distilled water, and room temperature condition fully reacts；(3) forerunner
The preparation of body：It is mixed after above-mentioned solution is filtered respectively, microwave heating is stirred to react 0.5 hour；(4) presoma is set
In autoclave, 200 DEG C of isothermal reactions 3 to 6d；(5) product to neutrality and is dried through distilling water washing, you can obtains size about
For 120 μm of analcime monocrystals.This method is relatively complicated and gained crystal grain is excessive.
Analcime crystal grain obtained by the above method is complete, coarse grains, and crystallinity is high, but specific surface area is relatively low, generally
In 100m2/ g or so, lower specific surface area are unfavorable for the application in absorption, separation etc..
CN201310000215.9 provides a kind of method with coal ash for manufacturing for nanometer analcime, including：（1）Flyash
It mixes with alkali, is roasted under high temperature；（2）After cooling, deionized water is added, heating stirring is combined with stirring at normal temperature, obtains colloidal sol；
（3）After stirring, by colloidal sol ultrasound, filtering；（4）Filtered solid is added in aqueous slkali, and hydro-thermal is brilliant at a lower temperature
Change；（5）After crystallization will through being filtered, washed, the powdered nanometer analcime of drying to obtain.Analcime crystal grain obtained by this method
Nanoscale can be reached, but granularity is still relatively bigger, and when using flyash as raw material, pretreatment process needs to consume big
The alkali of amount corrodes and seriously polluted, and whole preparation process is also relatively complicated.
Invention content
For existing deficiency, the present invention provides a kind of preparation methods of nano level superfine analcime.Synthetic method letter
Single, obtained analcime has higher purity and crystallinity, superfine nano analcime of the invention have smaller size and
Larger specific surface area.
The preparation method of the nano level superfine analcime of the present invention, including following content：
（1）Silicon source, alkali source, N- crassitudes and water are uniformly mixed, after closed hydro-thermal process, material is cooled to room
Then silicon source is added in the material after hydro-thermal process by temperature again, be uniformly mixed；
（2）By step（1）Material through aging, crystallization, washing, drying and roasting, obtain nano level superfine analcime.
Step（1）The alkali source is alkali metal hydroxide, preferably sodium hydroxide.
Step（1）The silicon source is Ludox, silica gel, white carbon, waterglass, silester -28, silester -32
Or one kind in silester -40, diatomite and silicon alkoxide or combinations thereof object, preferably Ludox, white carbon, silester -
28, one or more of silester -32 or silester -40.
Step（1）The silicon source be selected from sodium metaaluminate, aluminum nitrate, aluminium chloride, aluminum sulfate, aluminium oxide and aluminium hydroxide and
One or more of one kind in organo-aluminium alcoholate or combinations thereof object, preferably sodium metaaluminate, aluminium isopropoxide and aluminium secondary butylate.
Step（1）The hybrid mode is mechanical agitation, magnetic agitation or the either type of oscillation.
Step（1）Described in alkali source, silicon source, water, silicon source, N- crassitudes in terms of following substance, proportionate relationship
Meet：
SiO2/Al2O3Molar ratio is 5-80
N- crassitudes/SiO2Molar ratio is 0.05-0.25
H2O/SiO2Molar ratio is 20-100
OH-/SiO2Molar ratio is 0.5-0.9
Aforementioned proportion relationship is preferably：
SiO2/Al2O3Molar ratio is 20-60
N- crassitudes/SiO2Molar ratio is 0.10-0.20
H2O/SiO2Molar ratio is 40-60
OH-/SiO2Molar ratio is 0.60-0.80.
Step（1）The closed hydrothermal conditions are：It is hydro-thermal process 1-24 hours closed at 90-120 DEG C.
Step（2）The aging condition is：30 ~ 80 DEG C of aging temperature, ageing time are 0.5 ~ 10 hour, preferably 1-6
Hour, more preferably 2-5 hour, carry out under agitation, further preferably ultrasonic disperse and stir collective effect under into
Row aging；The wherein described ultrasound condition is：The energy density of ultrasonic disperse is 0.2-4kW/L, the time of ultrasound and stirring action
It is 2-5 hours；The mode of the stirring includes mechanical agitation and/or magnetic agitation.
Step（2）The crystallization process carries out in a kettle, and crystallization condition is：Crystallization temperature is 140-200 DEG C, excellent
160-190 DEG C is selected, crystallization 5-250 hours, preferably 72-170 hours, pressure was the self-generated pressure of reaction kettle.
Product washing described in the method for the present invention, dry and roasting process are this field conventional process, and the present invention takes
Treatment conditions be：Reaction product is washed to neutrality using distilled water, then 5-24 hours dry at 80-150 DEG C, roasting temperature
Degree is 500-800 DEG C, and roasting time is 2-10 hours.
The present invention first at higher basicities, by the silicon source hydro-thermal process of appropriateness, makes it be fully converted into solubility
The high activity silicate of ionic state.Meanwhile in hydro-thermal process silicon source, completely cuts off silicon source and organic matter is added, in relatively mild temperature
It, can be to avoid the crystallization of silicon source under degree.Then in hydrothermal synthesis analcime system, N- crassitudes can be affected with modulation
The growth pattern of zeolite precursor object is acted on along with stirring is used in conjunction with ultrasonic disperse, and which results in nanometer analcimes
It generates.N- crassitudes used in the present invention, dosage is less, belongs to large organic intermediate, can be produced using technical grade
Product, cost are more cheap.
The crystallite dimension 10-50nm of the superfine nano analcime of the present invention, specific surface area is up to 200-450m2/ g, favorably
In the application in terms of ionic adsorption, purification.
Description of the drawings
Fig. 1 is the X-ray diffraction spectrum for the nano level superfine analcime that the embodiment of the present invention 1 synthesizes.
Fig. 2 is the scanning electron microscope image for the nano level superfine analcime that the embodiment of the present invention 1 synthesizes.
Specific implementation mode
The method of the present invention is described in detail below by embodiment.The crystal form of analcime uses X-ray diffraction table
Sign, pattern and size carry out observation and dimensional measurement using scanning electron microscope.
Embodiment 1
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 90 DEG C it is closed
Hydro-thermal 24 hours is cooled to room temperature, then spare sodium metaaluminate powder is added in above-mentioned solution, and stirs evenly.Finally
Material proportion meets：Al2O3/SiO2=30, N- crassitude/SiO2=0.15, OH-/SiO2=0.75, H2O/SiO2=40.Later
By said mixture at 40 DEG C, ultrasound（1.0KW/L）And magnetic agitation 3 hours, it is then charged into reaction kettle in 175 DEG C of crystallization
120 hours.Products therefrom is washed with distilled water, and after 120 DEG C of dryings, is roasted 5 hours through 550 DEG C.The side's of turning out to be boiling is detected through XRD
Stone, scanned electron microscope observation are spherical-like morphology, and crystallite dimension is about 30nm, belongs to nano-scale range, specific surface area
270m2/g。
Embodiment 2
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 100 DEG C it is close
It closes hydro-thermal 24 hours, is cooled to room temperature, then spare sodium metaaluminate powder is added in above-mentioned solution, and stir evenly.Most
Whole material proportion meets：Al2O3/SiO2=40, N- crassitude/SiO2=0.20, OH-/SiO2=0.8, H2O/SiO2=60.It
Afterwards by said mixture at 60 DEG C, ultrasound（0.5KW/L）And stir 3 hours, it is then charged into reaction kettle in 180 DEG C of crystallization
140 hours.Products therefrom is washed with distilled water, and after 120 DEG C of dryings, is roasted 5 hours through 550 DEG C.Product is turned out to be through XRD detections
Analcime, scanned electron microscope observation are spherical-like morphology, and crystallite dimension is about 35nm, belongs to nano-scale range, specific surface
Product 212m2/g。
Embodiment 3
At room temperature, water, sodium hydroxide, Ludox, N- crassitudes are mixed according to a certain percentage, then 120 DEG C it is close
It closes hydro-thermal 6 hours, is cooled to room temperature, then aluminium isopropoxide powder is added in above-mentioned solution, and stir evenly.Final material is matched
Than meeting：Al2O3/SiO2=60, N- crassitude/SiO2=0.25, OH-/SiO2=0.9, H2O/SiO2=80.It later will be above-mentioned
Mixture is at 50 DEG C, ultrasound（2.0KW/L）And magnetic agitation 3 hours, it is then charged into reaction kettle small in 180 DEG C of crystallization 140
When.Products therefrom is washed with distilled water, and after 120 DEG C of dryings, is roasted 5 hours through 550 DEG C.Product detects the side's of turning out to be boiling through XRD
Stone, scanned electron microscope observation are spherical-like morphology, and crystallite dimension is about 18nm, belongs to superfine nano range, specific surface area
380m2/g。
Comparative example 1
The preparation method is the same as that of Example 1, the difference is that being added without N- crassitudes in system.Products therefrom is detected through XRD
Turn out to be the mixture of quartz, ZSM-12 and other unknown crystals.
Comparative example 2
The preparation method is the same as that of Example 1, the difference is that silicon source is not isolated, but silicon source is added simultaneously with silicon source.Gained produces
Object confirms to be mainly quartz and a small amount of modenite, analcime through XRD detections, and product is not very pure, cannot obtain target
Product.
Claims (8)
1. a kind of preparation method of nano level superfine analcime, it is characterised in that including following content：（1）By silicon source, alkali source, N-
Crassitude and water are uniformly mixed, and closed hydro-thermal process, material is cooled to room temperature, and silicon source is then added to hydro-thermal process again
In material afterwards, it is uniformly mixed；（2）By step（1）Material through aging, crystallization, washing, drying and roasting, obtain nanoscale
Ultra-fine analcime；Step（1）The silicon source is Ludox, silica gel, white carbon, waterglass, silester -28, silester -
32 or silester -40, diatomite and silicon alkoxide in one kind or combinations thereof object；Step（1）Described in alkali source, silicon source, water,
In terms of following substance, proportionate relationship meets for silicon source and N- crassitudes：
SiO2/Al2O3Molar ratio is 5-80
N- crassitudes/SiO2Molar ratio is 0.05-0.25
H2O/SiO2Molar ratio is 25-100
OH-/SiO2Molar ratio is 0.5-0.9；
Step（2）The crystallization process carries out in a kettle, and crystallization condition is：Crystallization temperature is 140-200 DEG C, and crystallization is anti-
It answers 5-200 hours, pressure is the self-generated pressure of reaction kettle.
2. according to the method for claim 1, it is characterised in that：Step（1）The alkali source is alkali metal hydroxide.
3. according to the method for claim 1, it is characterised in that：Step（1）The silicon source is selected from sodium metaaluminate, nitric acid
One kind in aluminium, aluminium chloride, aluminum sulfate, aluminium oxide, aluminium hydroxide and organo-aluminium alcoholate or combinations thereof object.
4. according to the method for claim 1, it is characterised in that：Step（1）The hybrid mode is mechanical agitation, magnetic force
The either type of stirring or oscillation.
5. according to the method for claim 1, it is characterised in that：Step（1）The closed hydrothermal conditions are：
90-120 DEG C hydro-thermal process 1-24 hours closed.
6. according to the method for claim 1, it is characterised in that：Step（2）The aging condition is：Aging temperature 30-
80 DEG C, ageing time is 0.5-10 hours, is carried out under agitation；The mode of the stirring is mechanical agitation and/or magnetic force
Stirring.
7. according to the method described in claim 1 or 6, it is characterised in that：Step（2）The aging is in ultrasonic disperse and stirring
Aging is carried out under collective effect；The wherein described ultrasound condition is：The energy density of ultrasonic disperse be 0.2-4kW/L, ultrasound with stir
The time for mixing effect is 2-5 hours.
8. application of the nano level superfine analcime prepared according to the method for claim 1 in terms of ionic adsorption, purification.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664898A (en) * | 1982-10-20 | 1987-05-12 | Toyo Soda Manufacturing Co., Ltd. | Process for preparation of mordenite type zeolite |
| WO2012124727A1 (en) * | 2011-03-14 | 2012-09-20 | 国立大学法人岡山大学 | Machinable zeolite bulk body, method for producing same and hydrothermal synthesis reaction solution therefor, and application therefor |
| CN103318910A (en) * | 2013-07-02 | 2013-09-25 | 广西大学 | Method for preparing large-size analcite by utilizing hydrothermal crystallization of geopolymer |
| CN103572362A (en) * | 2013-01-11 | 2014-02-12 | 济南大学 | Method for hydrothermally synthesizing analcime monocrystal |
| CN104030311A (en) * | 2014-06-27 | 2014-09-10 | 周青 | Method for preparing micron-scaled analcite |
-
2015
- 2015-11-11 CN CN201510761662.5A patent/CN106672991B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4664898A (en) * | 1982-10-20 | 1987-05-12 | Toyo Soda Manufacturing Co., Ltd. | Process for preparation of mordenite type zeolite |
| WO2012124727A1 (en) * | 2011-03-14 | 2012-09-20 | 国立大学法人岡山大学 | Machinable zeolite bulk body, method for producing same and hydrothermal synthesis reaction solution therefor, and application therefor |
| CN103572362A (en) * | 2013-01-11 | 2014-02-12 | 济南大学 | Method for hydrothermally synthesizing analcime monocrystal |
| CN103318910A (en) * | 2013-07-02 | 2013-09-25 | 广西大学 | Method for preparing large-size analcite by utilizing hydrothermal crystallization of geopolymer |
| CN104030311A (en) * | 2014-06-27 | 2014-09-10 | 周青 | Method for preparing micron-scaled analcite |
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